4m9tc Polymers For Packaging and Containers in Food Industry 8j9 p93

New Concepts in Polymer Science
Polymers for Packaging and Containers

in Food Industry

Previous titles in this book series:
Low-Temperature Behaviour of Elastomers
M.F. Bukhina and S.K. Kurlyand
Modern Polymer Flame Retardancy

S.M. Lomakin and G.E. Zaikov
Radiation Chemistry of Biopolymers

G.E. Zaikov and V.A. Sharpatyi
Polymeric Biomaterials.
Part I. Polymer Implants
M.I. Shtilman
Polybutilene Therephthalate (PBT),

Synthesis and Properties
M.A. Mikitaev, T.A. Borukaev.
Edited by G.E. Zaikov
Photodegradation and Light Stabilization of
Heterochain Polymers
F. Niyazi, I.V. Savenkova and G.E. Zaikov
Elementorganic Monomers: Technology,
Properties, Applications
L.M. Khananashvili, O.V. Mukbaniani
and G.E. Zaikov
The Structural Stabilization of Polymers:
Fractal Models
G.V. Kozlov and G.E. Zaikov
Biodegradation and Durability of

Materials under the Effect of Microorganisms
S.A. Semenov, K.Z Gumargalieva
and G.E. Zaikov
Fire Resistant and Thermally Stable Materials Derived from Chlorinated Polyethylene
A.A. Donskoi, M.A. Shashkina and G.E.
Zaikov
Polymers and Polymeric Materials
for Fiber and Gradient Optics
N. Lekishvili, L. Nadareishvili,
G. Zaikov and L. Khananashvili
Thermal Oxidation of Polymer Blends. The

Role of Structure
L.S. Shibryaeva, A.A. Popov and G.E. Zaikov
Polymers Derived from Isobutylene.

Synthesis, Properties, Application
Yu.A. Sangalov, K.S. Minsker and G.E.
Zaikov
Biocide Guanidine Containing Polymers:

Synthesis, Structure and Properties
N.A. Sivov
Ecological Aspects of Polymer

Flame Retardancy
S.M. Lomakin and G.E. Zaikov
Active Sites of Polymerization.

Multiplicity: Stereospecific and Kinetic
Heterogeneity
Y.B. Monakov, N.N. Sigaeva and N. Urazbaev
Molecular Dynamics of Additives in Polymers

A.L. Kovarski
Stationary and Non-Stationary Kinetics

of the Photoinitiated Polymerization
Yu.G. Medvedevskikh, A.R. Kytsya,
L.I. Bazylyak, A.A. Turovsky and G.E. Zaikov
Thermal Stability of Engineering
Heterochain Thermoresistant Polymers
E.V. Kalugina, K.Z. Gumargalieva
and G.E. Zaikov
Structure and Properties of

Conducting Polymer Composites
V.E. Gul'
Interaction of Polymers with
Bioactive and Corrosive Media
A.L. Iordanskii, T.E. Rudakova and G.E.
Zaikov
Immobilization on Polymers
M.I. Shtilman
The Concept of Micellar-Sponge

Nanophases in Chemical Physics of Polymers
Yu.A. Mikheev, G.E. Zaikov
Radiation Chemistry of Polymers

V.S. Ivanov
Structure of the Polymer Amorphous State

G.V. Kozlov and G.E. Zaikov
Reactive Oligomers
S.G. Entelis, V.V. Evreinov and A.I. Kuzaev
The Statistical Nature of Strength and Lifetime in Polymer Films and Fibers
B. Tsoi, E.M. Kartashov and V.V. Shevelev
Diffusion of Electrolytes in Polymers

G.E. Zaikov, A.L. Iordanskii and V.S. Markin
Cyclolinear Organosilicon Copolymers:

Synthesis, Properties, Application
O.V. Mukbaniani and G.E. Zaikov
Polymeric Composites
R.B. Seymour
Chemical Physics of Polymer

Degradation and Stabilization
N.M Emanuel and A.L. Buchachenko
Polymers for Packaging

and Containers
in Food Industry
L.A. Sukhareva, O.A. Legonkova and
V.S. Yakovlev.
Edited by G.E. Zaikov
LEIDEN BOSTON - 2008
Printed and bound In The Netherlands
ISSN 0928-1584
ISBN 978 90 04 16143 6
Copyright 2008 by Koninklijke Brill NV, Leiden, The Netherlands.
Koninklijke Brill NV incorporates the imprints Brill, Hotei Publishing,
IDC Publishers, Martinus Nijhoff Publishers and VSP.
All rights reserved. No part of this publication may be reproduced, translated, stored in a
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Fees are subject to change.
Contents
Introduction
1 Methods and technology of preserving the nutritive value of food
1.1 The nutritive value of foodstuffs
1.2 Methods and technology of preserving food products and raw materials
1.3 Technology of preserving the quality of foodstuffs in manufacturing,
transportation and sales
1.4 Application of chemical preservatives in food industry
1.4.1 General information on chemical food preservatives
1.4.2 Mechanism of action of chemical preservatives
1.4.3 Characteristics and application of chemical preservatives
1.4.4 Methods for identification of preservatives
1.4.5 Fat antioxidants
1.4.6 Effect of oxidation on the food value of fats
1.4.7 Inhibition of autooxidation processes
1.4.8 Characteristics and application of antioxidants and synergists
1.4.9 Comparative efficiency, methods of treatment and admissible
concentrations of antioxidants
1.4.10 Methods for identification of antioxidants
2 Polymer packaging materials for preservation of foodstuffs
2.1 Food polymers
2.2 Hygienic characteristics of packaging materials components
2.3 Methods of packaging foodstuffs
3 Combined packaging materials using cellulose and its derivatives
3.1 Internal stresses in coatings using cellulose
3.2 Moisture-resistant packaging materials based on cellophane
3.2.1 Justification of the composition of the coating
3.2.2 Copolymer-based coatings
3.2.3 Coatings based on lacquer compositions
3.2.4 Design of heat sealed seams
3.2.5 Justification of the choice of solvent
3.2.6 Wetting of hydrated cellulose film with some organic solvents
and solutions of SVN-80 on the basis of these solvents
3.2.7 Working-out of an optimal process regime for producing
cellophane SVN-80
1
5
5
9
17
24
24
26
28
34
35
44
46
49
63
65
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71
75
82
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115
118
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125
vi
CONTENTS
3.3 Modification of cellulose diacetate for packaging materials

3.4 Interaction of cellulose with water
127
130
4 Compositions for decorative finish and protection of packaging products

4.1 Bases of the formation of protective and decorative finish coatings
4.2 Application of aqueous dispersions of polymers for finishing products
4.3 The formation mechanism, structure and properties of finishing
packaging materials from aqueous dispersions
4.4 Characteristics of finishing packaging materials
4.5 Aqueous dispersions of polymers for finishing coatings, offset papers
and inks
4.6 Properties of finishing coatings from aqueous dispersions of acrylic
polymers
4.7 Specifics of forming coatings on paper and offprints
133
133
139
5 Technology of the development of canning containers

5.1 Purpose of canning containers
5.2 Field of application and efficiency of use
5.3 Requirements to the properties of coatings for canning containers
5.4 Coatings for protection of canning containers
5.5 Compositions based on oligomer systems
5.6 Oleo-resinous lacquers
5.7 Polyvinyl chloride-based lacquers
5.8 Oligoesters and water-base, water-soluble and water-dispersion binders
5.9 Compositions with high dry residue and ink powders
5.10 Coatings for protection of the outer surface of canning containers
181
181
183
184
186
189
191
192
193
195
196
6 Structure and properties of compositions for protection of canning

containers
6.1 Ways of improving the protective properties of coatings
6.2 Effect of the nature of the support on the structure and properties of
coatings
6.3 Structure formation in solutions of epoxyphenol compositions and
the properties of coatings
6.4 Dependence of the properties of can lacquers on the structure of
phenol-formaldehyde oligomers
6.5 Fields of application of canning containers and methods of their
modification
6.6 Structure and properties of coatings based on epoxy oligomers
6.7 Technology of producing protective polymer coatings
6.8 Specific features of forming epoxyphenol coatings for canning containers
7 Ways of increasing the protective properties of coatings for canning
containers
7.1 Coatings with enhanced adhesion to aluminium and its alloys
7.2 The role of solvent in the formation of the properties of coatings for
canning containers
7.3 Effect of the nature of epoxy oligomers on the properties of coatings
7.4 Water-base compositions for protection of canning containers
7.5 Modification of polyvinyl chloride compositions by thermoplastics
145
151
154
158
177
201
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202
203
208
212
216
219
222
231
231
232
236
237
240
CONTENTS
Effect of the structure of the block copolymer chain on the properties

of coatings
7.7 Development of the method for improving the protective properties
of polyvinyl chloride compositions by modification with block copolymers
7.8 Studies of the relaxation properties of coatings from polyvinyl chloride
compositions modified by thermoplastics
7.9 Modified perchlorovinyl coatings with increased shelf-life
vii
7.6
8 Ways of modifying the properties of metallized packaging materials

8.1 Purpose and fields of application
8.2 Methods of forming metallized layers on polymer materials
8.3 Protective coatings for metallized materials
8.4 Methods of modifying the structure and properties of epoxy coatings
8.5 Protective coatings from copolymers of regular structure
8.6 Combined metallized materials for dairy produce packing
8.6.1 Combined material based on polyethylene, paper and aluminium foil
8.6.2 Hermeticity of polymer packaging
8.6.3 Coextruded polyethylene films for packaging dairy produce and
their quality indices
9 Technology of forming and modifying multilayer metallized packaging
materials
9.1 Purpose and production of multilayer materials
9.2 Prospects of using metallized packaging materials
9.3 Polymer films as the base for metallization
9.4 Methods of modifying the properties of films
9.5 Structure and properties of film materials
9.6 Ways of protecting metallized packaging materials
9.7 Effect of modification on the properties of protective coatings from
epoxy compositions
9.8 Technology of producing protective coatings with improved performance
properties
9.9 Ways of thixotropic decrease of internal stresses in the formation of
coatings from polymer dispersions for finishing of packaging materials
9.10 Modification of finishing dispersions for paper and offprints by
polymer systems
9.11 Combined packaging materials with increased protective properties
9.12 Effect of pH of the medium on the specific features of structure formation
and the properties of coatings from polymer dispersions
9.13 Polyurethane chemically resistant coatings for protection of container
and packaging materials
9.14 Protective polyurethane coatings and adhesive compounds
10 Methods of developing polymer gas-selective systems for storage of fruits
and vegetables
10.1 Problems of storage of agricultural raw materials and foodstuffs
10.2 Selectively permeable polymer materials
10.3 Effect of diffusion characteristics of polymer materials on the formation
of a gas medium
241
242
246
249
253
253
254
258
260
264
267
267
269
272
277
277
282
284
288
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299
305
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321
325
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335
viii
CONTENTS
10.4 Methods of developing an optimal gas medium and the technology of

storage
10.5 Efficiency of using polymer materials and protective coatings in
long-time storage of fruits
340
340
11 Structure and properties of oligomer compositions for protection of transport

containers
345
11.1 Corrosion resistance of coatings for transport containers
345
11.2 Structural conversions in hardening of thermosetting oligomers
346
11.3 Formation kinetics of coatings from polymerization oligomers
351
11.4 Causes of internal stresses in formation of coatings
357
11.5 Effect of the nature of hardener and initiator on the formation and
properties of coatings for transport containers
366
11.6 Biodeterioration of container/packaging materials
381
11.7 Effect of the polymerization initiation method on the formation and
387
11.8 Studies of the possibility of using stabilized radicals in protective coatings 395
12 Biochemically stable coatings for protection of transport containers
12.1 Coatings based on Ftorlon copolymers
12.2 Structure of modified Ftorlon coatings
12.3 Coatings based on modified and ladder polyphenyl sesquioxanes
12.4 Photohardenable epoxy acrylates for protection of transport containers
12.5 Physicochemical bases of developing photohardenable coatings
12.6 Photochemical processes and structural transformations in formation
of coatings under the action of ultraviolet light
12.7 Properties of epoxy acrylate coatings for transport containers
12.8 Biocidal coatings based on styromal
401
401
402
403
405
406
13 Technology of the protection of large-tonnage foodstuff containers

13.1.1 Methods of protecting storage tanks for potable 96% ethyl alcohol
13.1.2 Objects and methods of studies
13.1.3 Results of studies
13.1.4 Technology of anticorrosion protection of the inner surface of
ethyl alcohol storage tanks
13.2 Bactericidal wear-resistant coatings for storage and processing of grain
and grain products
13.3.1 Modified coatings of tanks for storage of vegetable oil
13.3.2 Results of tests
13.4 Food-grade coatings resistant to the action of sign-variable temperatures
431
431
432
433
14 Ecology and safety of utilization of container/packaging materials

14.1 Methods of utilization of packaging materials
14.2 Accelerated degradation of polymers by biocides
14.3 Photodegradable polymers
14.4 Modified photodegradable polymers
14.5 Principles of developing modifiers for biodegradable materials
14.6 Industrial and domestic plastics wastes
14.6.1 Secondary plastic raw materials in the public reproduction process
14.6.2 Sources and turnarounds of secondary polymer raw materials
455
455
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456
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462
464
464
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410
421
425
436
440
444
448
452
CONTENTS
14.6.3 Economic assessment of secondary plastic raw materials

14.6.4 Collection and use of thermoplastic wastes from domestic
consumption sphere
14.6.5 Separation of plastic wastes from domestic garbage
14.6.6 Application of plastic wastes as fillers and additives
14.6.7 Mechanism of degradation
14.6.8 Energy efficiency of incineration of plastic wastes
14.7 Secondary raw materials based on packaging material wastes
14.8 Use of secondary energy resources
14.9 Economic and ecological aspects of utilization of secondary raw materials
14.10 Self-degrading polymer materials
15 Packaging of meat and meat products
15.1 Range of single-layer packaging materials in meat packaging
15.2 Combined film materials
15.3 Modern trends in the development of chilled meat packaging technology
15.4 Methods and equipment for packaging of meat and meat products
15.5 Active packaging technology
ix
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512
Conclusion
517
References
519
CONTENTS
Introduction
Development of the concept of long-term food storage is an independent field of scientific
and applied research using polymers of various chemical compositions and structures.
It includes elaboration of technology of storing food products and food staples using
advanced packaging materials. Their development is based on studies of temporal regularities of the quality of products depending on chemical composition, properties and structure. External factors are to be considered, too; they include conditions and terms of storage,
air temperature and humidity, biocide properties of container/packaging materials, quality
assessment criteria in turning out/accepting products and in long-time storage.
Based on the studies of the dynamics of the process, analysis of numerous results of
research, it became possible to predict the regularities in the change of quality and terms of
product storage, as well as the criteria of the impact of containers and packaging on them.
Food products are a complex object; various physico-chemical processes occur in
them in production and storage, thus changing their properties and nutritive value. Such
basic ingredients as proteins, lipids, carbohydrates are polyfunctional compounds, which
are involved in diverse intra- and intercellular interactions.
Despite the diversity and complexity of food products, they are an integral biological
system with its characteristic features. The basis of the organization of biologically active
food systems are variability, preservation and stability.
A determining factor in the development of the scientific approach to storage of food
products is the variability of the properties, and storage appears to be the unity of changes
and preservation, variability and stability.
The properties of food products and their changes in storage should be considered
under conditions of the multi-factor relationship of internal and external effects.
Stability of food products in storage is characterized by processes, which lead to a decrease of the consumer properties of foodstuffs. The directedness of these processes is determined by internal factors and initial properties of a product: the peculiarities of chemical
composition, ratio of the main components, activity of the enzyme systems, occurrence of
natural antioxidants. This system is affected by external factors capable of inhibiting or activating the active processes in food products. There is an exchange between the medium
and the product an exchange of mass, energy and information.
A system becomes stable and reliable when it is capable of reacting to the influence
of an external medium by changing it in accordance with its inherent properties. Food products, which are biological systems, do not passively obey the influence of the external medium but actively counteract it, following its own processes due to its potentialities, its
resistance to the effects of individual factors. Therefore, the ability of food products to react
to an external effect is considered to be an essential factor of self-preservation.
INTRODUCTION
Of great importance in long-time storage of food products are polymers for containers
and packaging. For an open system, a container is a barrier between a product and external
factors. The requirements to containers are dictated by the properties of a product and the
character of its mass exchange with the external medium.
In products suitable for long-time storage, biological (microbial, enzymic) processes
are completely or almost completely excluded. Products with low moisture content (not
higher than 10%) can be attributed to such products. Products with average (10 to 40%) and
high (over 40%) moisture content are capable of retaining their properties for a rather limited period of time. Preservation (sterilization, freezing, sublimation etc.) makes it possible
to considerably increase their storage time. Therefore, products suitable for long-time
storage are those with low moisture content or preserved in various ways.
The basis of long-time storage of food products is the maximum preservation of consumer properties by regulating the initial-quality change as a result of product ageing, effects of external factors, choice of containers and packaging materials.
The main processes in food products in long-time storage, which govern the guarantee
storage times, are as follows:
for products with low moisture content: exchange of moisture with the external medium and the oxidative process;
for frozen meat: heat exchange and oxidation reactions;
for sterilized preserves: changes in the protein and lipid composition as well as interaction of the product with containers metal.
Of great importance is the development of container/packaging materials for storage
and transportation of high-calorie foodstuffs under extreme conditions. They are manufactured for persons whose activity is related to prolonged physical and neuro-emotional
stresses under unfavourable conditions.
The assortment of these foodstuffs comprises dairy, meat, fish, fruit-and-vegetable and
other products, preserved by methods of thermal sterilization, sublimation drying, partial
dehydration, including:
dairy products sources of readily assimilable calcium, complete protein and fat.
They include milk beverages and curd products of sublimation drying, with added coffee,
cocoa, nuts, sea-buckthorn oil; puree from dried apricots, cranberry etc.;
sublimation-dried sour-milk products providing normalization of intestinal microflora, which is especially important in long-term consumption of preserved food;
high-fat sterilized milk preserves, including cheeses, sterilized curd products, which
are distinguished by a high content of readily assimilable protein, optimal calcium to phosphorus ratio, increased content of potassium, high energy value;
fish products (preserves and products of sublimation drying): sources of complete
readily assimilable protein, fats with a high content of polyunsaturated fatty acids, oilsoluble vitamins, major nutrients and trace elements;
meat and meat-and-cereal products (preserves, lunch packs of sublimation drying):
sources of complete protein with a balanced amino acid content owing to a combination of
animal and plant protein, minerals, as well as fats with a sufficient amount of polyunsaturated fatty acids and oil-soluble vitamins in their composition;
fruit-and-vegetable products (fruit concentrates, vegetable side dishes, juices, kissels
and compotes of sublimation drying): sources of readily assimilable carbohydrates, minerals (potassium, trace elements), vitamins, pectins, organic acids;
confectionary products distinguished by a high nutritive value at a minimum weight
and volume;
INTRODUCTION
dehydrated beverages (tea, coffee) with readily assimilable carbohydrates added.

Ready-to-eat products need minimum preparation, are portioned and are convenient
to use directly from the packaging container.
Lately, an important role is allotted to the biological safety of products, which is related to the consumption of food produced from genetically modified plants. Only in the recent
years, the global acreage of transgenic crops, such as soy, maize, tomatoes and potatoes increased more than 20-fold. Food products from them are already supplied to the table of
American and Russian consumers.
Norms and methods for the integrated assessment of the safety of genetically modified
sources of food are intensively worked out at present. Much attention is also given to the
development of advanced containers and packaging materials.
Principles of creating active packaging for food production have been proposed. Traditional basic qualities of food packaging are usually related to its inertness due to the intrinsic barrier properties of the polymer matrix. At present, the functions of packaging are
much broader. The quality of a packaging is assessed by its involvement in the preservation
of the nutritive value of a product, by its activity determined by such functions as the ability
to regulate the speed and temperature of foodstuff heating in a microwave oven; to create
an optimal gas medium inside the envelope; to change directionally the intranutrient composition of a product; to introduce flavouring materials, preservatives, gas absorbents,
moisture adsorbents, antimicrobial preparations; as well as to use special coatings to improve the appearance and decorative properties of a packaging.
The purpose and functions of polymer and combined aseptic packaging have broaden.
The modern approach to packaging engineering of the 21 century is considered with
account for three directions of the development of active packaging, which, as the result of
introducing special additives, affects the quality of food products.
The first way of creating active packaging is based on the principles of forming a regulated modified gas medium using special membranes, adsorbents of oxygen, ethylene, for
instance, in storage of fruits and vegetables.
The second way is to impart a biocide activity to the packaging with respect to pathogenic microflora in the process of production and storage. The third way: in production of
food products (cheeses, uncooked dry-cured sausages) the packaging should regulate the
biochemical transformations in the product for directed regulation of its properties. In this
connection, immobilized bacterial cells and enzymes are introduced into the active
packaging.
A topical problem is to develop ecologically harmless container/packaging materials
and coatings due to the aggravated situation with providing healthy food in the right quantities. A decrease in the level of production, crumbling of structural industrial links, the unfavourable ecological situation stipulate a sharp increase of the losses of agricultural and
food products, generally lead to such negative consequences as the rise of the deficit of protein and vitamins in the food ration, pollution of food with metabolic products of pathogenic
bacteria, including with carcinogens.
Ecologically safe packaging materials are created by modifying traditional polymers
with polyfunctional additives, which perform the functions of structure formers, plasticizers, antibiotics, relaxants of internal stresses, and stabilizers. Scientific bases of creating
packaging materials for foodstuffs have been developed. Additives providing the production of materials, which are biochemically resistant to the impact of microflora and aggressive media of food productions, are introduced into the composition of their base. Methods
of regulating the processes of mass transfer and distribution of structure-forming additives
INTRODUCTION
along the thickness of the packaging materials with the aim to form an optimal structure
and operational properties have been developed.
Fundamental works have been carried out on the development of packaging materials
and coatings based on various polyolefins, ftorlons, epoxy polyesters and other polymers
of mesomorphic structure, which provide for the production of packagings with polyfunctional properties.
Special attention is given to the development of scientific principles of creating
self-degrading packaging materials with regulated service life and biodegradation upon disposal.
Valuable characteristics of these materials are determined by the necessity of combining the biocide properties with respect to foods in storage with the ability to be degraded
in soil under the action of microflora.
1
1.1
Methods and Technology

of Preserving the Nutritive
Value of Food
The nutritive value of foodstuffs
Special attention should be paid to the control of losses of food products in their processing,
storage, transportation and sale. This could not be done without scientifically grounded
rational application of polymer materials, which are used to preserve food products. In this
connection, it is necessary to consider the specific properties of both food itself and of polymers in contact with it (packaging materials, containers, various coatings).
To preserve food well, it is necessary to know which of its specific properties should
be retained until it reaches consumers table, bearing in mind the concepts healthy food
and tasty food from the viewpoint of food biochemistry. Man can not exist without food.
It provides the organism with necessary substances for growth and is a source of energy,
which is transformed into heat required for the bodily functions of the human organism.
For a long time, the only index of food value was its caloric value. Energy is constantly
consumed throughout human life to maintain the normal body temperature, for mental and
physical work. Usually, a human in normal condition should consume an amount of food,
which corresponds to energy consumption by its caloric value.
The amount of energy required for the human organism, internal consumption including, is determined in special chambers used to measure the amount of heat evolving in the
lying position, during physical or mental activities. Naturally, depending on the intensity
of work, the amount of energy evolved and, therefore, the requirement of its replenishment
at the expense of the caloric value of food would be different.
The human organism receives energy mainly due to oxidation of food. Actually, food
is not assimilated completely, and its real caloric value is slightly less than the amount
of heat evolved in its oxidation. Carbohydrates and fats burn almost completely. In oxidation of carbohydrates and proteins, the energy evolved per 1 kg is 16.8103 kJ; of fats,
37.8103 kJ.
The basis of food are proteins, fats and carbohydrates. All foods essential for health
consist of proteins, fats and carbohydrates, and also of some other components. For the
organism, it is not the same if it receives these calories by consuming carbohydrates or fats.
The latter are more difficult to assimilate, and they come to the blood flow later. Proteins
are indispensable for the organism. Apart from the fact that they replenish the energy
consumed, they provide for the restoration of expended cells and tissues and ensure the
development of the human organism at the young age.
POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY
Food does not only deliver energy for work and is required for us to move, think, for
the heart to pump blood through the body, to maintain normal body temperature; it also provides material for the incessant regeneration of tissues and cells. The most active constituent
parts of cells and tissues, consisting of proteins, are to be regenerated first of all. Various
types of proteins can be distinguished. They perform various functions in the organism.
Proteins of connective tissues fasten muscles and bones in tendons. Proteins, of which
muscles consist, are capable of contracting and stretching, in accordance with orders from
the brain, to bring into motion organs of the human body. Proteins of the blood deliver
oxygen required for oxidation of tissues (without which the human organism is not capable
of maintaining life and performing work) and pick up the waste product, carbon dioxide.
Cutaneous coverings, hairs, mucous envelopes also consist of proteins.
Of no less importance in comparison with the above is the regulatory function of proteins. They regulate the vital processes in cells and organs. From the point of view of chemistry, these proteins catalyze and regulate chemical processes. Digestion is also one of these
processes.
Proteins in question are enzymes. Participating in the regulation of vital processes,
protein molecules are subjected to changes, as a result of which they lose their valuable
properties. Thus, it is necessary that the replacement for spent proteins come with food.
Therefore, sources of energy fats and carbohydrates are interchangeable. From the viewpoint of their energy functions, they can be replaced with proteins. Proteins themselves are
indispensable, as they are valuable for the organism not only as an energy source but also
as building material for cells and as catalysts and regulators of biochemical processes.
Therefore, the value of food products is determined not only by their caloric value but
also by the content of protein substances. The hierarchy of food products by this parameter
differs from that obtained from comparison of foodstuffs by their caloric value.
Consider the protein content in different food products consumed in this country, %:
Soy
Dry pea
Cheddar cheese
Boiled hen
Beef
Cod
Mutton
Pork
Eggs
Wheat flour
34.9
23.8
23
20.6
17
16.5
15.7
15.2
12.8
10.5
Rice
Cow milk
Potato
Cabbage
Carrot
Butter
Margarine
Marmalade
Sunflower oil
Sugar
7.6
2.8
2.0
1.8
1.2
0.6
0.3
traces
none
none
Food products can not be characterized by their caloric value alone. Despite the high
caloric values of sunflower oil and sugar, the human organism would not function in a
normal way, however large amounts of these high-calorie products are consumed. It is imperative that food of man contains fats, carbohydrates and proteins. In the human organism,
protein molecules break up to form smaller molecules, amino acids. Amino acid molecules
can be of different size and structure. Their common feature is the presence of amino and
carboxyl groups in the molecule. It has been established that amino acids required for the
vital activities of the human organism can be divided into nonessential and essential. Nonessential amino acids can be synthesized by the human organism from fragments of molecules. Essential amino acids can not be synthesized and should be obtained with food.
CHAPTER 1
Apart from proteins, fats and carbohydrates, the human organism requires vitamins.
They are essential. Certainly, vitamins can be injected or swallowed in pill form. But the
most useful method is to introduce vitamins with food. As molecules of amino acids are
fragments of large molecules of proteins, so vitamins are ready-made fragments of the most
important enzymes regulating the metabolism. Vitamins are divided into water-soluble and
fat-soluble. For example, vitamin C ascorbic acid belongs to the former. The human organism is not capable of synthesizing it, despite its comparatively simple chemical structure, probably, because the mankind has been almost always surrounded by natural sources
of vitamin C, which occurs in almost all fresh vegetables and fruits. This vitamin is present
in dill (0.15%), horseradish (0.2%), red pepper (0.25%), black currant (0.3%), winter pine
needles (0.220.28%), dry briar (15%) and in other vegetables, fruits and greens. Ascorbic acid is unstable and is easily destroyed in cooking, drying, preservation and in long-time
storage in air. Deficiency of vitamin C in food causes a severe disease, scurvy.
One of fat-soluble vitamins is widely known vitamin A, which is involved in the synthesis of rhodopsin required for good vision and is contained in fish liver oil, carrot and
other products. Vitamin A occurs mainly in products of animal origin. Its highest amount
is in beef liver and cod. The liver stores 90% of all vitamin A in the animal and human organism. Good sources of this vitamin are hens and quails eggs, butter, dairy cream and
sour cream. Though plant products contain no vitamin A, some of them (carrot, red mountain ash, sea buckthorn berries) contain a large amount of carotene up to 10 mg per 100 g
product. Under the action of carotenase in the intestines, carotene is converted to vitamin
A. Carotene is a rather unstable, readily oxidizable compound. For this reason, chopped
vegetables and greens should not be left unused for a long time, as carotene in them would
lose biological activity. Greens and vegetables should be cut immediately before a meal.
As carotene does not dissolve in water but dissolves well in fats and oil, it would be assimilated better if an edible fat is added to vegetable dishes. For instance, grated carrots could
be dressed with mayonnaise or sour cream.
The daily requirement of vitamin A is 0.50.7 mg for children aged from one up to
ten years old; 1 mg for older-age children and adults; 1.25 mg for pregnant women; 1.5 mg
for breastfeeding women.
For persons whose work is associated with a heavy load on the organs of vision, those
who work evening or night shifts or have contact with substances causing irritation of the
mucosa of the eye, the daily intake of vitamin A should be increased 1.52-fold.
Deficiency of vitamin B can cause polyneuritis. Vitamin B2 (riboflavin) is required for
normal sight. The absence or deficiency of PP (nicotinic acid) leads to a heavy disease, pellagra, and vitamin B2 contains the element cobalt required for the vital activity of the cells.
Thus, besides fats and carbohydrates, the human organism should receive with food a
set of essential amino acids, vitamins, cellulose for normal functioning of the gastrointestinal tract. But even this is not sufficient for food to be wholesome and to contain all elements required for the vital activities of the organism. The important components are salts,
which contain such elements as potassium, sodium, calcium, phosphorus, fluorine, as well
as various trace elements in small amounts. Sodium is an important constituent of the blood
and together with potassium is required for the normal functioning of the nervous system.
Human bones consist of calcium phosphate. Adenosine triphosphoric acid is a kind of an
energy storage device in the human organism. Phosphorus-containing nucleic acids code
for the program of building up and operating each cell of the organism and, therefore, the
program of constructing the entire organism, i.e., heredity. Protein molecules also include
sulfur. The absence of iodine makes impossible the normal functioning of the thyroid gland.
Iron is a component of blood hemoglobin. Fluorine is required for the normal state of the
teeth.
However, food should be not only wholesome but also tasty and even attractive to the
eye. By its appearance and aroma, it should cause a reflectory secretion of the substances,
which contribute to the digestion and assimilation of food. Therefore, a broad diversity of
gastronomy should not be reduced to carbohydrates, fats, amino acids, vitamins and salts.
In spite of the seeming rationality of introducing a certain amount of nutrients into the organism, the human can not live on tablets or powders of even the most perfect and wellbalanced diet. It is not by chance that even at the dawn of cosmonautics, when each extra
gram of load in the spaceship significantly complicated the mission, even then cosmonauts
did not swallow powders or pills consisting of amino acids, carbohydrates, fats and other
components. The taste, smell and appearance of food is not a caprice but an essential requirement of the human organism. The diversity of taste hues can be reduced to a combination of four main gustatory properties: sour, sweet, bitter and salty. The edges of the
tongue are the most sensitive to sour taste; the base, to bitter taste, the tip, to sweet and salty
tastes. All acids have a sour taste. Cooking salt, as is known, possesses a salty taste. However, salts of most metals are not salty in taste, but bitter. In general, the relation between
the chemical structure of a substance and its taste has been investigated to date obviously
insufficiently. Peptides have a taste, which depends on which amino acids they consist of.
High-molecular-mass compounds, whose molecules are characterized by molecular-mass
magnitudes of the order of tens and hundreds of thousands are, as a rule, tasteless. This pertains to polysaccharides and polypeptides (proteins). As for the taste of amino acids, the
sweet ones are D-tryptophane, D-histidine, D-phenylalanine, L-alanine, glycine (in decreasing order). L-Tryptophane, L-phenyl alanine and the so-called L-isomers are bitter.
D-Alanine, D- and L-aspartic acids, D-glutamic acid are tasteless or have a very weak taste.
Food products are sometimes artificially flavoured, for example, to add a sweet taste.
Herewith, it is known that sugar is not the very sweet substance. Saccharine, for instance,
is 400500 times as sweet as sugar, but is not assimilated by the human organism.
Glycine (an amino acid possessing a sweet taste) is agreeable to the taste and wholesome. It is widely used in production of soups, condiments, marinades; it softens a bitter or
salty taste and eliminates an unpleasant off-flavour of some products. Glycine is present in
large amounts in fish, prawns, molluscs.
D-Tryptophane and maltol are used to enhance sweetness. Addition of maltol in the
amount of 15 ppm makes it possible to decrease the consumption of sugar by 15%.
Preparation of food boiling, broiling, roasting, fermenting, pickling, junketing etc.
is accompanied with complex chemical reactions, as the result of which a large amount of
various volatile compounds are formed. Their content in food is negligible but the flavour
of food changes depending on the ratio of these compounds in the steams.
In individual cooking, it is easier to follow the preservation of useful substances, taste,
colour and smell. It is far more difficult to bring the valuable properties of food to the consumers table, when food products are mass produced in meat-, milk- or food-packaging
plants; when these products should be preserved in the process of production, transportation
and storage in refrigerators, in the process of selling them up to the moment when the food
gets into the human organism.
Considering the problem of food preservation, one should not be abstracted from the
fact that foodstuffs are involved in the common closed process of interaction of the human
organism with the environment. The late 1970s and early 1980s witnessed the formation of
a new interdisciplinary science of food and nutrition, trophology (the Greek word
CHAPTER 1
means aliment). Trophology combines together the earlier disconnected links of the chain
and various aspects of the science of food, such as the distribution of nutrient substances in
the cell or in the organism; the mechanism of the transfer of nutrient substances along the
food chains; the role of trophological processes in the circulation of substances in the biosphere; evolution of species and evolution of the biosphere. As far as the life of each organism and the maintenance of life depend essentially on the equilibrium between the synthesis
and decomposition of nutrient substances, the biosphere can be considered as a troposphere,
and all organisms as links of the planetary food chain, a food hierarchy forming a closed
circle. The new science of trophology should combine together the earlier scattered links
of this chain.
An integrated view of the trophological process made one to approach the evaluation
of food in a new way. While it was believed earlier that the organism needed as much food
as it consumed, it was not food in general that was meant but the nutrients assimilated by
the organism amino acids, carbohydrates, fatty acids, vitamins, essential salts. All the
other components of foodstuffs were considered to be an unnecessary ballast, which complicates the bodily functions of the human organism. At present, one of the fundamental
conclusions of trophology is that, apart from the main flow of nutrients, four more flows
come to the organism. One of the most important flows is that of physiologically active substances formed in the stomach and in the intestines. The so called hormones and mediators
are implied.
If one takes account of all hormone-producing cells in the human gastrointestinal tract,
the result would be the largest endocrine gland in the human organism. This gland secretes
hormones, which control the essential metabolic functions and assimilation of nutrients.
Three other flows are formed in the gastrointestinal tract with the participation of bacterial
flora. The bacterial flora is required for the human organism and higher animals to exist.
Only the proportional ratio of all four flows creates normal conditions for the vital activities
of the organism. The so-called ballast substances, which until recently were to be withdrawn from food to make it closer to an ideal meal, are in reality also required for the
human organism. On removal of, e.g., food fibres cellulose or lignin from food, the cholesterol metabolism is disturbed, which can cause stones in the gall bladder or else a stomach or intestinal disease. Therefore, ballast-free elementary diets are applicable only in the
case of some defects of the enzyme systems.
1.2
Methods and technology of preserving food products and raw

materials
Large amounts of food products in the CIS countries are lost at the stages of raw-material
production, processing, transportation, storage and, finally, sales. A considerable amount
of potatoes, milk, grain, meat perishes as the result of losses in harvesting, transportation
and storage.
The use of polymer materials makes it possible to preserve the quality and significantly
reduce the losses of food products.
At the stages of raw-material production, polymer materials are mainly used in growing the agricultural produce, in raising and sagination of domestic animals. One of the important areas of polymer use to increase the crop yield is the presowing treatment of seeds.
It consists of spraying the seeds with a polymer suspension, which includes nutrients, trace
elements, plant-growth regulators, insecticides and other biologically active substances.
The basis of film-forming compositions are water-soluble polymers with specific
10
physicochemical and physicomechanical properties and the possibility of providing a

hydrophilic/hydrophobic balance in the system. Protective films reliably protect seeds from
the action of low temperatures, from premature germination under unfavourable conditions.
The properties of the coatings are programmed depending on the biological peculiarities of
plants. This is achieved by chemical modification of a polymer (e.g., polyvinyl alcohol) in
the process of film formation and polymer structure change both at the molecular and
supramolecular levels.
The climatic conditions in many cases make it necessary to grow fruits and vegetables
under coverage. The major factor, which limits the possibility of growing vegetables, berries, fruits and other crops in unprotected areas is insufficient warmth. The temperature conditions can be adjusted using hothouses, hotbeds, covers and other cultivation
constructions. Only these agricultural constructions can significantly improve the temperature conditions in the plant-vegetation zone. These constructions prove economically efficient if fabricated using polymer-film materials, which, though inferior than silicate glass
with respect to life time, are cheap, transportable and easy to erect. The major factor causing
the ageing of polymer films is solar radiation in the ultraviolet and infrared regions of the
spectrum.
Application of polymer-film materials in cultivation constructions in agriculture is
rather efficient; however, it creates the problem of utilization of used films. Upon use and
loss of consumer properties, the polymer film retains mainly a two-dimensional structure.
It pollutes the ground and is not degraded or assimilated by the environment for about 80
years. Therefore, the use of polymer films in agriculture leads to the necessity to solve the
problem of utilization of used films or their transfer into a state in which they are assimilated
by the environment, i.e., to control the polymer degradation processes. Photochemical degradation of polyolefins leads to the formation of 2 and 2, which are assimilated by
plants. Some organometal compounds, as well as complexes of variable-valence metals
with dialkyl dithiocarbamate (usually used as thermostabilizers of plastics), catalytically
degrade products of photooxidation of polymers, e.g., hydroperoxides, in storage. Besides,
complex compounds of metals are capable of absorbing the light energy. In the interaction
of organometal compounds with hydroperoxides, the so-called Norrish reactions occur. Depending on the content of sensitizers (the ScottGilid system), polymer is subjected to degradation or the system exerts a thermostabilizing action on it. The ScottGilid system is
easily introduced into polymer together with other additives and pigments.
The requirements imposed on photodegradable polymers used in agriculture and in industries are rather stringent. They should have a guaranteed service life, good mechanical
properties, be rapidly and completely degradable after the induction period, polymer degradation products formed should not be toxic, polymers should not change their properties
in storage, the polymer composition should be easily processable into items produced.
These polymers should not be expensive.
Polymer films used to fabricate cultivation constructions strongly warm up (to a temperature of 6085C) in places of the contact with the supporting structures of the frames.
Film covers on hothouses are subjected to the action of negative temperatures, which in the
North regions reach 19 to 40C. Calculations show that in the North-West and Central
European regions of the Russian Federation, in the Urals, in Western and Eastern Siberia,
in the Ukraine, Belarus, Uzbekistan, Latvia, Estonia, Moldova, Turkmenistan the thickness
of films from light-stabilized polyethylene for covering hothouses should be no less than
0.15 mm. Research showed that harvest quality and crop yield are practically the same at
different UV transmission degrees. Therefore, films with UV radiation-absorbing
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11
stabilizing additives can be used when growing most agricultural crops in hothouses. The
most widespread type of film used in hothouses in Western and Eastern Europe and the
USA are polyethylene films. This is due to their comparatively low cost, simple production
technology, possibility of manufacturing wide formats and other advantages, e.g., the simplicity of introducing various modifying additives. For these purposes, polyethylene of specials brands was manufactured.
Of film materials used for growing agricultural produce under coverage, mention
should be made of heat-resistant polymer films for disinfection of hothouse grounds with
live steam. This is the basic method of disinfecting hothouse grounds. It was invented in
Holland, but a Russian development is also available. According to this method, to increase
the efficiency of steaming (which kills all kinds of pests of agricultural crops) the ground
to be steamed is covered with a polymer film, which contributes to faster and deeper steaming. The ground is covered with the film, which is fixed with sand bags along the perimeter.
Live steam at a temperature of 115120C is fed under the film. The ground and the film
is acted upon with steam of a slightly lower temperature (90100C). One cycle of steaming
provides for holding the film at a high temperature (90100C) for 12 h, and then for
another 12 h to cooling.
Apart from growing fruits and vegetables in hothouses, films are also used to arrange
small-size covers cultivation constructions whose size does not allow the handling of
plants and harvesting inside these constructions. Such constructions include skeleton covers
for growing plants, tunnel film covers; to some extent, special perforated films are also applicable. In the latter case, the supply of heat to the ground in the spring and the warming-up
of the soil are much greater than in an open plot. A wide-format film 2030 m thick is
also efficiently used for covering sown crops and plantings without wireframes (the edges
of the film are buried into the ground 510 cm deep). The thin film does not prevent the
plant growth and provides for the hothouse effect required. Only perforated films are used
for this purpose. Though skeleton-free coverings are less efficient as compared with skeleton ones, their total economic efficiency is higher.
Removal of the films should be done by hand and is associated with pollution of the
environment, in connection with which a number of problems arises. One of the efficient
ways of solving them is to use films with a given lifetime, upon expiry of which the films
are degraded under the action of light, moisture and other natural factors to produce forms
assimilable by the environment. Degradation of the film on skeleton-free covers can start
in 20 to 70 days, but this time strongly depends on weather conditions.
Besides the described methods, polymer films are successfully used to make winter
coverings of fruits and berries, hay etc.
Mulching is an agrotechnical technique to prevent evaporation of moisture and formation of a soil crust, to maintain an optimal temperature of the soil and to suppress the growth
of weeds. Film mulching is used both in unprotected grounds, and inside film-covered hothouses and tunnels. Polyethylene films are the most widespread; they can be transparent,
semi-transparent, non-transparent, light- and heat-reflecting (white and aluminiummetallized). The greatest warming-up of the soil is observed in mulching by lighttransparent films, the use of which ensures a 4050% greater heat supply to the soil than in
an open plot. Semi-transparent films decrease the soil warming-up from 50 to 8090% depending on their integral light transparency. Reflecting films smooth the total amplitude of
soil temperature variations owing to the warming-up during the day and the delayed cooling
during the night. Coating the soil with cuts from metallized polyethylene films reduces the
extent of damage (owing to the illumination of the low side of the leaves) of undersized
12
vegetable plants by some species of insects (aphids, flea beetles and bugs). Black mulching
films detain evaporation of moisture, but prevent penetration of solar radiation to the soil
surface. Film mulching enhances the biological activity of the soil; herewith, the amount of
microorganisms in the soil and their activity change, the illuviation of readily soluble nitrogen fertilizers from the soil is delayed.
Mulching of the soil in cultivation constructions can be done most rationally by used
films for covering hothouses, as well as secondary polyethylene films.
Mulching by light-reflecting films in winter hothouses, when there is not enough light,
has become widespread. It improves the illumination conditions and increases the early harvest by 1525%. Additional illumination at the expense of the light reflected by the film
accelerates the ripening of strawberries, salads, kohlrabi in winter hothouses. A black film
for mulching, PE-157 brand SM (GOST 10354-82), was developed and is manufactured in
the CIS countries. Light-transparent photodegradable films PE-108-70 and PE-108-71 are
used for short-time mulching of vegetables and berries, potatoes and other crops. Besides
them, CIS industries also manufacture film materials of other types used for mulching in
unprotected and protected ground. In agriculture, fibre- and tissue-reinforced films are used
for growing and storing vegetables and fruits. By their optical characteristics, they are
slightly worse than polyethylene non-reinforced films. Reinforced films can be used at a
temperature from 60 up to +60C. They are mainly used for erecting cultivation constructions of protected ground (greenhouses, hothouses, coverings). The service life of the constructions is in this case longer (as compared with non-reinforced coatings), especially in
regions with increased wind and snow loads. Buildings and constructions from reinforced
polymer film materials are conditionally divided into three types: awnings, pneumatic constructions, skeleton constructions.
Skeleton constructions are distinguished by large reliability and do not require the use
of high-strength air-impenetrable materials. They are best of all to be used for growing and
storing horticultural produce. Skeleton-film warehouses and storages of horticultural and
other agricultural produce can be built quickly (35 days) and require no large capital investments or additional lighting. If it is necessary to make the premises darker, two-layer
coatings are used, the lower layer of which is light-impenetrable and which are fabricated
from, e.g., polyethylene filled with carbon black.
Foodstuffs can be protected from harmful substances getting into them by correctly
using the protective properties of polymer materials. It is important not only to grow a heavy
crop, to harvest it, but, which is especially important, to preserve it (not only from the point
of view of quantity, but also quality) up to the very moment of food consumption.
The problem of food preservation interested the man since long time ago. It was solved
differently at different times by different peoples.
The problem of food preservation emerged in connection with the need to store up food
reserves for oneself, ones own tribe, equpping an expedition, equipping an army etc.
Subsequently, formation and development of microbiology made it possible to lay the
scientific foundation under various technological techniques of food preservation. It proved
that the vital activities of microorganisms, which contribute to the spoilage of food, manifest themselves under conditions of a certain temperature regime, certain humidity, absence
of substances aggressively interacting with substances from which microorganisms consist,
etc. If the conditions do not correspond to those required for the development of microorganisms, the latter perish or their vital activities are temporarily stopped and, therefore, the
process of food spoilage stops, too.
A widespread technological technique of preserving food products is drying. The
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13
technique is based on the fact that most chemical processes determining the vital activities
of bacteria occur in an aqueous medium. Removal of water leads to the inhibition or interruption of chemical reactions contributing to the development of microorganisms and accompanying food spoilage.
In cells of fresh products, the food substances are, as a rule, in solution. In the course
of drying, the concentration of this solution increases until it becomes so high that the solution can not be absorbed by the cells of various microorganisms any more. At the extent
of drying, corresponding to the above situation, a food product can be stored without deterioration of its quality for a long time. The content of moisture in it should be observed not
to be higher than a certain limit: 1214% for dried vegetables, 1825% for dried fruits. The
smaller is the moisture content in the product after drying, the greater the guarantee of its
preservation is, the less the conditions for spoilage are.
However, the lower the moisture content in a dried product is, the more complicated
and, therefore, expensive the process of drying is. Besides, some substances useful for the
organism can be destroyed in the process. During the drying, water is evaporated from particles of the product and vapours formed are carried away. Drying is performed most often
using hot air, which, being a heat carrier, communicates a heat energy to water molecules.
Owing to the acquired energy, water molecules overcome weak physical and physicochemical bonds and pass from the product into the vapour. The higher the temperature of the air
is, the more water molecules pass into the vapour, i.e., into the heated air.
The moisture capacity of the air is different at different temperatures. This method is
used to increase the storage life of fruits, vegetables, milk, meat, fish and other foodstuffs.
In drying apples and pears, mainly early varieties are used. Primarily fruit drops are
dried. It is best to dry fruits of one variety. In the summer, fruits usually dry up in 34 days.
Before drying, fruits are washed. Washed fruits are examined to cut the damaged parts, the
cores are excised and the fruits are cut into slices not more than 1 cm thick. Small fruits and
pears can be cut into two or four parts.
A method of preserving products by drying at low temperature freeze-drying is of
an ever increasing importance at present.
The process of sublimation (removal of moisture at low temperature, when a product
is preliminarily frozen) can be greatly accelerated by removing water vapour by direct
pumping out (evacuation), condensation of vapours on a chilled surface, absorption of vapours by hygroscopic substances. The use of the method of freezing for preserving food
products revealed the phenomenon of structure breakdown of plant and animal tissues by
growing crystals of ice. To avoid this undesirable phenomenon accompanied by the loss of
a number of useful specific properties of food products, the following technique is used.
Products are chilled so rapidly that ice crystals have no time not even to grow but to be
formed. Products prepared for freeze-drying are frozen and placed into a chamber, from
which the air and vapours are pumped out. If pressure in the chamber decreases from the
initial magnitude (of the order of 760 mm Hg) down to 11.5 mm Hg, water could not be
in a liquid state under these conditions and passes from the solid state (ice) into the gaseous
state by omitting the liquid state, i.e., it evaporates. Transition of a substance from the solid
state into the gaseous state by omitting the liquid state is called sublimation. The vapours
formed are pumped out by vacuum pumps, and water is gradually removed from the frozen
product. It dries at a low temperature.
One of the main requirements to drying, as to the other preservation methods, is the
maximum preservation of the nutritive value of food products. Numerous studies of the biological and nutritive value of food products subjected to various methods of drying have
14
been carried out with this in mind. The results of studies convincingly showed that the best
integrity of food products and their nutritive value is provided for by the method of freeze
drying. This refers equally to products of both plant and animal origin.
Removal of water from a food product drying is a forced measure, which is due to
the necessity to inhibit the chemical reactions occurring in storage. After the storage, the
product should restore its initial properties and the initial content of moisture. Therefore,
the reversibility of the drying process is essentially determined by the capability of the dried
product to swell again in contact with water. A relative increment (with respect to the mass
of the dry product) of mass in swelling is called the extent of swelling. The extent of swelling of freeze-dried mutton was 3.5%, whereas that of heat-dried mutton only 2%. In other
words, meat after freeze-drying increased its mass 4.5-fold in 4045 min, after which no
increment was observed: all water, which the freeze-dried meat was capable of absorbing,
was absorbed. The process of water absorption is also observed in heat-dried meat. However, this process was slower than in freeze-dried meat, and it was completed only after
2.53 hours of swelling. The mass of heat-dried meat, after it absorbed the maximally possible amount of water, increased only three times. This difference in the swelling of
freeze-dried and heat-dried mutton is explainable by the denaturation of proteins and thickening of muscle tissue. Freeze-dried meat, being boiled after 12 months of storage, preserved its culinary and organoleptic properties. The caloric value of freeze-dried mutton is
3.5 times as large as that of raw meat. Heat-dried meat is close to freeze-dried meat by its
caloric value. However, by its organoleptic properties (taste, smell, appearance)
freeze-dried mutton is much better than that of heat drying. Fat on freeze-dried mutton
chops does not differ from raw meat. A heat-dried duck broth is usually turbid and has an
unpleasant taste. A broth from freeze-dried meat tastes good and has the specific flavour of
a duck broth.
A similar pattern is observed in comparison of freeze-dried and heat-dried fish. Thus,
proteins of freeze-dried meat of pike perch preserve their properties better than proteins of
heat-dried meat. Only insignificant changes in the composition of its proteins were observed during the storage of freeze-dried pike-perch meat. The specific composition of liver
oil determines its oxidation susceptibility. After a 12-month storage of freeze-dried meat of
pike perch, vitamin B1 was totally preserved. The extent of swelling of freeze-dried
pike-perch meat reached an equilibrium value in 3040 min and was 3.5. The swelling
equilibrium of heat-dried meat was established only in 3 h and was characterized by the
swelling extent of 2.2. It is known that the culinary properties of heat-dried meat of pike
perch leave much to be desired. But the broth from freeze-dried pike-perch meat, obtained
by boiling for 1517 min, has a good taste and flavour. Similar results were also obtained
in comparative studies of heat-dried and freeze-dried fillet of common carp. The caloric value of freeze-dried common carp meat proved almost five times as high as that of raw meat.
Freeze drying involves freezing of a product. However, it should be noted that freezing
of food products is of independent significance, not necessarily associated with drying of a
product. Chilling of foodstuffs can be used both for drying and with the aim to inhibit the
spoilage process without freezing the product itself. This goal is pursued in storing products
in refrigerators. But cold can also be used for freezing products with the aim of their further
processing. In the former case, products should be kept intact during the chilling, having in
mind not only mechanical damage but also the integrity of cell viability. Herewith, the biochemical processes continue in the products stored but, naturally, at a slower pace. The metabolic processes in, e.g., chilled fruits and berries are active, they breathe and ripen.
Freezing of foodstuffs is accompanied by significant changes in their tissues and cells. The
CHAPTER 1
15
moisture in them freezes and turns into crystals of ice, which grow and partially destroy
cells. Moisture freeze-out is, in turn, accompanied by dehydration of the liquid part, in
which the nutrient materials of the cells are dissolved. During the unfreezing of such products, the moisture formed in thawing of ice crystals can not be absorbed by the cells, which
underwent irreversible changes. Unfrozen products abundantly ooze juice. However, undesirable phenomena associated with the growth of crystals in freezing could be avoided. For
this purpose, the process of freezing should be very quick not to let ice crystals to be formed.
The matter is that for crystals, in particular, ice crystals, to be formed, their constituent molecules and atoms should be arranged in space in a strict order relative to one another. The
lower the temperature, the larger the viscosity of the liquid is. Therefore, if the cooling is
performed quickly, then, starting from some temperature, the rearrangement of the structure
has no time to be completed. The temperature is so low that a crystal should have formed,
but the structure remains the one corresponding to the liquid state. Molecules can not move
in space, but perform vibratory heat motions. There are no crystals and, thus, no irreversible
changes of the cells and tissues of frozen products take place. Therefore, to obtain a higher
quality of frozen products in modern refrigerating industry, the freezing process should be
performed quickly, with an intensive removal of heat, at as low temperature as possible. In
rapidly frozen products, the cell envelopes mainly remain unbroken. Therefore, there is no
juice oozing out after such products are unfrozen. Modern freezing installations usually provide for the coolant temperature within 25 to 35C. A product is frozen to 18 and is
stored at this temperature. During the storage, periodic temperature increases should be
avoided, as an increase of even several degrees is accompanied by the recrystallization of
ice, growth of separate crystals with all ensuing consequences.
To manufacture high-quality fast-frozen products, it is necessary to provide for the
freezing of manufactured semi-finished products in a fast freezer, storage of frozen products
in a refrigerator chamber of the plant, transportation of the products in refrigerator railroad
cars or refrigerated road vehicles for their sales. In shops, these products should also be
stored in distribution refrigerators or chambers. After purchasing rapidly frozen produces,
consumers should keep them in refrigerators, without allowing even for a short-time thawing. Manufacturing of high-quality frozen products is associated with expenditures for complex refrigerating equipment. However, when comparing various methods of foodstuff
preservation (sterilization, drying, pickling, marinading, addition of preservative agents), it
should be stated that in fast frozen foodstuffs the quality of the product preservation of
taste, culinary merits, vitamins, aromatic substances proves the highest.
At present, the domestic industries manufacture a broad range of fast-frozen foodstuffs. They include various kinds of fruits and vegetables, as well as products of a high
degree of doneness, such as vegetable, meat-and-vegetable and fish first and second
courses, fruit juices.
The process of freezing proceeds the most qualitatively and efficiently in special fastfreezing machines. Storage and transportation of frozen products requires their packaging
in hermetic and moisture-proof containers. If these conditions are not observed, during the
storage of frozen products in chambers at a temperature of 15 down to 18 the moisture
will be sublimed into the air bathing the products. The moisture that passed from the product
to the air is condensed at cold pipelines, walls, ceilings as frost. The layer of accumulating
frost prevents the transfer of heat from the freezing product to the coolant. Thus, nonhermetic or moisture-permeable packagings will cause the loss of weight of a freezing product, deterioration of its quality and worsening of heat-exchange parameters. Usually, loose
frozen products are poured onto tables covered with tin-plate sheets and packaged into
16
containers. Above, we mentioned the necessity to maintain the temperature of a frozen

product constant both in storage and in transportation, as otherwise ice-crystal growth will
take place with the ensuing consequences.
Fish meat is in most cases less prone to deterioration when frozen by traditional methods. However, during the storage in refrigerators evaporation of moisture takes place, which
is accompanied by the penetration of ice crystals into the tissues. To prevent losses and
quality deterioration of fish products, a new cryotechnology for processing polymers from
aqueous solutions was developed. A protective coating is formed on fish products without
any additional energy expenses. Two types of food coatings, Polyol-1 and Polyol-2, were
developed. The second coating contains preservative agents for the inhibitory action on microflora and a structure former to produce an elastic transparent coating with a long lifetime.
Fresh fish is to be coated, which makes it possible to preserve additionally large quantities
of a valuable product lost at the stage of preliminary freezing. The process for the Polyol-1
protective coating was implemented at the Gurievrybprom Production Enterprise of the
Kaspryba All-Russian Industrial Association for long-term refrigeration storage of frozen
fish.
An incorrect choice of material for containers and packagings of frozen products,
the same way as an incorrect packaging of a product, can render null all professional actions
of sorting, calibration, washing, cleaning, cutting, chopping, freezing and other process
operations.
Considering the methods of preserving food products, we can not but dwell on one of
the classical methods preservation by heat. Vegetables for preserves, the composition of
which includes, besides vegetables, only water and some salt and sugar for good taste, are
subjected to washing, calibration, cleaning, cutting and blanching. The caloric value of such
preserves is not high, but they keep almost all valuable properties of preserved vegetables.
This applies to their taste, flavour and food value. Most vegetable natural preserves are sterilized by heating above 100C. For instance, green peas are preserved, when their grains
are green, soft and sugary. Usually at this stage of ripeness, their grains contain 57% sugar,
2030% vitamin C, proteins and mineral substances. Prepared grains of green peas are
blanched at 9098 for 34 min, after which the grains are immediately cooled to avoid
overcooking. Green-pea grains thus prepared are packaged into tin-plate or glass containers, and a hot filling is poured in. The filling consists of sugar (23%) and salt (23%) dissolved in hot water and should be filtered before use. Sealed containers are subjected to
sterilization by heating to kill microorganisms, which cause spoilage of the product. In industrial conditions, such a sterilization is performed in autoclaves hermetically closed cylindrical steel boilers. The higher the sterilization temperature is, the sooner the sterilization
is completed, i.e., the less time is required to kill microbes. However, too high sterilization
temperature can lead to a deterioration of the quality of the preserves: darkening of the product, an unpleasant flavour etc. These changes are usually due to undesirable chemical reactions between the components of the product at too high temperatures, which do not occur
at lower temperatures. The sterilization temperature is determined by the resistance of microbes to high temperatures, which essentially depends on the acidity of the sterilized product. Usually, bacteria not forming spores perish during the boiling. Sporulating bacteria
perish only at a long-time heating up to 110120. In an acidic medium, e.g., in tomato
or sorrel puree, bacteria do not develop. However, in such products spoilage is due to molds
and yeasts, which perish in boiling. Products with a low acidity are sterilized at temperatures of 112120. Large containers are heated up slower, low flat cans are heated up
faster than high ones.
CHAPTER 1
17
Besides temperature, size and shape of cans, the sterilization time is also determined
by the consistence of the product. The more densely the product, e.g., paste, fills a can, the
more time is required for the necessary temperature to be established in the middle of the
packaging. Besides the thermal conductivity of the contents of the packagings, the sterilization time is also determined by the thermal conductivity of (iron, glass or polymer) containers, as well as the initial temperature of cans. Therefore, its own regime of thermal
sterilization should be chosen for each kind of preserves and each type of cans, based on
the above conditions.
1.3
Technology of preserving the quality of foodstuffs in manufacturing,

transportation and sales
In production of foodstuffs, of great importance for preventing losses and spoilage, as well
as corrosion of food equipment is the use of antiadhesion coatings.
An optimal coating for baking rye bread was developed and is used at the St.-Petersburg Bread-baking Plant No 12. Besides the economy of oil, the antiadhesion coating saves
a considerable amount of flour, eliminates expenses for oiling and cleaning of molds, facilitates the application of automatic machines and, which is of no small importance, enable
increasing the quality of baked goods. In molds free of burnt deposits the required temperature is easier to maintain, losses of bread are much smaller, the work of oven operators is
much easier. Antiadhesion polymer coatings are applicable in other branches of food industry, e.g., in meat and dairy industry. Some components of the equipment in food industry,
in particular, shelves and racks for storing and ripening cheese are made from wood and
have a number of disadvantages: they are short-lived, are characterized by a highly labourintensive service due to stickage of cheese and integrated sanitation treatment, during which
wood warps. Besides, labour-intensive process operations can not be mechanized in this
case. Shelves and racks can be fabricated from cheep carbon steel coated with a polymer
coating, which should possess a low adhesiveness to foodstuffs and necessary physicomechanical and sanitation properties. The most important requirements to such coatings in
operation are the stability of antiadhesion and physicomechanical properties, protection of
the metal equipment from corrosion under conditions of high humidity within the temperature range of 10 up to 80. Material with the required properties can be produced by targeted modification of non-critical and physiologically harmless polymers, e.g., highdensity polyethylene (HDPE). To eliminate the cracking of HDPE-based coatings in their
operation in aggressive moist media, HDPE was modified by polyethyl siloxan PES-5, as
the result of which HDPE was stabilized, and the antiadhesion properties of the coating improved.
The most labour-intensive operations in fabrication of molded meat products include
dislodging of a product from the mold and the subsequent cleaning of its surface. Interlaying materials cellophane and cooking parchment paper are used inefficiently to provide for the separation of a product and a mold. Animal fat is used for greasing the molds
in production of meat loafs, as the result of which a deposit is formed on the molds. The
quality of the products and the sanitary condition of the production shop deteriorate in this
case, the molds should be subjected to systematic cleaning, which makes difficult the mechanization and automation of the processes. All these drawbacks can be eliminated by using
antiadhesion coatings.
In the process industries of the agroindustrial complex, of great significance is the protection of equipment from corrosion. In this respect, it is difficult to overestimate the role
18
of antiadhesion coatings which by their sanitary characteristics are permitted to be used in

contact with food products. The problem of corrosion is very significant, though achievements in this field are quite a few, the domestic developments including.
One should take into account the losses of manufactured food products in storage,
transportation and sales by commercial enterprises. Various compositions for the protective
coating of food products are known. Thus, a composition was invented, which protects
cheeses from drying and molding. A composition for coating sausages and a method of producing a casing on them were proposed. A composition for applying a protective coating
on fish and fishery products was also developed.
The most promising method of long-time preservation of the nutritive properties of
food products is their low-temperature preservation. However, a considerable amount of
weight of a product is lost in freezing and subsequent storage due to evaporation of moisture, the quality of a product deteriorates, oxidation of lipids and denaturation changes of
proteins occur. One of the rational ways to retain the quality of products is to create coatings
impermeable for oxygen and moisture on their surface. For this purpose, aqueous solutions
of biologically inert polymers, e.g., polyvinyl alcohol (PA) are used. PA acquires water resistance in the process of film formation at low temperature. During the freezing of the
polymersolvent system, as the result of a phase transition accompanied by an abnormal
increase of its volume, PA undergoes mechanochemical transformations (cryolysis). Cryocracking of macromolecules is accompanied by the emergence of active cryolyzates, whose
interaction leads to the formation of insoluble spatial structures.
The topicality of the problem of using advanced polymer materials determined the necessity of international forums exhibitions and symposia dedicated to this problem. The
cost of a packaging was on average 8% of the cost of product. There is a tendency in European countries to sell foodstuffs in packagings convenient for preparation of food in microwave ovens.
Great attention is paid to the process evaluation of the packaging systems from the environment-protection point of view. Among the main tendencies of the packaging business
in the USA, it is necessary to note the development and commercial production of ecologically pure packagings, a decrease of pollution of the environment. There is a tendency to
move from multi-layer to single-layer packagings, e.g., single-layer bottles from polyethylene terephthalate (PET), which are easy to identify and reprocess. Packagings are used,
in which deep-freeze dishes can be warmed in microwave ovens (PET). Thus, Gortons
place fish sticks into a packaging, which is equipped with elements from metallized PET
film above and below. The elements are susceptible to the absorption of microwaves, which
leads to the effect of a crunchy crust. Special attention is paid to the use of renewable resources (wood, plants). In this respect, of interest is the packaging material based on ethrol,
which under certain processing conditions can be transferred to a liquid-crystalline state.
Packaging in a film material in liquid-crystalline state is rather promising.
Polymer packaging materials found wide use throughout the world, Russia including.
Expanded production of polymer film materials is restricted only by deficit of the initial
materials. For this reason, it is possible to organize production of polyisoprene hydrochloride-based polymer films with good sanitation parameters, in contact with fats including, which easily yield to two-dimensional strain and shrink after orientation at 70C. The
initial materials are polyisoprene (whose output reaches several million tons per year), HCl
and methyl chloride (which should be subjected to recuperation), a small amount of sorbic
acid (used as food stabilizer at present). The method of producing a film-forming material
based on polyisoprene hydrochloride was developed well back in 1960s.
CHAPTER 1
19
Multilayer films became widespread in the world practice as packaging materials. The
first domestic multilayer film for packaging non-fat food products was a film from polyethylene and cellophane, which was improved and found widely used for packaging food
products (not of increased fat content). Cellophane is produced from naturally renewable
raw materials, is biologically harmless (at a corresponding control of production), possesses
the barrier properties, which significantly deteriorate when it is moistened. A disadvantage
of cellophane is its incapability of heat sealing, which greatly worsens the packaging process of food products. A combination of these materials produces a film heat-sealed material with high barrier properties. However, as the inner layer is polyethylene, this material
can not be in contact with fatty food products. Progress in the development of multilayer
film materials in this and other countries was accompanied by the emergence of multilayer
films with different combinations of paper, foil, various polymer films and binders. The
problems one comes across in this case are pollution of the environment and interaction of
a foodstuff with the packaging. Regularities of the interaction of a foodstuff with the packing and with the environment are being revealed. The most important processes of this king
are penetration of oxygen, water vapours, light and carcinogens from the atmosphere into
a foodstuff through polymer films. Substances contained in the foodstuff can get to the environment through the packaging. These processes are undesirable.
In the recent years, the use of the vacuum freeze drying of food products has become
more widespread, and the popularity of this method has increased. Production of foodstuffs
by this method has both positive and negative aspects.
The positive aspects include the high quality of these products; by their nutritive and
gustatory properties, they are comparable only with natural deep-frozen products (studies
by E.I. Kaukhcheshvili). A positive quality is also the capability of long-time storage (up
to 1 year and more) under non-regulated conditions of the environment. A drawback is the
high cost of vacuum freeze preservation; as shown by B.P. Kamovnikov, average reduced
costs for the removal of moisture from an object of vacuum freeze drying exceed similar
expenses for heat drying 1520 times.
A quite natural and justified idea would be to reduce the costs of preserving freezedried products several times without decreasing the high consumer properties. Calculations
show that, though this is difficult, this problem is quite realizable technically: to solve it,
the freeze-drying process should be performed not in a vacuum, but at an atmospheric pressure. This would, first, make it possible to exclude the expensive and energy-intensive vacuum equipment from the process. Second, at an atmospheric pressure heat-and-mass
transfer could be intensified (especially at the final stage of drying) due to the convection
of the drying agent, which is out of the question under vacuum conditions. In other words,
for production of daily-consumed freeze-dried products the vacuum freeze-drying should
be replaced with atmospheric freeze-drying (AFD).
In a general case, the process of preservation by the AFD method includes the following major operations: sorting and treatment of raw materials, freezing, removal of moisture
by freeze drying at negative temperatures, cold and hot completion of drying to a given final
moisture content, prepackaging and packaging of the dried product. The properties of the
preserved products crucially depend on the condition of raw materials and the quality of
performing each of the above operations. Herewith, the preservation process has its peculiar
features for each particular kind of product, depending on the properties of raw materials
and requirements to the final product.
It should be pointed out that materials dried by the AFD method are rather hygroscopic
and have a large specific surface of the dry carcass.
20
Objects of drying
Raw materials for production of

medical preparations / biostimulants
Foodstuffs
Foodstuffs of animal origin
Endocrine / enzyme raw

materials of animal origin
Crude drugs of plant origin
Figure 1
Foodstuffs of plant origin

Sea foods
Classification of objects of drying.
For this reason, long-term storage without reduction of quality can be possible only in
a reliable hermetically sealed packaging. With any other conditions equal, the duration and
quality of storage are basically determined by the quality of packaging. For instance, the
use of metal tin-plate cans or multilayer metallized films for fabrication of packages and
the filling-up of these containers with a dry product with gaseous nitrogen makes it possible
to provide for the storage of plant products in the off-season period.
As the preservation by the AFD method is a sufficiently complex process, and the preserved products are usually intended for long-time storage, the requirements to the initial
raw materials are high. The nutritive value and vendibility, structural mechanical properties
and admissible terms of storage, the temperature level of processing and duration of individual process operations all these are largely determined by the properties of the raw materials. Along with the diversity of the chemical composition of various food products, they
are characterized by one common property: they contain a considerable amount of water.
As objects of processing (including by preservation by the AFD method), products are
classified by their physical nature into objects of animal and plant origin and sea foods. By
their consumer properties, a separate group is endocrine / enzyme raw materials, which are
usually not used as a source of food, but are an essential source in production of medicines
and biologically active substance.
A classification of objects of drying is presented in Fig. 1. The purpose of products is
taken as the first-rank classification criterion. Two large groups are singled out here foodstuffs and raw materials for production of medical preparations and biostimulants.
The second rank of classification is chosen to be the characteristic of dividing the
objects by their physical nature. Individual groups of objects of drying singled out at the
second-rank level differ significantly by their composition, physicochemical and other
properties (Table 1.1). For this reason, the possibility of using methods of vacuum or atmospheric freeze drying for their preservation and the choice of drying regimes should be decided upon separately for each group of products close by their properties.
A complex interaction of these components with water and with one another forms the
properties of food products. The amount of water in a product also determines the conditions of its storage, which would not reduce its quality.
Meat used for preservation by the AFD method should conform to a number of requirements. Cartilages, large vessels and connective tissue are removed during the trimming in
the preparation of meat for drying. These inclusions considerably differ by their heat transfer properties from muscle tissue, their presence would lead to nonuniform drying, worse
21
CHAPTER 1
rehydration of the dry product, would reduce vendibility and gustatory qualities of culinary
products made using the dry product. A high content of fatty tissue is inadmissible. The
melting temperatures of animal fats are rather low (e.g., beef fat, 3252C; pork fat,
2848C; chicken fat, 2338C). For this reason, at the stage of residual moisture removal
(completion of drying) fat can melt and fill free pores, which would sharply increase the
duration of drying and formation of non-drying inclusions (lenses) in the depth of the specimen. Besides, at the stage of storage of dried meat the oxidative transformations of the lipid
fractions can drastically deteriorate the organoleptic parameters of the product. These
changes can be the largest in pork and poultry meat, as fats of these kinds of meat contain
many unsaturated fatty acids.
Table 1.1
Product
Pasteurized milk
No fat curd cheese
Common beef
1st category hens
Hens eggs
Azov-sea carp
Potato
Cabbage
Mushrooms
Apples
Black currant
Apricots
Plums
Bulb onion
Water,
%
Proteins,
%
Fats,
%
Carbohydrates,
%
Fibre,
%
Ash,
%
88.5
77.7
71.7
61.9
74.0
75.3
75.0
88.5
88
85.6
85
86
87
86
2.8
18.0
20.2
18.2
12.7
18.4
2.0
1.3
1.8
0.4
1.0
0.9
0.8
1.7
3.2
0.6
7.0
18.4
11.7
5.5
0.1
0.1
0.8
4.7
1.5
0.7
0.7
19.7
7.0
1.1
11.3
8.0
10.5
9.9
9.5
1.0
1.2
1.5
0.6
3.0
0.8
0.5
0.7
0.7
1.2
1.1
0.8
1.0
1.0
1.11
1.0
0.4
0.5
0.9
0.7
1.3
1.0
Energy value,
100 g/kJ
243
360
602
1008
657
506
374
138
79
192
167
192
180
180
The requirements to the raw materials intended for preservation by AFD are satisfied
the most by meat of young animals. The muscle fibres of this meat are more thin and elastic,
meat possesses a relatively lower mechanical strength, the content of fat in it is small.
An important factor in producing a high-quality product is the dependence of the properties of meat not only on the tissue and chemical compositions, but also on the depth of
autolysis. According to the obtained recommendations, meat after a 3- or 4-day holding at
24C should be used for preservation by freeze drying.
When choosing the AFD regimes for milk and dairy products, it should be taken into
account that the properties of milk proteins change in heating and freezing. Thus, in freezing
(down to temperatures below 10C), the colloidal properties of milk proteins change, their
solubility decreases. Milk fat in the milk mass is distributed in the form of balls up to 5 m
in diameter, each of which is enclosed by an envelope containing a protein complex. In the
contact of lipid fractions with oxygen of the air during the AFD process or in storage of a
dry product, the product can rancidify and suffer a deterioration of taste. For this reason,
when packaging dry milk and dairy products it is necessary, as in the case of packaging dry
meat products, to use hermetic vapour- and light-impenetrable containers filled with inert
gas. Products prepared from no fat milk are more resistant.
22
Milk sugar (lactose) is close by its nutritive value to common beetroot sugar. However,
a larger content of reducing sugars in milk and dairy products (e.g., in mare milk, up to 7%)
creates conditions for sugar-amine reactions in storage of dried products. For their maximum inhibition, it is necessary to remove moisture from dairy products in the process of
drying up to 23%. In practice, during the preservation by the AFD method this condition
is achieved by drying dairy products in air convector heaters (furnaces) at temperatures of
4050C upon completion of the moisture removal by the icevapour phase transition.
Freeze drying of milk, curd, many fermented milk products makes it possible to preserve maximally the high quality of the product produced. And for such products as, e.g.,
acidophilic paste and Mechnikovs sour milk, it has no alternative.
The recent decade is characterized by an increased production of new kinds of products based on combinations of meat raw materials with proteins of plant and animal origin.
Among protein preparations used for partial replacement of meat raw materials, compositions used the most are milk proteins (sodium caseinate, milkprotein concentrate etc.) as
well as soy proteins (soy isolate, soy concentrate, soy flour and grits). Numerous experiments have proved that a rational level of the substitution of protein for meat raw materials
is from 10 up to 30%, depending on the kind of protein used.
Introduction of rehydrated protein preparations into the meat system raises the stability
of the dried meats lipid fraction to oxidation and increases the storage times, raises the resistance to thermal denaturation, provides for the balance of the amino acid composition,
improves the organoleptic properties of culinary products prepared from reconstituted dry
products. An especially important fact is the possibility of drying and freeze drying of meat
products with protein additives at a higher temperature as compared with meat products
containing no protein fillers. A temperature increase could be 56C without the loss of
quality, which enables saving energy and in some cases using a simpler equipment.
Milk and soy proteins are widely used at present for enrichment of meat products. Milk
proteins are added into chopped meat as sodium caseinate. The substitution of sodium ions
for calcium available in milk has a positive effect on the increase of solubility of the protein
and imparting it with the properties of a water-binding and fat-emulsifying component.
Precipitation of casein with whey proteins yields preparations containing all milk proteins, the so called coprecipitates with up to 80% protein in the dry residue.
Processing of soybeans to obtain food proteins is performed in several directions,
which enables production of soy flour and grits containing about 50% protein: soy concentrate (produced from soy grit, from which soluble carbohydrates are removed and protein
passes into an insoluble form), the content of protein up to 70%; soy isolate (highly purified
protein preparations without taste and smell), the content of protein up to 90%. Integrated
studies of the chemical composition of some kinds of protein preparations show that all protein preparations are characterized by a high protein content and a low fat content.
Soy protein preparations contain essential vitamins and mineral salts.
A comparative analysis of the amino acid composition indicates that plant protein
preparations are characterized by a lower content of sulfur-containing amino acids as compared with proteins of animal origin. However, when soy proteins are used in a complex
with proteins of animal origin (muscle protein, caseinate, blood plasma) their biological activity increases due to the mutual enrichment with essential amino acids.
In the freeze drying of eggs, a mixture of egg white and yolk (a melange) or only white
is used. A promising procedure is the use of eggs for preparing products with a whipped
structure meat, milk or fruit souffle, which are then preserved by the AFD method.
The presence of various enzyme systems in eggs leads to the development of autolytic
CHAPTER 1
23
changes in their storage, the general tendency of which is similar to the autolysis process
in animal tissues, so dietary or fresh eggs are used as the initial product. According to the
operating standard, the former are the eggs that come to the consumer no later than 7 days
from the day of laying and not kept in solutions. Fresh eggs are those that were kept at a
temperature of +2 to 2C for no more than 30 days.
Along with animal and poultry meat, fish is an essential source of complete proteins;
proteins of fish meat are easily assimilated by the human organism. Constituents of fish
meat are basically represented by proteins, lipids and water. The chemical composition of
tissues is rather inconstant and depends on the fish species, age, time of capture etc. Thus,
the relative moisture content is on average from 53 (eel) up to 81% (cod, pike perch); protein substances, 10 up to 24%. Variations are even larger in the fat content from 0.20.4
up to 30%. Fatty meat contains less water than lean meat. However, the total content of
water and fat in the fish body remains practically always a constant value close to 80%.
For atmospheric freeze drying, only the meat of fish with a minimum amount of fat
could be used, as it could be oxidized both during the drying and in storage. We should note
that, owing to a high degree of unsaturation, fish fats are easily oxidized; herewith, some
of these products can be toxic. As the result of postmortem processes, fish meat undergoes
significant physicochemical changes. The initial stage of rigor mortis is characterized by
intensive glycolysis of glycogen, accumulation of lactic acid in muscles and a pH decrease.
The further development of the processes finally leads to contraction and tension of muscles. With the course of time, rigor occurs owing to the further irreversible protein changes,
determined as maturation and autolysis. Meat becomes more tender.
Sea is also a source of other valuable foodstuffs (e.g., prawns, crabs) and raw materials
for medical industry (various algae). Freshwater reservoirs are habitats of such a valuable
source of protein and biologically active substances as chlorella. These objects can be successfully preserved by the AFD method. The qualitative indices of dry semi-finished products conformed to the imposed requirements.
A characteristic feature of all plant products is a large water content, 6696%. The
main carbohydrates of fruits and vegetables are sugars, starch, cellulose and pectin substances. Studies of plant-origin products show that the chemical composition of even one
species changes depending on the extent of ripeness, variety, growth conditions etc.
Fruits and vegetables contain all known vitamins, except vitamins B12 and D (calcipherol). Vitamins C, A (as provitamin A, carotene), vitamin K occur in largest amounts.
Plant products are the main source of vitamin C. The change of its content in the food ration
due to freezing, freeze drying and subsequent storage of the dry product is (together with
the organoleptic indices) an essential criterion of quality of the entire preservation process.
Vitamin C is easily destroyed by heating and under the action of oxygen of the air.
Thus, in the presence of oxygen of the air it breaks down already at a temperature of 50C.
This should be taken into account when choosing the temperature regime at the stage of
completion of the drying, as well as when choosing the design of the device for AFD.
Fruits and berries contain a considerable amount of sugars, from 79% (black currant,
garden strawberries, apples) up to 2025% (dog-rose, grapes). In vegetables, the content
of sugars is usually at a level of 46%. Sugars are represented by glucose, sucrose and fructose, the quantitative ratios between which are different for each kind of product. Changes
in the properties of sugars in the course of the process have a strong effect on the quality of
the ready-made product. The action of high temperatures is inadmissible, they can contribute to the caramelization of sugars, induce reactions of melanoidin formation as a consequence of the interaction of sugars with amino acids. As the result, browning of the product
24
takes place. Note that plant products with a significant sugar content, e.g., bananas, are practically unsuitable for preservation by the AFD method.
Fruits and vegetables contain 0.23% of cellulose, which is mainly used for construction of envelopes and cell walls. The composition and content of the cell walls determine
the mechanical properties of tissue. Cellulose is characterized by a high chemical resistance. Preservation of fruits and vegetables by the AFD method usually envisages the destruction of cellulose the preparation of purees and pastes, comminution.
The pectin substances of plant-origin products include complex polysaccharides. In
fruits and vegetables, they are 0.12% of the total mass of a product. Significant amounts
of pectin are in apples, quince, plums, apricots. Pectins have the property of forming stable
colloidal solutions. The condition of the pectin substances in a dry product largely determines the degree of its rehydration.
As shown by the experience of preserving a broad assortment of fruits, vegetables and
berries by the method of vacuum freeze drying, the ultimate choice of this or that variety
with the aim to obtain a high-quality dry product can be made only based on the experimental check in each particular case. It was found that particular varieties of plant-origin products, good by their initial quality parameters, were unsuitable for preservation (due to the
loss of shape in drying, instability in storage, bad rehydration). In full measure, this is also
valid in the case of the AFD method.
The AFD method has a great potential for preserving flavouring/spicy plants added to
foods for flavour and to excite appetite. Many savoury herbs in the form of spices have a
strong bactericidal action. In the European part of Russia, these are widely used dill, parsley,
parsnip, coriander (cilantro), peppermint and estragon (tarragon). Leaves of these plants
contain various aromatic oils, vitamin C, provitamin A, biologically active substances.
1.4
Application of chemical preservatives in food industry
1.4.1 General information on chemical food preservatives

Chemical preservatives are synthetic chemical substances used for slowing down or preventing undesirable changes in foodstuffs and technical products of biological origin
caused by microorganisms bacteria, molds, yeasts.
Chemical food preservatives include sulfurous anhydride and some salts of sulfurous
acid; benzoic, sorbic, propionic acids and some of their salts; methyl, ethyl and propyl esters
of para-oxybenzoic acid. Hexamethylene tetramine; formic, boric and salicilic acids;
formaldehyde, hydrogen peroxide have not been used lately in most countries.
Preservatives make it possible to increase the storage times of ready-made products
and raw materials, as well as prevent spoilage of raw materials in processing. Preservatives
are usually used when other methods are not possible.
Application of chemical preservations is restricted as, being toxic for microorganisms,
they are harmful for man and animals. Therefore, they are used at very small concentrations,
harmless for higher organisms and man.
In food industry, chemical preservatives are used mainly in combination with heating,
freezing, drying, irradiation etc. Their actions add up.
The method of treating a product with preservatives depends on the kind of product
and its condition. Liquid and comminuted products are usually thoroughly mixed with the
preservative. Lump products are subjected to surface treatment, e.g., by immersing a product into a solution or by sprinkling it with a solution.
25
CHAPTER 1
Treatment of the surface of a product is especially expedient when there are no microorganisms inside it.
Preservatives cause damage to microbial cells, reversible (bacteriostatic or fungistatic
action) or irreversible, as a consequence of which cells die (bacteriocidal or fungicidal
action).
At a bacteriostatic action, microorganisms remain alive, but are not capable of propagation. If they are transferred to a favourable medium, propagation becomes possible again.
However, microorganisms gradually die even at a bacteriostasis, depending on the concentration and duration of action of a preservative. In practice, bacteriocidally acting substances differ from bacteriostatic ones only by a greater pace of microbial die-off.
The rate of bactericidal action increases with the increase of the concentration of a
chemical substance and temperature.
Bacterial cells can develop, propagate, produce toxins only under certain conditions.
Bacteria, e.g., are sensitive to pH of the environment. A significant change of pH leads to
a change of the surface amphoteric structures of the cell and, owing to this, to a disturbance
of cell equilibrium followed by cell death. In particular, the osmotic exchange between the
cell and the environment is disturbed. In some microorganisms, a pH decrease causes an
activation of the ribonuclease autolytic system, which is unfavourable for cell viability.
Bacteria, with few exceptions, can develop in media with pH 4.29.4; yeasts develop
in a more narrow pH interval (4.06.8); and mold fungi, within even broader pH limits
(1.211.1).
Many preservatives of acidic type are more efficient at low pH, as a major part of them
are in a non-dissociated form (Table 1.2).
Table 1.2
Preservative acid
Sulfurous
Bromoacetic
Salicilic
Formic
p-Chlorobenzoic
Benzoic
p-Oxybenzoic
Acetic
Sorbic
Propionic
Dehydroacetic
Bisulfite
Boric
Dissociation
constant
1.7102
2.05103
1.06103
1.77104
9.3105
6.46105
3.3105
1.8105
1.73105
1.4105
5.3108
1.02107
7.31010
Non-dissociative (real) part, %, at pH

2
37
83.0
90
98.3
99
99.3
99.7
99.8
99.8
100
100
100
100
5.5
32.8
49
85.0
91
93.9
96.8
98.2
98.3
99
100
100
100
0.55
4.65
8.6
36.1
52
60.7
75.2
84.7
85.2
88
95
99.9
100
0.04
0.48
0.94
5.35
9.7
13.4
22.3
35.7
36.6
42
65
99.0
100
0.001
0.049
0.094
0.56
1.06
1.52
2.94
5.26
5.46
6.7
15.8
90.7
100
7
0
0.0049
0.0094
0.056
0.107
0.15
0.30
0.55
0.57
0.71
1.9
49.5
100
Owing to this, molecules of an acid can penetrate into microbial cells, whereas penetration of ions into cells is impossible or barely possible.
As the dissociation constant of a preservative acid decreases, even at a neutral or weakly acidic reaction, the number of non-dissociated molecules, which guarantee its action, increases. The weaker a preservative acid, the closer the pH can be to the neutral point; the
preservative action of the preservative does not decrease. Non-dissociating preservatives,
26
e.g., esters of para-oxybenzoic acid, are relatively independent of pH and can change at the
neutral reaction.
1.4.2 Mechanism of action of chemical preservatives
The mechanism of action of chemical preservatives on microorganisms has been little studied to date.
Common methods of determining the inhibitory doses of chemical preservatives can
not reveal the mechanism of their action. They can only establish the concentrations, at
which the propagation of microorganisms slows down. In practice, it is believed that a preservative is efficient if it prevents the growth and propagation of microorganisms.
The probable mechanism of action of chemical preservatives on microorganisms, proposed comparatively recently and accepted at present, is presented below.
Compound
Probable effect
Cationic and anionic surfactants
Disturbance of cytoplasmic cell membrane. Denaturation

of enzyme protein
Phenols, chlorophenols, naphthol

sulfonates, cinnamic acid
Disturbance of cytoplasmic cell membrane. Reaction

with genetic-mechanism proteins
Fatty acids, alcohols and high-molecular- Disturbance of cytoplasmic cell membrane. Competitive
mass aldehydes
inhibition of enzymes by low-molecular-mass acids
Chloroacetic acid
Effect on the cell wall. Competitive inhibition
Benzoic acid, p-chlorobenzoic acid,

p-oxybenzoic acid and its esters
Effect on the cell wall. Competition with coenzyme for

apoenzyme
Salicilic acid
Effect on the cell wall. Competition with nicotinamide

adenine dinucleotide. Competition with amino acids used
by enzyme
Boric acid
Reaction with phosphorus metabolism enzymes
Sulfur dioxide, sodium sulfite, sodium

bisulfite
Reaction with aldehydes formed in dissimilation of

carbohydrates. Reduction of SS bonds in enzyme
protein
Chlorine, chloramines, nitrogen trichloride, peroxides, nitrates and other

oxidants
Breakdown of sulfhydryl groups in enzyme proteins.

Breakdown of sulfhydryl groups in genetic-mechanism
proteins.
Ethylene oxide and other epoxides
Reaction with carboxyl and other active groups in

enzyme protein
Fluorides, fluorosilicon compounds and

fluoroborates
Reaction with prosthetic groups of enzymes. Reaction

with active groups of enzyme protein
Formaldehyde
Reaction with active groups of enzyme protein. Reaction

with active groups of genetic-mechanism protein
Salts
Precipitation of enzyme proteins
Exchange between the bacterial cell and the environment is on the level of a limiting
surface (the envelope); a number of differentiated protoplasmic structures, which create
conditions required for active exchange of the cell with the environment, also occur here.
Any substance violating this topography of the cell causes a disorganization of surface
structures, which is equivalent to cell damage. In these cases, we observe bacteriostasis, or
death, of the cell.
CHAPTER 1
27
Under the action of chemical compounds, the metabolism in the microbial cell changes. Metabolism in any cell is inseparably linked with the activity of the enzymes.
The action of certain chemical substances on some enzymes can lead to the termination
of preparation of nutritive material for assimilation, to the associated lack of nutrients and,
therefore, to the interruption of the growth and propagation of microorganisms, i.e., to a
bacteriostatic effect. If the stores in the cell are depleted, it dies. The total damage of certain
enzymes, in particular, dehydrogenases, can lead to the cessation of the oxidative processes
and associated processes of synthesis, i.e., to the termination of life. Depending on the reversibility or irreversibility of the reaction, the effect will be bacteriostatic or bacteriocidal.
Chemical substances, depending on their specific reactivity, can affect cell enzymes
by interacting with the functional groups of an enzyme. The catalytic action of an enzyme
is determined by several functional groups sulfhydryl, disulfide, indole, imidazole etc.
The breakdown or blockage of a group interacting with substrate or coenzyme leads to the
cessation or deceleration of the catalytic reaction.
The mechanism of blockage of active groups of enzymes can be different. For instance, the sulfhydryl group is blocked via oxidation
2R
SH
R' + H2O.
or substitution of hydrogen
R
SH + R'OH
Formaldehyde is characterized by a small selective reactivity. Depending on pH of the

medium, it can block various functional groups: at pH 9.5, free amino acids; at pH 6.0, the
imidazole group of histidine, at pH 5.0 and lower, formaldehyde is predominantly bound
by amide and guanidine groups; it also reacts with indole and sulfhydryl groups.
The preserving action of sulfurous acid is also based on its capability of damaging the
enzymes of the microbial cell. Substances capable of acting as reducers and oxidizers inhibit the activity of the enzymes. The enzymes containing the functional SS group, on
whose presence their catalytic activity depends, are inactivated by such reducing substances
as SO2, H2S, HCN, dithionate or HCOH. The SS bonds are split to form HS groups.
Besides, sulfurous acids, by reacting with aldehydes formed in carbohydrate exchange, capture them and violate the normal metabolism in the microbial cell. Thus, acetaldehyde sulfonate formed in this reaction is not accessible to corresponding enzymes.
In this case, inhibition of activity of the enzyme system is achieved by blocking the
substrate, which becomes inaccessible to microbial enzymes.
A possible explanation of the mechanism of inhibiting the growth of mold was proposed, proceeding from the supposition that sorbic acid is degraded to final products under
the influence of mold enzymes by the type of the -oxidation of fatty acids. At the same
time, it was established that cyanide selectively inhibits oxidation of butyric acid to -ketobutyric acid under the action of mold enzymes. Dehydrogenase, which catalyzes the conversion of butyric acid to crotonic acid, was not inactivated by cyanide, but the enzyme
system catalyzing the conversion of crotonic acid to -oxybutyric acid, was inactivated totally. This means that ,-unsaturated fatty acids accumulate in the medium; this accumulation inhibits the dehydrogenase system of molds. When sorbic acid is added to a food
product, the final product of the reaction catalyzed by mold dehydrogenase is in excess, and
dehydrogenase can not function.
28
At a high mold contamination, the concentration of all enzyme systems increases, owing to which the dehydrogenase activity can not be inhibited. Sorbic acid at a high mold
contamination of a product is not active.
Chemical substances can inhibit an enzyme reaction by acting on a prosthetic group
of the enzyme, by attaching themselves to coenzyme or else to the protein part of the enzyme in such a way that the bond between coenzyme and the protein component of the enzyme (apoenzyme) becomes impossible.
If a chemical substance is similar by its structure to coenzyme, it competes with coenzyme by capturing apoenzyme, as the result of which the enzyme is inactivated. This, in
particular, is one of the mechanisms of action of benzoic acid and its salts, which compete
with coenzyme for apoenzyme. The efficiency of action of benzoic acid in media with a
lower amino acid content is higher than in food products, and under certain conditions nicotinic acid interferes into inhibition by benzoate.
Both inhibition and die-off of microorganisms can depend on various reasons, on one
or several all at once. Therefore, when choosing a preservative, not only its concentration
and time of action should be taken into account, but also the possibility of a simultaneous
damage to a large number of vital mechanisms. To develop preservative formulae with an
extended range of action, one should know the causes of microbial die-off under the action
of a preservative.
As most preservatives possess a specific action with respect to various microbial species, and spoilage of food products is determined by a large number of microbial species,
the development of combined compositions of preservatives has certain advantages. The
additive action of two substances is possible owing to the fact that one substance, by acting
on the cell envelope, facilitates penetration into the cell of another substance, or one of the
preservatives decreases pH, and then the efficiency of action of the other preservative increases.
The efficiency of action of a composition made up from two or more preservatives can
be increased by adding synergists, i.e., the substances, which possess no preservative action
by themselves, but can enhance and maintain the preservative action of a preservative.
Citric, tartaric and malic acids, as well as inorganic acids, their salts etc. can serve as synergists.
The action of double and triple combinations, consisting of a preservative (sorbic,
formic, benzoic acids or para-oxybenzoic acid esters) and an antibiotic (nisin or tylosin, or
both), was studied. A preservative is used to expand the antimicrobial range.
1.4.3 Characteristics and application of chemical preservatives

All methods of increasing the resistance of food products by using chemical preservatives
have their advantages and disadvantages. First of all, taste can become worse, and the nutritive value can decrease. For instance, sulfurous acid degrades vitamin 1 to a significant
extent. Some preservatives are capable of disguising the true quality of a product, and a stale
product can be passed off as a fresh product. For instance, formic acid possesses this capability with respect to meat products. Partially for this reason, preservatives of this kind are
banned in most countries.
Benzoic acid (benzenecarboxylic acid; phenylformic acid) is present in most berries
(0.5%).
CHAPTER 1
29
COOH
Benzoic acid
Benzoic acid is a colourless crystalline substance, difficult to dissolve in water and

rather easily dissolving in ethanol. It is used as a preservative; its efficiency increases in an
acidic medium. The activity of benzoic acid against yeast fungi is higher than against molds.
Sodium benzoate (the sodium salt of benzenecarboxylic acid; the sodium salt of phenylformic acid) is an almost colourless crystalline substance.
COONa
Sodium benzoate
This salt dissolves well in water, worse in ethanol. The preservative activity is exhibited best of all in an acidic medium at pH lower than 5.0.
In studies of acute toxicity of benzoic acid and its sodium salt, LD50 for rats was 2700
mg/kg body weight; for rabbits and dogs, 2000 mg/kg body weight in peroral introduction.
In rats, prolonged feeding of food containing 0.5 and 1% of benzoic acid was found to
have no harmful effect on their growth, fertility and life expectancy. No deviations from
the norm were found in autopsy, either.
The dose causing no significant toxic effect in rats is 1% benzoic acid or sodium benzoate in food, which is equivalent to 500 mg/kg body weight per day.
Benzoic acid is used for preservation of food products usually at a concentration of up
to 0.1%; sodium benzoate, at a concentration not exceeding this amount in terms of benzoic
acid. Though the preservative action of benzoic acid is higher than that of sodium benzoate,
the latter is used more often due to its better solubility in water. The solution should have
pH lower than 4.5, then sodium benzoate is converted into free acid. Already at a 0.1% concentration, sodium benzoate is a strong preservative for many food products. It is efficient
for acidic or slightly acidified products, such as fruit juices, marinaded vegetables.
Benzoic acid and its salts found use mainly for preserving products of plant origin.
In some cases, they are used for preservation of fish products. For instance, in Italy the
use of benzoic acid and its sodium, potassium and calcium salts is permitted for processing
of semipreserved fish products, caviar etc.
Ice containing 0.1% benzoic acid is known to be used for preservation of fish and fish
fillet, and packaging of these products with ice containing 0.150.30% sodium benzoate
enables their storage fresh for several days more than in a packaging with common ice. To
avoid coagulation of fish surface layer proteins, pH of ice is maintained higher than 4.0.
Besides, benzoic acid or its salts added at a concentration of 0.3% to a 5% solution of cooking salt with pH 4.05.0, into which a fish fillet is immersed for 2 min, considerably increases its storage time. Besides, the saline solution improves the taste of fish.
In many countries, benzoic acid and its salts are used for preservation of liquid eggs
and egg yolk.
Sodium benzoate is considered to be a good preservative for oleomargarine. It does
not affect the vitamin content.
30
Information on the use of benzoic acid or its salts for preservation of meat products is
scarce. Preservation of meat salads and protective gelatin coatings for meat products by
benzoic acid is known to be used.
There are indications that a 0.06% addition of benzoic acid increases twofold the stability of fresh sausages and other meat products. For their longer storage, it is recommended
to add 4 g of a preservative mixture per 1 kg of sausage: 8.5 parts of benzoic acid, 8.5 parts
of sodium benzoate, 8.3 parts of cooking salt. This method significantly inhibits the growth
of all bacterial species.
In Russia, of products having a relation to meat industry, benzoic acid is allowed for
preservation of food gelatin at a concentration of 0.07%.
Methyl, ethyl and propyl esters of p-oxybenzoic acid possess an ability to exhibit a preservative action in a neutral medium.
COOR
OH
p -Oxybenzoic acid ester
In the formula, R is CH3, C2H5 or C3H7.

These esters are colourless crystalline substances with almost no smell. All of them
are hard to dissolve in water and are easily soluble in ethanol.
In acute experiments on mice, LD50 for methyl and propyl esters of p-oxybenzoic acid
was more than 8000, and for their sodium salts 2000 mg/kg of body weight. In similar experiments for the sodium salt of ethyl ester of the same acid, LD50 was about 2500 mg/kg
body weight.
In chronic experiments (96 weeks), methyl ester of p-oxybenzoic acid was introduced
to rats with food in the amount of 2 and 8%. Animals given the feed containing 2% of the
preparation did not differ from controls. In rats, which received feed containing 8% of the
preparation the weight increase went down in the initial period of the experiment, and then
levelled out. Histological studies revealed no significant changes in organs of rats. The
same results were obtained in experiments with propyl ester.
The dose causing no significant toxic effect in rats is a 2% addition of each of the three
esters to food, which is equivalent to a daily dose of 1000 mg/kg body weight.
Esters of p-oxybenzoic acid, mainly ethyl and propyl esters, and their mixtures were
earlier rather broadly used in the West as preservatives for a number of confections marzipan pastes, marmalades etc., mayonnaise, some fish semipreserves, caviar, especially crab
preserves etc. Lately, they are not used in most countries.
In some countries, for instance, Norway, esters of p-oxybenzoic acid and its sodium
salts are permitted to be used at a 0.05% concentration to increase the stability of some fish
semipreserves, special types of cheese, as well as for surface treatment of cheeses. However, before paraffin treatment of cheeses, the preservative should be removed. Preservatives are introduced into compositions containing cellulose esters intended for the surface
coating of salty meat products.
In Italy, ethyl and propyl esters of p-oxybenzoic acid are permitted to be used for preserving semipreserved fish products, caviar, mayonnaise etc. They are used instead of benzoic acid for preservation of meat salads and edible gelatin coatings for meat products.
31
CHAPTER 1
Ethyl ester of p-oxybenzoic acid at a 0.75% concentration makes it possible to store edible
blood without its organoleptic properties changed.
Sorbic acid (1,3-pentadiene-1-carboxylic acid; ,-pentadiene-a-carboxylic acid;
trans-2, trans-4-hexadiene acid) is represented by colourless needlelike crystals with moderately sharp smell:
CH 3CH
CHCH
CHCOOH
Sorbic acid
The technical requirements to edible sorbic acid abroad (in the USA) are as follows:
Melting temperature (dry sample)
Titration (dry sample)
Water content
Heavy metal content
Ash content
Transmission of light (5% methanol solution at 425 m)
133.0137.0C
99.0101.0% (w/w)
3.010.0% (w/w)
1 mg% (maximum)
0.2% (maximum)
95% (minimum) for a layer of 1 cm
Sorbic acid is soluble in cold water only slightly (0.15% at 20C), but is much more
soluble in hot water (3.8% at 100C). The salts of sorbic acid are better soluble in water.
The solubility of sodium sorbate in water is 32%, it does not essentially change depending
on temperature within the range of 060C. The solubility of potassium sorbate is more
than 50% at 20C, and calcium sorbate dissolves in the amount of 1.2% at 25C.
The solubility of sorbic acid in various solvents at 20C is shown in Table 1.3.
Table 1.3
Solvent
Glacial acetic acid
Acetone
Benzene
Carbon tetrachloride
Cyclohexane
Anhydrous ethanol
20% ethanol
Solubility,
g/100 g solvent
Solvent
11.5
9.2
2.3
1.3
0.28
12.9
0.29
Ethyl ester
Glycerol
Cottonseed oil
Anhydrous propylene glycol
25% sodium acetate
15% sodium chloride
Water
Solubility,
g/100 g solvent
5.0
0.31
0.58
5.5
2.1
0.038
0.15
Sorbic acid, having two unsaturated bonds in its structure, is a rather reactive compound. Its autooxidation leads to the formation of peroxides. It should be especially protected from the action of sunlight, otherwise the quality of the crystalline preparation
worsens, which manifests itself in a melting temperature decrease, yellowing and rancidity.
Sorbic acid is used as an antimicrobial substance. It possesses a high activity against
molds and yeast fungi and, to a smaller extent, against bacteria. Its optimal pH is 4.5. The
fungistatic activity increases in the presence of acids and cooking salt. Sorbic acid is found
in berries of mountain ash Sorbus aucuparia L.
In peroral introduction to rats, the lethal dose (LD50) of sorbic acid was 10,500 mg/kg
body weight.
Chronic experiments on rats were conducted for 1000 days on two generations of
32
animals. Rats were given feed, which contained 5% of sorbic acid. No deviations in weight
increment and fertility from control animals were observed.
A dose causing no toxic effect in rats is 5% of sorbic acid in feed, which is equivalent
to 2500 mg/kg body weight per day.
In subacute and chronic experiments on animals, sorbic acid was found not only to be
non-toxic but possessed a number of favourable biological properties.
Sorbic acid is used to inhibit the growth of yeasts and against molding of fruit and vegetable juices, marinades, brines, smoked fish, flour confections etc., as well as to prevent
damage of cheeses and margarine by mold. It is also used to impregnate packaging paper
for food products.
Sorbic acid strongly inhibits the growth of molds and yeasts on smoked fish, if
0.050.1% of this preservative is absorbed by fish tissues during their soaking in a brine,
which contains sorbic acid.
Usually, sorbic acid is used at a concentration of 0.020.2% of the weight of a product
and has no influence on its colour and taste within these limits.
In meat industry, sorbic acid did not find wide use; however, there is information that
it is used to inhibit the growth of mold on fermented sausages, for preservation of meat salads and edible gelatin coatings of meat products. A number of studies on the use of sorbic
acid for increasing the stability of meat products yielded positive results.
An aqueous 0.5% solution of sorbic acid was used to remove mold from the surface
of semi-smoked sausages. Wiping and rinsing of sausages in a solution of the acid made it
possible to increase the storage time by 59 days. The loaves wiped with the solution and
kept in it for 15 min could be stored 20 days more than those wiped with water. By adding
0.2% sorbic acid to sausage goods, their storage times can be increased by three days.
Treatment of the surface of raw pork and beef sausages, raw fish fillet, eviscerated
poultry etc. by immersion for 0.12 min into an aqueous solution of 0.15.0% sorbic acid or
its water-soluble salt and up to 0.2% antioxidant impedes microbial and oxidative spoilage.
The treatment of packaged fresh meat by sorbic acid and an antibiotic in combination
with ionizing irradiation is also efficient in inhibiting microbial spoilage.
Deceleration of microbial growth in beef at 2C, achieved by combining ionizing irradiation (105 rad), oxytetracycline (1 mg%) and sorbic acid (0.1%), is shown in Table 1.4.
Table 1.4
Treatment
Control
Irradiation
Oxytetracycline
Sorbic acid
Irradiation + oxytetracycline
Irradiation + sorbic acid
Irradiation + sorbic acid + oxytetracycline
Tenfold population growth, days

yeasts and molds
bacteria
>20
3.59.0
3
>20
4
817
1523
25.5
46
78
35
14
817
1633
However, meat treated in this way is of much lower quality, dehydration is observed,
as well as undesirable changes of colour and decreased flavour.
A promising way of increasing the storage times of eviscerated and cooled poultry carcasses in packagings is a two-stage treatment, which included acid hydration and use of sor-
CHAPTER 1
33
bic acid. Part of a carcass is treated for 2 h in an ice-cooled solution of 2-substituted sodium
phosphate. Herewith, pH < 5.5 is achieved on the surface. Then, after excess liquid leaks
off, the carcass is treated with a hot (70C) solution of sorbic acid. A mixture consisting of
70% propylene glycol, 20% water and 10% glycerine is used as a solvent. The sorbic acid
concentration of 0.11 mg per 1 cm2 of the product surface is achieved in 210 sec of drizzling. Control samples were spoiled in 5 days of storage at 7C, while test samples were
not spoiled in up to 18 days.
In some countries, it is permitted to add 0.1% sorbic acid and its sodium salts, which
are used along with sorbic acid, into animal fats (except butter), margarine, egg yolk or a
mixture of yolk and white. The solubility of the potassium salt in cold and hot water and
wateralcohol mixtures can be considerably decreased in the presence of cooking salt and
saccharose. They are active at pH 6 and lower.
Methods of commercial synthesis of sorbic acid have been developed in this country
to date. Sorbic acid possesses a high efficiency with respect to molds and yeasts.
Sulfur dioxide (SO2), sodium sulfite (Na2S03), sodium metabisulfite (Na2S2O5), sodium bisulfite (NaHSO3) are soluble in water and are used as antimicrobial substances, as well
as for preventing the browning of food products.
In acute experiments on mice at the intravenous injection, LD50 was 130 mg/kg body
weigh for sodium bisulfite and 175 mg/kg for sodium sulfite.
Chronic experiments were performed in several groups of rats, 1824 animals in each
group. The daily ration given to rats for 12 years included sodium bisulfite in the amount
of 0.0125, 0.025, 0.05, 0.1, 0.25, 0.5, 1 and 2% of the feed. No toxic phenomena were found
in rats given 0.05% sodium bisulfite for 2 years.
Addition of sulfite to the feed at concentrations of 0.1% or higher caused growth inhibition in rats, possibly as the result of the degradation of thiamine in the feed.
The dose causing no significant toxic effect in rats is 0.05% sodium bisulfite in the
feed, which is equivalent to 15 mg/kg body weight per day in terms of sulfur dioxide.
Sulfur dioxide found wide use for preservation of fruits, juices etc., but its application
for products of animal origin is very limited. In Russia, this preservative is permitted to be
added into food gelatin. The content of sulfurous acid in dry product should not exceed
0.1%.
In Norway, the content of sodium bisulfite in vacuum-packaged salt fish fillet is permitted to be up to 0.14%.
In England, sulfur dioxide is permitted to be used for preservation of raw sausages in
the amount of 45 mg% of the weight of a product. In Scotland this addition of sulfur dioxide
is permitted for chopped raw meat for the three summer months.
The treatment of sausage filling with sodium metabisulfite (in terms of 0.5 g SO2 per
kg of filling) increases its storage time at 5C 2- or 3-fold. One of the undesirable phenomena in SO2 treatment is, as was pointed out earlier, a considerable degradation of vitamin B1.
It has been proposed to treat the surface of hen and duck carcasses with metabisulfite.
Carcasses are to be immersed into a bath with a 1% metabisulfite solution at a temperature
of 6366C and be held for 1 min. Then the carcasses are dried on a dressing rail and packaged into boxes. The treated carcasses are stored 35 times longer than controls at 810C.
A method was recommended to preserve gut raw material using a 0.5% solution of
metabisulfite. The method is of particular importance for enterprises located in the thermal
belt or those that prepare guts for long-time storage and transportation. Thus, a six-month
storage of beef casings, bungs, rounds, hog and sheep casings as raw materials at a temper-
34
ature of 1524C and beef, hog and sheep casings as semifinished products at 2940C did
not lead to any deviations from the norm during the subsequent use in sausage production.
To preserve non-food raw material and condemned materials (from non-infected animals), not processed by meat-processing plants for dry animal feeds in the period of mass
livestock dressing, it is recommended to add dry sodium or potassium pyrosulfite
((Na2S2O5 or K2S2O5) in the amount of 2% of the weight of raw materials.
The same preservatives are proposed to be used for preservation of blood intended for
feeding, which was earlier preserved by potassium oxide or diluted sulfuric acid in the presence of cooking salt. Defibrinated blood preserved using 1% potassium pyrosulfite to the
weight of the blood can be stored for two months in the summer time at room temperature.
In gelatin production, sulfurous acid or hydrogen peroxide or both substances consecutively are usually used for preserving and whitening of high-quality broths intended for
producing photographic gelatin.
For preservation of glue, a number of preservatives are used, including sulfur dioxide
and sodium bisulfite.
Aliphatic acids. Fatty acids containing from 1 up to 14 carbon atoms are efficient inhibitors of molds. Propionic acid and its sodium and potassium salts prevent molding of
bread and baked products. Salts of propionic acid found use in dairy industry, in particular
in preventing molding on some types of packaged cheeses.
In meat industry, propionic acid and its salts found no use, because they deteriorate
the organoleptic properties of meat products. However, it is possible that further research
in this direction would find a possibility of using propionic acid and its salts for mold control in sausage production.
Formaldehyde, formic acid, salicilic acid, boric acid, borax, mono-, di- and trichloroacetic acids, hexamethylene tetramine (urotropin) etc. found application as food preservatives. At present, their use is banned in most countries, but in some countries hexamethylene
tetramine, formic and boric acids are still permitted to be used for preservation of caviar
and other fish products.
1.4.4 Methods for identification of preservatives
Quantitative determination of preservatives in products is made by gravimetric, titrometric,
spectrophotometric, chromatographic and other methods.
A number of methods have been proposed for determining the content of sorbic acid
in products. In most of them, the acid is isolated from a product by steam distillation. The
distillate is used for the assay directly or is used to extract sorbic acid with ether to reduce
the effect of minor impurities present in the distillate. In some cases, sorbic acid is isolated
by extraction. However, this method is not applicable for fats and products containing large
amounts of fat.
In the distillate or extract, sorbic acid can be determined titrometrically.
A simple method is the iodometric determination of sorbic acid in distillates or extracts
from margarine, dairy products etc. The error of the method is 2.25.0%.
The widespread spectrophotometric method of determining sorbic acid in products is
based on the ability of sorbic acid solutions to absorb light in the ultraviolet region of the
spectrum. The light absorption maximum of the solution at pH 5.9 corresponds to the wavelength of 256 m, and at pH 4.0, 262 m.
The spectrophotometric method of determining sorbic acid, developed for cheese, was
applied for other food products (bread, cakes, syrups, meat produces etc.).
CHAPTER 1
35
Later, a more precise spectrophotometric method was recommended.

The content of sorbic acid in margarine was determined by the light absorption in the
ultraviolet region of the spectrum at 260 m.
The basis of one of the spectrophotometric methods is the reaction of sorbic acid with
2-methyl-mercaptobenzthiazol-p-ethyl toluene sulfonate (benzthiazol), which leads to the
formation of a green product, whose light absorption is measured at a wavelength of
652 m. Other chemical preservatives benzoic, sulfurous, salicilic, formic, cinnamylic,
propionic acids and a mixture of p-oxybenzoic acid esters give no green coloration with
benzthiazol and do not prevent the determination of sorbic acid. The method is recommended for determining sorbic acid in food products (cheese, butter etc.).
The method of paper chromatography was proposed for determining the content of
preservatives in bread and baked products. Formic, propionic, benzoic, salicilic, sorbic,
p-chlorobenzoic, p-oxybenzoic acids and p-oxybenzoic acid esters were identified.
For separation of p-oxybenzoic acid and some of its esters, methods of paper chromatography were also described, but they are lengthy and are inferior to thin-layer-chromatography methods in this respect.
The method of thin-layer chromatography was successfully used to separate p-oxybenzoic acid and its methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, heptyl, octyl,
nonyl, dodecyl, phenyl and benzyl esters. A mixture of 10% acetylcellulose and polyamide
(1:1, w/w) was used as the stationary phase; a two-component system consisting of a
hydrocarbon solvent and glacial acetic acid (50:10, v/v), as a mobile phase.
The separation of methyl and propyl esters of p-oxybenzoic acid was achieved on a
thin layer of silica gel using a mobile phase from a mixture of pentane and glacial acetic
acid.
A major part of the methods of determining sulfurous acid is based on its capability of
being readily oxidized. There are volumetric and gravimetric method of determining sulfurous acid.
A comparatively exact and fast assay is the iodometric method of determining sulfur
dioxide using formalin, which binds sulfurous acid.
1.4.5 Fat antioxidants
Under the action of oxygen of the air, fats undergo oxidative processes, which even at the
early stages are accompanied by a decrease of nutritive value and subsequently lead to
spoilage (unpleasant odour and taste, sometimes change of colour and consistency of fat).
The modern views on the mechanism of oxidative reactions of organic substances are
based on the BachEngler peroxide theory and the theory of degenerate branched chain reactions by N.N. Semenov.
In accordance with the peroxide theory, the first product of oxidation of most organic
and many inorganic substances are peroxides. When peroxide is formed, two atoms of the
oxygen molecule still remain bound to each other. Therefore, in the oxygen molecule there
is no complete rupture of bonds between atoms, which would require a large consumption
of energy (117 kcal/mol). Thus, oxidation of organic substances via peroxide formation
proceeds comparatively easily.
Peroxides were found even in freshly produced fats, because their oxidation begins already at the technological processing: in preparation of raw fat for rendering, during the rendering and in subsequent operations. Formation and accumulation of peroxides is greatly
affected by the method of rat production. Comparison of the results of peroxide numbers
36
determination for pork rendered fats, obtained by various investigators, shows that the peroxide numbers of a fat rendered in an open heater are 0.0130.035, and for that rendered
on a centrifugal machine, 0.0000.025.
The chemical composition of initial raw material and the changes that occurred in technological processing determine subsequently the rate of spoilage of fats in storage. The
spoilage rate of a fat present in food products also depends to a great extent on these factors.
Many investigators, in particular, by the example of oxidation of fatty acid esters, have
convincingly shown that at least at the first stages of oxidation all peroxide products formed
are hydroperoxides
R1
CH
CH
CH
R2
OOH
In the formation of hydroperoxide, oxygen attacks the CH bond at the -position to

the double CC bond, which possesses an increased reactivity in oxidation processes. Abstraction of the -methylene atom H from the compound containing double bonds between
carbon atoms leads to the formation of active free radical CHCH=CH, which requires
an energy consumption of about 80 kcal/mol. This energy is required in the onset of the reaction for breaking the CH bonds. The further development of the reaction by the chain
mechanism requires a very small amount of energy or no energy at all.
It has been proven experimentally that with the abstraction of the hydrogen atom the
double bond is not broken, but that this phenomenon is accompanied by the displacement
of double bonds in fatty acid molecules. Herewith, coupled double bonds
C
appear in the molecules of polyunsaturated fatty acids (containing two or more double
bonds), which initially contained only isolated double bonds.
The possibility of the presence of cyclic peroxides
R1
CH
CH
R2
in oxidation products has not been proven to date by direct methods. While hydroperoxides
were isolated and studied, cyclic peroxides were not, possibly because of their extreme instability or because they do not exist. In most cases, the proof of the emergence of cyclic
peroxides at the advanced stages of oxidation is based on the determination of the general
content of peroxide compounds by the iodometric method and the determination of only
hydroperoxides by the polarographic method. However, the quantitative differences obtained are within the limits of error of the determination methods.
Hydroperoxides are comparatively unstable compounds easily undergoing various
conversions, which lead to the rupture of the OO bond and the formation of free radicals.
The bond rupture energy in peroxides is considerably lower than in the oxygen molecule
and makes 3040 kcal/mol. As the result of dissociation or other conversions of peroxides,
the system forms more stable oxidation products as compared with peroxides the so called
secondary oxidation products aldehydes, ketones, low-molecular-mass acids etc. While
hydroperoxides have no smell or taste, many of the secondary oxidation products of relatively low molecular masses are involved in the formation of a specific smell and taste of
spoiled fats.
The quantum yields determined in photochemical oxidation prove to be much larger
CHAPTER 1
37
than unity (according to Einsteins law of photochemical equivalence, one quantum of light
induces only one chemical reaction), which is a direct proof of the chain nature of the oxidation reactions.
Other proofs of the chain mechanism of the oxidation processes can be the phenomena
of initiation (excitation) and retardation (inhibition) of the oxidation reactions. In the former
case, oxidation is accelerated in the presence of substances capable of decomposition into
free radicals; in the latter, of being inhibited by addition of minor amounts of substances
capable of interrupting the chain reaction of oxidation by capturing free radicals that lead
the oxidation chain. Oxidation of fats proceeds via formation of free radicals and pertains
to the class of slowly evolving chain branched reactions.
Free radicals are highly active particles. Reactions between free radicals and between
free radicals and molecules proceed easily; new free radicals are formed in the process to
continue the chain reaction.
It is well known that the smaller the activation energy E, the easier the reaction between two reacting chemical compounds is. If two molecular compounds participate in the
reaction, the magnitude of the activation energy is usually several tens of kilocalories per
mole. In the case of the reaction of free radical with a molecule, the magnitude of the activation energy is not large or equals zero, i.e., E is within the range of 010 kcal/mol.
Besides the reaction product (in this case, hydroperoxide), a new free radical (R) is
formed in the chain reaction mechanism. This radical again enters into the reaction and continues the initiated chain of chemical conversions. Herewith, more new molecules of the
initial substance are involved into the oxidation reaction. Thus, the development of the oxidation chain occurs and the involvement of new molecules of the fatty acid or triglyceride.
The chain of oxidative conversions develops until the chain-leading free radicals R
and RO2 disappear from the system, i.e., as the result of recombination of two radicals. An
inactive compound is formed, and the chain terminates. The sooner this happens, the less
fatty-acid or triglyceride molecules get oxidized.
Occasionally, the molecular product of the chain reaction in the system where the oxidation process occurs hydroperoxide breaks down to form new free radicals, i.e., the
chain branches, as each newly formed free radical initiates a new oxidation chain.
The slow development of the oxidation reactions is due to the fact that the branchings
of the chain in these reactions are as if retarded and occur only at times when hydroperoxides break down to free radicals. These retarded branchings are called degenerate
branchings.
Below, we present a generally accepted scheme of a degenerate branched chain
reaction:
RH + O2
R + HO 2
R +O
RO 2
RO 2 + RH
RO2H + R
RO2H
RO + OH
RO 2 + RO2
R +R
RO 2 + R
Chain initiation (formation of free radical R)

Chain continuation
Degenerate chain branching
Chain termination
Here RH is the molecule of an oxidizing substance, e.g., a fatty acid; RO2H is the
hydroperoxide molecule; R and RO2 are free radicals leading the oxidation chain; RO and
OH are free radicals formed in the breakdown of the hydroperoxide.
Peroxide numbers, % iodine
38
0.5
0.4
0.3
0.2
0.1
0
0
10
Time, h
15
20
25
Figure 1.2 A kinetic curve of peroxide accumulation in oxidation of pork rendered suet. Oxidation
temperature, 90C.
The slow development of fat oxidation in the initial stage is due to the delay of chain
branching. This stage of oxidation is known under the name of the induction period or
initiation period.
However, at later stages of oxidation, when a large amount of free radicals accumulate
in the system, the oxidation process is sharply speeded up. The typical autocatalytic character of the kinetic curves for oxidation of fats and related substances is clearly seen by the
example of the oxidation of pork rendered fat.
The ability of hydroperoxides to break down to form free radicals, as well as the dependence of the oxidation rate on the extent of oxidation in the cases when hydroperoxides
are basically the only reaction products, indicates that degenerate branching in liquid-phase
oxidation reactions is due to the breakdown of hydroperoxides in the reaction
ROOH
RO + OH or 2ROOH
RO 2 + RO + H 2O .
Below, we will show that oxidation of both melted and solid animal fat proceeds according to the same kinetic law.
The rate of fat autooxidation is commonly characterized, not only in research but also
in practice, by the length of induction period, i.e., the length of time during which no pronounced changes in them are observed. This period serves as a preparation to fast oxidation.
In the beginning of the induction period, there is no sign of any oxidation products accessible to chemical determination, then peroxides start to be found, and at their sufficient
amount, due to the autocatalytic character of the process, oxidation begins to develop at a
very high rate, the induction period ends. Upon completion of the induction period, the peroxide accumulation curve sharply rises (see Fig. 1.2).
It should be pointed out that, in an ideal representation, the induction period should be
understood to be only that part of the segment of the curve in which peroxides are not found
by common chemical (or physicochemical) methods. In practice, in modern production processes, it is difficult to obtain fat not containing peroxides found analytically. In the main,
freshly produced fats always contain peroxides in minor amounts. Therefore, for practical
purposes a more suitable definition of induction period is that, which is given initially. It is
all the more correct as the notion of induction period is conventional, because oxidative
changes not registered by chemical methods are observed in fats in the cases when the presence of peroxides is not yet possible to detect by common analytical methods. It is known
CHAPTER 1
0.5
0.4
39
0.3
0.2
0.1
8
10
Time, h
12
14
Figure 1.3 Kinetic curves of accumulation of fat samples taken at different stages of the technological process (oxidation temperature, 100C): 1, after rendering; 2, from the collector; 3, from a
container.
that hydroperoxides at a concentration of 10 6 mol/l can not be found by common chemical

methods.
At the same time, the kinetic methods make it possible to register changes in fat at very
early stages of oxidation. Studies of fat samples taken from the same commercial batch at
different stages of the technological process and containing no peroxides determinable by
the iodometric method (peroxides were found in none of the samples) showed that the stability of fat to oxidation as determined by the kinetic method (Fig. 1.3) was different.
Secondary oxidation products include comparatively stable intermediate and end
products of oxidation alcohols, carbonyl compounds, esters, acids, as well as compounds
with mixed functions, such as oxy acids, epoxy compounds etc.
It could be said that all secondary products of oxidation emerge as the result of conversions of hydroperoxides; what is more, part of the secondary products are formed immediately at the breakdown of hydroperoxides and the other part, as the result of further
reactions.
The primary character of hydroperoxides as the first molecular products of oxidation
and the secondary character of carbonyl compounds, alcohols, epoxy compounds and acids
is graphically illustrated by curves plotted based on the literature data on the oxidation of
methyl oleate under the action of ultraviolet light at 35C (Fig. 1.4).
The mechanism of formation of secondary oxidation products has been little studied.
Only with a small fraction of probability, it could be suggested that ketones are formed from
hydroperoxides:
R1 CH R 2 + R
R1 C
R2 + RH
OOH
R1
C
OOH
OOH
R2
R1
R2 + OH ,
where R is either radical OH or any of the radicals leading the main chain of oxidation.
It is probable that alcohols are formed from hydroperoxides in degenerate branching
of chains
nmol O2 / 100 g nonvolatile

oxidized substrate
40
50
2
4
5
0
100
Time, h
200
Figure 1.4 Kinetic curves of oxidation of methyl oleate at the action of ultraviolet light: 1, peroxide
oxygen; 2, carbonyl oxygen; 3, hydroxyl oxygen; 4, oxirane oxygen; 5, carboxyl oxygen.
ROOH
RO + OH
RO + RH
ROH + R
One of the possible routes of forming epoxy compounds is the intramolecular reaction
of the hydroperoxide of the unsaturated compound
R1
CH
CH
CH
R2
R1
OOH
CH
CH
OH
CH
R2
According to one of the most probable points of view, acids can be formed from ketones by their oxidation to -ketohydroperoxide, which subsequently breaks down to form
aldehyde and acid
H
R1
C
O
CH2
R2
R1
CH
OOH
R2
R1C
O
OH + R2
C
O
It has been proven experimentally that acids are not formed directly from hydroperoxides and emerge as the result of the further conversion of secondary oxidation products,
most probably, ketones. As seen from the above reaction, formation of acids proceeds with
the rupture of the carbon skeleton of the molecule. Studies of the composition of the acids
formed in oxidation of fatty acids and hydrocarbons confirm this, because in practice only
acids with a shorter carbon chain than in the initial compound could be isolated from the
oxidizing mixture.
The described mechanisms of formation of secondary oxidation products are basically
hypothetical and were proposed mainly based on the studies of hydrocarbons of the olefin
and paraffin series. However, they can be accepted with an equal degree of probability for
oxidation of fatty acids.
This can be done based on that in such acids being part of fats as, e.g., oleic, linolic or
linolenic acids, oxidation at the initial stages affects carbon atoms removed from the ester
group by a chain of at least six methylene groups. Therefore, the ester group can have no
influence on the oxidation process, and oxidation proceeds the way it does in the respective
unsaturated hydrocarbon.
CHAPTER 1
41
mol O2 / mol ester
1.0
0.8
0.6
0.4
0.2
1
100
50
Time, h
Figure 1.5 Dependence of the rate of oxidation of fatty acids in the air at a temperature of 37C on
the number of double bonds in them: 1, ethyl oleate; 2, ethyl linoleate; 3, ethyl linolenate; 4, methyl
arachidonate.
mol O2 / mol ester
1.0
0.8
0.6
0.4
0.2
1
100
50
Time, h
Figure 1.6 Kinetic curves of oxidation of pork suet at different temperatures: 1, 90C; 2, 100C; 3,
110C; 4, 120C.
Products of oxidation of fats and oils, as well as fatty acids and their derivatives are
found to have oxidation products belonging to the same groups of organic compounds,
which were found in hydrocarbons of the olefin and paraffin series, i.e., alcohols, carbonyl
compounds, epoxy compounds, acids etc.
For instance, carboxyl compounds of oxidized fats identified by chromatographic,
spectrophotometric and other methods include n-hexanal, 2,4-decadienal, propionic aldehyde, 2-hexanon, 2-octanon, 2-nonanon, 2-decanon, n-pentenal, acetaldehyde etc.
The reactivity of fatty acids increases with the increase of the number of double bonds
in the molecule. Figure 1.5 shows a dependence of the oxidation rate of unsaturated fatty
acid esters on the number of double bonds.
Formation of free radicals in the system is facilitated with the temperature increase.
Herewith, the chain initiating rate and, therefore, the oxidation rate, increases. Kinetic
curves of pork fat oxidation illustrating this are presented in Fig. 1.6.
If chain initiation occurs mainly according to the reaction RH + O2, then the rate of
42
mol O2 / mol ester
1.0
0.8
0.6
0.4
0.2
1
100
50
Time, h
Figure 1.7 Effect of oxygen pressure on the rate of oxidation of ethyl linoleate at 45C.
initiation should depend on oxygen pressure. The occurrence of this dependence at small
conversion rates has been established in oxidation of ethyl linoleate. From Fig. 1.7, it follows that the rate of ethyl linoleate oxidation on oxygen pressure becomes pronounced at a
pressure less than 200 mm Hg. However, it should be noted that the pressure range in which
a pronounced dependence of the oxidation rate on oxygen partial pressure is still pronounced can change within broad limits in transition from one compound to another.
Processes of oxidative spoilage of fats, as well as other chain reactions, are also affected by light and ionizing radiation, which contribute to the emergence of free radicals in the
system.
The action of light of certain wavelengths and especially UV light on fats increases
the rate of emergence of free radicals, which leads to a fast oxidative spoilage of fats.
In the use of ionizing radiations to increase the stability of meat and meat or other food
products in storage, the most serious negative consequence of irradiation is oxidation of
fats. The emergence of free radicals in the presence of oxygen leads to the formation of peroxide radicals RO2 and, therefore, peroxides and products of their conversion.
Variable valence metals iron, copper and others, which get into fats from the equipment in their processing, are efficient catalysts of oxidation processes.
The catalytic acceleration of the oxidation reactions by these metals is based on that,
depending on the valent state, they can either attach an electron or donate it to any valent
saturated particle, which leads to the activation of radical breakdown of hydroperoxides according to the following mechanism:
ROOH + Fe2+
Fe3+ + RO + OH
ROOH + Fe3+
Fe2+ + ROO + OH+
Iron is not consumed in this process and, therefore, being present as traces, it contributes to the emergence of radicals RO and RO2, which initiate the chain process of oxidation. By the example of metal-catalyzed oxidation of methyl linoleate, it has been shown
that metals accelerate the oxidation process only in the presence of the peroxides of oxidized material or of specially added peroxides.
From literature data, it follows that lead has the largest catalytic efficiency, which is
followed by copper, iron, tin, zinc and, finally stainless steel.
Traces of metals contribute to spoilage of animal fats, which is called tallowiness. In
practice, tallowiness is observed, e.g., in excessive intensive mechanical treatment of fats,
CHAPTER 1
43
owing to a lengthy contact with metal apparatuses or long-time storage of fat in a metal container. Tallowiness occurs without a significant accumulation of peroxides. The main oxidation products in this case are oxy acids and, possibly, polymerization products.
The catalytic activity of variable-valence metals increases considerably if they enter
into the reaction with some specific organic compounds, especially proteins.
Meat and blood pigments myoglobin and hemoglobin, as well as their derivatives are
strong catalysts of oxidation of lipids of meat, meat products, fatback.
This, in particular, is confirmed by the acceleration of linoleate oxidation in the presence of extracts of hog muscle tissue. Coagulation of proteins considerably decreases the
catalytic activity of meat pigments. Hemoglobins of different animals differ insignificantly
by their catalytic action on the process of linoleate oxidation.
A decrease of temperature contributes only moderately to the decrease of the rate of
oxidation catalyzed by meat and blood pigments.
Fresh meat pigments, as well as their derivatives are nonspecific catalysts, e.g., hematin also contributes well to oxidation of hydrocarbons and also fatty acids.
Though fat oxidation catalyzed by heme compounds has been known since long, the
mechanism and chemistry of this process have not been made clear until now, possibly owing to the exceptional complexity of this phenomenon.
There is no doubt that both forms of iron (Fe2+ and Fe3+), which are components of
heme compounds, initiate the breakdown of hydroperoxides and, thus, accelerate oxidation
of fat. But there is also no convincing proof that the Fe3+-containing pigment is capable of
accelerating oxidation of lipids in the absence of hydroperoxides, though, according to the
literature data, this is believed to be possible.
The presence of oxidation products in fats is revealed, as well as the extent of the oxidation process is assessed by using chemical, spectrophotometric, chromatographic, polarographic etc. methods.
Methods of determining compounds of peroxide character have become widespread.
Especially frequently, the iodometric method of determining peroxides is used. The
ironrhodanide, indophenol, ironchlorideindophenol, polarographic, stannochloride
etc. methods are used more rarely.
The content of peroxides in edible fats and oils, as well as in food products is expressed
in different way. In the Russian Federation, it is accepted to express the content of peroxides
in percent iodine; in the UK, in millilitres of a 0.002 N solution of thiosulfate per gram of
fat (Lee number). In the USA, the peroxide content is expressed predominantly in milliequivalents or millomoles of active oxygen of peroxides per 1000 g of fat.
There is a certain dependence between the magnitude of the peroxide number and the
organoleptic rating of the quality of fats and fat-containing products, because peroxides in
them accumulate in parallel with the emergence and development of rancid smell and taste.
In fatty tissue separated from a freshly killed animal, it is impossible to find fatty peroxides, because they are not a normal metabolic product in the animal organism. However,
fatty peroxides can be formed in the organism of the alive animal in pathological cases, e.g.,
under the action of ionizing radiation.
As we pointed out, peroxides emerge in fat during the technological treatment and storage. Delays of the raw materials before rendering, high temperature, the presence of atmospheric oxygen, the contact with metal equipment, long-time treatment, effect of light,
incorrect condition of storing the final product all these contribute to the emergence and
further accumulation of peroxides in fat.
The relation between the organoleptic evaluation of the extent of fat spoilage and the
44
content of peroxide compounds in it has been discussed in the literature over a period of
many years. Investigators proposed various values of peroxide numbers, which, in their
opinion, corresponds to organoleptically established spoilage.
The values of peroxide numbers characterizing the extent of oxidative spoilage of animal rendered fats are in most cases inapplicable for assessment of the extent of oxidative
spoilage of other types of fats and oils, as well as fat-containing products. While the peroxide number of 0.1 in percent iodine, as a rule, indicates that the spoilage of pork, beef, mutton and bone rendered fats did occur, the same magnitude of the peroxide number for
fatback, vegetable oils and many fat-containing products, including meat products, will be
organoleptically assessed as good-quality foodstuffs.
Methods of determining carbonyl compounds in autooxidizing fats are of great importance, as, on the one hand, the presence of these compounds indicates the extent of oxidation
and, on the other hand, testifies the development of rancid taste determined organoleptically. It is commonly accepted that aldehydes and ketones, together with low-molecular-mass
acids, are a cause of rancid smell and taste. Heptyl, nonyl, hexyl and butyl aldehydes have
long been referred to as substances, which determine rancid smell and taste of fats.
An unpleasant smell of meat and meat products formed under the action of ionizing
radiations depends to a significant extent on the presence of carbonyl compounds.
Carbonyl compounds in oxidized fats and those that are components of meat, meat
products and other food products are determined by methods based on the conversion of
carbonyl compounds to their bisulfite, hydroxylamine, diphenylcarbazide, 2,4-dinitrophenylhydrazine and other derivatives. The methods using 2,4-dinitrophenylhydrazine are the
most widespread. The formed 2,4-dinitrophenylhydrazones of monocarbonyl compounds
and corresponding osazones of dicarbonyl compounds are converted, by addition of alkali,
into intensively stained quinoid compounds, whose light absorption is measured. Separation of the mixtures of carbonyl compounds into classes or individual compounds is done
by methods of column, thin-layer, paper and gas chromatography.
The reaction with 2-thiobarbituric acid is used in determining such a product of oxidative spoilage of fats as malonic dialdehyde.
The content of ,-dicarbonyl compounds, which are characterized by stability in
heat treatment of fats, is determined by treating the fat under study by alkali during the heating. Then the fluorescence or light absorption of the solution is measured.
Epoxy compounds, which were found to emerge in pork fat only in utmost stages of
oxidation, are determined using methods of splitting the oxirane ring with anhydrous hydrogen chloride in absolute ether or with hydrogen bromide in glacial acetic acid followed
by titration with excess hydrogen chloride or bromide. A method of determination by trimethylamine hydrochloride was also described.
More detailed information on the methods of quantitative determination and identification of products of oxidative spoilage of fats can be found in a number of literature sources, which contain references to original papers.
1.4.6 Effect of oxidation on the food value of fats
In long-time storage of fats their quality deteriorates, which leads to a decline of category
quality (in some cases, edible fats are transferred into the technical-grade category) and related material damage. The terms of refrigerator storage of frozen meat depend primarily
on oxidation of fats. Fat oxidation often affects the quality of long-stored smoked sausages,
fatback, as well as fat-containing dried meat and concentrated feeds.
45
CHAPTER 1
However, considerably earlier, long before oxidation can be detected organoleptically,

the food value of fats begins to decrease. As the action of oxygen of the air affects easiest
of all the unsaturated components of fats, the first to get oxidized are polyunsaturated fatty
acids vital for the human and animal organism. Essential polyunsaturated acids are linolic,
linolenic and arachidonic acids. All these natural acids have a cis-configuration. All of them
have a strong biological action, owing to which they are united under the name of vitamin F.
Of polyunsaturated acids, arachidonic acid has the largest biological activity. It occurs
only in lipids of animal origin. Linolic and linolenic acids are synthesized by plants. In the
animal organism, they are capable of converting into arachidonic acid.
Linolic and linolenic acids are contained in large amounts in vegetable oils. Of animal
fats, considerable amounts of linolic acid occur in pork fat.
The data on the content of polyunsaturated fatty acids in fats of slaughter cattle are given in Table 1.5.
Table 1.5
Product
Rendered pork fat

Pork fatback
Fat of salted cooked ham
Rendered beef fat
Rendered mutton fat
Bone fat
Rendered camel fat
Rendered horse fat
Content of acid, %
linolic
linolenic
arachidonic
Number of
samples
studied
9.940.72
11.221.24
10.002.35
2.810.50
3.090.61
4.130.96
4.320.14
11.771.74
0.570.15
0.660.22
0.620.26
0.630.18
0.920.14
0.910.15
1.480.10
5.381.91
0.620.16
0.630.35
0.670.25
0.110.03
0.100.03
0.140.01
0.390.02
0.260.01
11
38
15
7
4
4
4
4
The absence of polyunsaturated fatty acids in the food of rats was found to lead to dermatites, loss of weight, interruption of growth, loss of hair; affection of kidneys, mammary
glands and other organs. At a prolonged insufficiency of vitamin F, animals die. A timely
delivery of polyunsaturated fatty acids into the organism protects animals from death.
As we have already pointed out, autooxidation of fats leads to the formation of hydroperoxides and a related displacement of double bonds. Unsaturated fatty acids with conjugated double bonds, e.g., 9,11-octadiene acid, possess no biological activity.
Along with a decrease in the amount of polyunsaturated fatty acids in autooxidized
fats, the content of fat-soluble vitamins A and E decreases. In coloured animal fats, provitamin A carotene breaks down. If oxidation affects the fat being in contact with meat
and blood pigments (myoglobin, hemoglobin) or their derivatives, then the B-complex vitamins thiamin, riboflavin, pyridoxine, biotin etc. also break down.
The food value of fats decreases not only in long-time storage, but also in heat treatment. Profound chemical changes have been established to occur in heat treatment of fats:
formation and breakdown of peroxides, formation of compounds with conjugated double
bonds, increase in the content of free fatty acids, decrease of iodine numbers, increase of
viscosity, formation of epoxy compounds etc.
Many investigators have proven the harmful effect of oxidized fats on the animal organism. This issue is dealt with in numerous reviews. Intensive research is under way in
this field. For instance, it has been found that feeding chickens small amounts of oxidized
animal fat leads to the retardation of growth and sexual development. Substances isolated
46
from the unsaponifiable fraction of oxidized beef fat were found to cause chicken diseases
(ascites, hydropericardium, oedema) at their amounts of 10 5 106% in food.
Some authors postulated a relationship between the activity of various enzymes and
their sulfhydryl groups. In living organisms, these groups are associated with the functions
of muscle contraction, nerve activity etc. Inhibition of sulfhydryl groups of enzymes by lipid peroxides has also been postulated.
It has been experimentally found that SH groups of cysteine, glutathione and also papain get totally oxidized in the presence of linolic acid peroxides.
It is believed that the harmful effect of oxidized fats on the organism is determined
mainly either by their direct toxic effect or by the degradation of vital components of food
they cause due to oxidation. There is no common point of view on this issue yet, and it is
still debated in the literature.
The toxicity of hydroperoxides isolated in pure form was established by direct experiments. Besides, it is known that inclusion of more than 1% rancid fat into the ration of piglets leads to the development of symptoms of vitamin E insufficiency. Inclusion of oxidized
(at 180C) soybean oil into the ration has the same effect as insufficiency of vitamin E, and
leads to the decrease of the content of polyunsaturated fatty acids in organs and tissues of
animals, which stipulates the vitamin E insufficiency.
Thus, there is no doubt as to the harmfulness of oxidized fats both as the consequence
of the loss of food value and of the accumulation of oxidation products which inflict harm
to the human and animal organism.
1.4.7 Inhibition of autooxidation processes
The oxidation reaction, as any chain reaction, can be inhibited by adding inhibitors, in this
case oxidation inhibitors, or antioxidants.
Antioxidants inhibit the chain process of oxidation by entering into reaction with free
radicals RO2 or R and, thus, break the oxidation chains.
Schematically, the mechanism of action of antioxidants can be presented as follows:
InH + RO 2
RO2H + In ,
where InH is antioxidant; RO2 is free hydroperoxide radical; RO2H is hydroperoxide of,
e.g., a fatty acid, In is free radical of the antioxidant.
As a consequence of the principle of the indestructibility of free valence, a new free
radical emerges from the antioxidant, but this radical possesses a very small activity and is
not capable of participating in chain continuation. The reaction is broken, and oxidation is
inhibited. The free radical enters into the recombination reaction with other low-active free
radicals to form a stable product, In + In In In.
Herewith, one molecule of antioxidant is consumed for each chain-breaking act, and,
therefore, its concentration constantly decreases in the process of oxidation. After all inhibitor is consumed, the chain process is resumed and will develop at almost the same rate as
before the inhibitor was introduced.
Figure 1.8 presents kinetic curves characterizing the accumulation of peroxides in pork
fat with an antioxidant and the decomposition of the antioxidant as the result of oxidation.
Another reaction of the death of low-active free radical In is possible in the case of its
emergence from substances of phenolic nature. If the concentration of free radicals RO2 or
R is large, they can interact with low-active free radicals of the inhibitor
0.30
0.25
25
0.20
20
0.15
15
0.10
10
2
0.05
5
0
8 10 12
Time, h
14
16
47
Content of antioxidant, mg %
CHAPTER 1
18
Figure 1.8 Kinetic curves, which characterize accumulation of peroxides in pork fat with an antioxidant and its breakdown as the result of oxidation at 110C: 1, peroxide numbers; 2, content of
butyloxytolyene.
In + RO 2
InRO2
or
In + R
InR.
From the chain theory of inhibition of oxidation processes it is seen that inhibitors
should be introduced at an earlier stage of the technological process of fat production, when
free radicals in the system are not many. Some antioxidants are capable of inhibiting the
process at sufficiently advanced stages of oxidation, but they are quickly consumed, so their
action is short.
By the example of inhibiting pork fat at the stage of rather well advanced oxidation,
the possibility of inhibiting the oxidation reaction was shown, but if the antioxidant were
introduced into fat at an earlier stage of oxidation, its efficiency would have been several
times larger. This is illustrated by the kinetic curves of Fig. 1.9.
The chain reaction of oxidation could be inhibited not only by increasing the breakdown of chains, as it takes places in the case of phenolic and some other antioxidants
(quinones, amines), but also by decreasing the rate of free radical formation by the degenerate branching reaction. Introduction of substances (e.g., some thio compounds), which interact with hydroperoxides without forming free radicals, into the oxidizing system also
makes it possible to reduce the oxidation reaction rate.
Sulfurous compounds are much less active in inhibiting the oxidation processes than,
e.g., antioxidants of the type of alkylphenols, even if they are introduced in considerable
amounts. However, being added into the oxidizing system together with an antioxidant of
phenolic nature, they enhance the efficiency of its action significantly. Herewith, the length
of the induction period proves larger than the sum of the induction periods stipulated by
each substance separately.
This non-additive antioxidative action of a combined addition of two (or more) substances was called synergism.
In processes of inhibited oxidation, synergists are commonly substances, which by
themselves either possess no antioxidative action at all, or are weak antioxidants but enhance the efficiency of action of other inhibitors.
48
0.16
1
4
0.12
0.08
0.04
6
Time, h
10
12
Figure 1.9 Kinetic curves of oxidation of pork fat at 100C in the presence of 0.01% butyloxyanisol
introduced into fat at various stages of oxidation: 1, initial, oxidized up to the peroxide number; 2,
0.008; 3, 0.026; 4, 0.045.
Synergists include thio compounds, phosphatides, some organic and inorganic acids,
amino acids, polyphosphates etc.
The listed groups of substances are so diverse from the chemical point of view that one
can not assume the existence of a synergic-action mechanism common for them.
One thing is considered to be undoubted, though, that in the case of a synergism each
of two components is involved in the oxidation inhibition process in a different way.
For some synergists, a credible view of the mechanism of their action is as of hydrogen
donors, which leads to the restoration of the initial form of the antioxidants. For instance,
the reversible conversion of quinones to hydroquinones creates a possibility, when the same
molecule of the inhibitor breaks several chains. This mechanism of the process is what explains a sharp increase of the efficiency of action of the inhibitor.
The synergic action of some amino acids is stipulated by their ability to reduce oxidized phenolic antioxidants.
Ascorbic acid and its fatty-acid ethers are readily oxidized and reduced
OH OH
C
2H
+2H
Due to their ability to donate hydrogen atoms, these compounds can regenerate oxidized phenolic antioxidants. Simultaneously, ascorbic acid is a metal deactivator, forming
neutral monometal salts at the expense of one of the enol atoms of hydrogen.
Metal deactivators are substances, which inhibit the catalytic activity of metals. Deactivators are used in the cases when the oxidizing system in the process of oxidation is in
contact with the metal surface and, corroding it, forms salt catalysts from variable-valence
metals.
A strong metal deactivator is citric acid, which forms complex compounds with metal
ions. These compounds are capable of binding iron traces occurring in fats and take them
out of the reaction. Polyoxycompounds sorbitol, sugars and their derivatives also possess an ability to bind metals.
CHAPTER 1
49
Owing to the synergism between oxidation inhibitors, there is a possibility of increasing the antioxidative efficiency of a number of substances and, besides, decreasing their
concentration in the oxidizing system. The use of additives, which deactivate traces of
variable-valence metals in many cases getting into a product in the process of production,
enhances the inhibition of the oxidation process even more.
Thus, studies of the mechanism and chemistry of the oxidation processes and their inhibition enabled practical applications of particular antioxidants and efficient antioxidative
compositions for increasing the storage times of fats, and in some cases, of fat-containing
products.
1.4.8 Characteristics and application of antioxidants and synergists
At present, a large amount of substances possessing the properties of oxidation inhibitors
are used in practice.
Storage times of edible fats and technical fats, as well as fat-containing food products
are extended using individual antioxidants, mixtures of antioxidants, as well as compositions of one or several antioxidants with various synergists and metal deactivators.
A commercial product butyloxyanisol (BOA) consists of a mixture of two isomers:
2- and 3-tert-butyl-4-oxyanisols (3- and 2-tert-butyl-4-methoxyphenols).
OCH3 CH
3
C
OCH3
CH3
CH3
CH3
OH
2-tert-butyl-4-oxyanisol
OH
CH3
CH3
3-tert-butyl-4-oxyaniso
The ratio of the isomers depends on the manufacturing method of BOA. The 3-isomer
possesses a slightly larger antioxidative efficiency than the 2-isomer. Both isomers exhibit
some synergism, so that the mixtures containing a large amount of isomer are close to pure
3-tert-butyl-4-oxyanisol by their efficiency. In commercial mixtures, the content of 3-isomer is no less than 85%. The antioxidative efficiency of butyloxyanisol increases up to a
concentration of 0.02% in the substrate.
Butyloxyanisol is represented by waxlike crystals of cream or rose-cream colour,
which possess a phenolic smell. The melting temperature of the mixture of isomers is
4855C. Each isomer melts at a temperature of about 65C.
Butyloxyanisol does not change the colour of food products and at small concentrations has no effect on their taste and flavour. It is rather stable to the action of high temperatures and can be added into products subjected to searing, boiling and baking. It is also
capable of inhibiting oxidation of not only pure fats, but also fats added into products. The
solubility of butyloxyanisol at 25C is as follows (in percent): in water, 0; ethyl alcohol, 25;
pork rendered fat, 50; propylene glycol, 50; cotton oil, 30; peanut oil, 40.
At a concentration of 0.010.02%, butyloxyanisol was proved by several investigators
to protect pork rendered fat from oxidation well (Fig. 1.10).
Butyloxyanisol is widely used alone or in combination with other antioxidants
nordihydroguaiaretic acid, propyl gallate, butyloxytolyene, tocopherol to inhibit oxidative processes in animal fats and fat-containing products. The efficiency of action of the
50
0.20
1
0.16
0.12
0.08
0.04
0
0
Figure 1.10
oxyanisol.
4
6
Time, h
Kinetic curves of oxidation of pork fat at 100C: 1, no antioxidant; 2, with 0.01% butyl-
antioxidant is enhanced by adding such synergists as citric acid, triethylphosphate,

methionine, lecitin and thiodipropionic acid.
An idea of the synergistic effect of a mixture of butyloxyanisol and thiodipropionic
acid added to lard can be given by the data presented below.
Inhibitor
No additives
0.01% butyloxyanisol
0.01% thiodipropionic acid
0.01% butyloxyanisol + 0.01% thiodipropionic acid
Induction period, h
2
38
19
81
Butyloxyanisol in combination with other antioxidants and synergists inhibits rancidification of fats in pork, turkey, in various fish-liver oils, and in diverse vegetable oils, in
fried potatoes, and in dough items.
Pork rendered fat used for frying some chips, alone or in combination with vegetable
oils, should be subjected to obligatory antioxidant treatment. Usually, a composition of butyloxyanisol, propyl gallate and citric acid is used, which is introduced either into the frying
fat, or into salt, or partially into the fat and salt. Approximately 0.1% of the antioxidant composition is added.
Butyloxyanisol proved an efficient antioxidant of packaging materials intended for
storage of fat-containing products, dehydrated soups, as well as frozen pork. A mixture consisting of butyloxyanisol, nordihydroguaiaretic acid and ascorbic acid increases the stability
of chopped pork and turkey.
Addition of 0.003% butyloxyanisol and 0.001% citric acid to dry-cured sausages is
permitted in the USA.
Investigation of the toxicity of butyloxyanisol enables assigning it to the group of
CHAPTER 1
0.20
0.16
51
0.12
0.08
0.04
0
0
10 12 14 16 18 20
Time, h
Figure 1.11 Kinetic curves of accumulation of fat peroxides in oxidation of beef fat: 1, no antioxidant; 2, in the presence of an antioxidant mixture (0.01% BOT + 0.005% PG + 0.005% citric acid).
Oxidation temperature, 122C.
low-toxic food supplements. The acute-toxicity test of this inhibitor showed its LD50 for
rats to be within 29005000 mg/kg weight and for mice 12502000 mg/kg weight.
A prolonged feeding of animals the food containing a moderate amount of butyloxyanisol did not lead to any deviations in their organism.
The dose causing no significant toxic effect in rats is 0.5% BOA in food, which is
equivalent to 250 mg/kg body weight per day.
Butyloxytolyene (2,6-di-tert-butyl-p-cresol; 2,6-di-tert-butyl-4-methylphenol) is a
screened phenol. Depending on its purity and manufacturer, it is known under the names of
BHT (BOT), Ionol CP (ionol), antioxidant AC-1, AC-3, topanols OC, A, O etc.
CH3
CH3
CH3
CH3
CH3
OH
CH3
CH3
2,6-di-tert-butyl-p-cresol
Butyloxytolyene is represented by colourless crystals without taste and smell with the
melting temperature of 70C. Butyloxytolyene is not soluble in water and propylene glycol,
but is well soluble in fats. At 25C, 40% of the antioxidant dissolves in pork rendered fat
and beef fat. The presence of iron traces does not change the colour of products.
The crude preparation has a yellow colour and characteristic smell. It is purified by
vacuum distillation followed by recrystallization from ethanol or only recrystallization, depending on the impurity of the antioxidant.
In the UV region of the spectrum, butyloxytolyene has two absorption maxima at
wavelengths of 284 and 277 m.
Butyloxytolyene alone or in a mixture with other antioxidants and synergists (butyloxyanisol, propyl gallate, citric acid) increases the resistance to oxidation of beef fat, pork
fat, milk fat and butter, cotton oil and shortenings.
An antioxidative mixture consisting of butyloxytolyene, propyl gallate and citric acid
increases the resistance to oxidation of beef fat ninefold (Fig. 1.11), as well as protects
against oxidation carotene contained in fat. A pronounced synergic effect is observed at the
combined presence of butyloxyanisol and butyloxytolyene in lard.
52
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
3
0
4
Time, h
Figure 1.12 Kinetic curves of accumulation of peroxides in oxidation of a mixture of ethyl esters of
linolic and linolenic acids: 1, control; 2, with 0.02% BOT; 3, with 0.3% BOT. Oxidation temperature,
60C.
The antioxidative properties of BOT are carried over to products, e.g., biscuits containing fats produced with this antioxidant; however, this effect is smaller than with BOA.
The efficiency of action of BOT increases with the increase of its concentration in the
substrate.
Butyloxytolyene inhibits the development of oxidation not only in edible fats but also
in most diverse systems subject to oxidation: resins, technical fats, waxes, oils, plastics etc.
At large concentrations, butyloxytolyene inhibits oxidation even in such readily oxidizing systems as mixtures of linolic and linolenic acid esters (Fig. 1.12). It is also used as
an antioxidant of packaging materials intended for storage of fat-containing products.
Butyloxytolyene homologues 2,6-di-tert-hexyl-, 2,6-di-tert-heptyl- and 2,6-di-tertoctyl-4-methylphenols are no less efficient, and 2,6-di-tert-amyl-4-methylphenol is more
efficient as an antioxidant of pork rendered fat than 2,6-di-tert-butyl-4-methylphenol.
Acute toxicity studies of BOT on rats showed its LD50 to be within the limits of
17002450 mg/kg weight; for mice this value was 2000 mg/kg body weight. The content
of up to 0.8% BOT in rat ration does not lead to significant pathological changes provided
the content of fat in the feed is less than 5%. Addition of 10 or 20% lard to the food enhanced
the harmful effect of BOT.
As the result of long-time toxic studies of this antioxidant on animals, it was concluded
that it can be used as a food supplement, though it is considered to be necessary to continue
studies, in particular, on the effect of BOT on lipid metabolism.
Gallic acid (3,4,5-trioxybenzoic acid) is a constituent part of tannin and is contained
in tea and pomegranate juice:
OH
HO
OH
COOH
Gallic acid
Gallic acid is a white powderlike substance, which darkens in the light. It melts at a
temperature of 235C (to decomposition). It dissolves in water, ethyl alcohol and is poorly
soluble in fats. In the presence of iron, it stains blue-black.
CHAPTER 1
53
Gallic acid is a very strong phenolic antioxidant capable of acting synergistically with
other antioxidants. Its antioxidant efficiency in stabilization of carotene of animal fats and
vegetable oils proved to be high. In spite of this, its addition into edible fats is not permitted.
Possibly, this is due to the fact that, being well soluble in water, it dissolves in fats very
poorly. Esterification of the carboxyl group of gallic acid by normal aliphatic alcohols
makes it possible to improve its solubility in fats and to decrease its solubility in water.
Lower esters of gallic acid are poorly soluble in water and fats, higher esters are in fact insoluble in water but are comparatively well soluble in fats.
Propyl gallate PG (normal propyl ester of gallic acid):
OH
HO
OH
CO
OC3H7
Propyl gallate
Propyl gallate is a light-cream fine crystalline powder without smell with a light bitter
taste. Its melting temperature is 146148C. In concentrations applied, it does not affect
the organoleptic properties of fat. In the presence of iron traces, this antioxidant stains the
product. The emergence of a blue-black coloration it can be eliminated or weakened by citric acid or another metal deactivator. Propyl gallate dissolves in ethyl alcohol, propylene
glycol, glycerol and is rather poorly soluble in fats and oils. It inhibits efficiently the oxidation of pork rendered fat, milk fat, herring oil, cotton oil. It is also successfully used in a
mixture with other antioxidants and synergists (BOA, citric acid). Propyl gallate lends a
high resistance to oxidation to neutral and slightly acidic fats and fatty products, not subject
to the action of high temperatures. It is unstable to heating and the action of weak alkali.
The decomposition rate of propyl gallate in lard was studied under conditions of broiling. The data of this study are given in Table 1.6.
Table 1.6
Heating time, h
0
1
2
8
16
Content of propyl gallate in lard, %, at temperature, C

162
190
0.0058
0.0052
0.0050
0.0032
0.0002
0.0058
0.0048
0.0037
0.0008
0.0000
The antioxidative activity of gallic acid ethers (isoamyl gallate, nonyl gallate, butyl
gallate, methyl gallate, propyl gallate) in pork fat are characterized by the data presented in
Fig. 1.13. Addition of 0.01% of each gallate increased the resistance of fat to oxidation
68-fold.
Octyl and dodecyl gallates (esters of gallic acid with n-higher fatty alcohols octyl
and dodecyl alcohols):
54
0.20
0.15
0.10
0.05
0
0
11
13
Time, h
Figure 1.13 Kinetic curves of accumulation of peroxides in oxidation of pork fat with additives of
different gallates: 1, control; 2, isoamyl gallate; 3, nonyl gallate; 4, butyl gallate; 5, methyl gallate; 6,
propyl gallate. Oxidation temperature, 110C.
OH
HO
OH
OH
CO
Propyl gallate
HO
C6H17
OH
CO
C12H25
Dodecyl gallate
By their appearance, both antioxidants are crystalline substances of light-cream colour

without smell, with a weakly bitter taste. They have no effect on the organoleptic properties
of fat. The melting temperature of octyl gallate is 9495C; of dodecyl gallate, 96.597C.
These esters are almost insoluble in water, well soluble in glycerol, ethyl alcohol and
satisfactorily soluble in fat.
Octyl and dodecyl gallates in the presence of iron and its salts change the coloration
of food products. To eliminate the coloration, it is recommended to use metal deactivators.
Higher gallates are widely used for protection of fats and fat-containing products from
oxidation. They also inhibit the oxidation of fat-soluble vitamins and carotene.
Higher gallates are added to edible fats in various amounts depending on the purpose
of the product. Addition of 0.005% octyl gallate to lard increases its storage time up to approximately one year; and of 0.01%, up to two years.
Higher gallates inhibit well the oxidative processes in pure fat, as well as in fats present
in food products. They are efficient for protection from oxidation of dry dairy products.
The data on the toxicological studies of propyl, octyl and dodecyl gallates are consolidated in materials of the World Health Organization. According to these data, acute toxicity of these compounds in peroral introduction to animals is as follows:
Antioxidants
Propyl gallate
Propyl gallate
Octyl gallate
Dodecyl gallate
Animals
LD50 (mg/kg weight)
Mice
Rats
Mice/rats
Mice/rats
20003500
36003800
4700
6500
CHAPTER 1
55
According to other data, LD50 for propyl gallate is 1700 mg/kg weight for mice and
2600 mg/kg weight for rats. However, chronic experiments have found a slight adverse effect of this compound. A retardation of growth and lower resistance to partial starvation was
observed in rats given fat with propyl gallate in their diet.
No essential differences were found between control and test groups of three generations of rats given a diet containing 7% of fat and 0.2% of octyl and dodecyl gallates.
Experiments on long-time feeding (over the space of 13 months) white rats a higher
dose of dodecyl gallate (0.4% in the ration) did not lead to a change in the behaviour and
appearance of rats; no difference in weight was observed, either.
The data of a morphological study of the blood as well as the hemoglobin content in
the blood varied in rats of the test and control groups within the same limits. No effect of
dodecyl gallate on the redox enzymes of the blood was found; there were no changes in the
organs of test-group animals.
Based on the studies conducted, no harmful effect of fat with dodecyl gallate on test
animals was revealed.
The dodecyl gallate concentration of 0.01% (twenty times smaller than in the test animals) in edible fats can be considered permissible.
Nordihydroguaiaretic acid (NDGA) is contained in considerable amounts in leaves
and stems of the plant Larrea divaricata:
OH
HO
OH
CH3 CH3
CH2
CH
CH
CH2
OH
NDGA
NDGA 4,4(2,3-dimethyl tetramethylene)-dipyrocatechin.
NDGA is a white or yellow-gray crystalline powder with the melting temperature of
184185C. At a concentration of up to 0.1%, it does not change the colour, taste and smell
of pork rendered fat.
NDGA is weakly soluble in water and diluted acids. Its solubility in fats is about 0.5%,
but upon heating up to 125150C it reaches approximately 5%. In cooling, a major part
of NDGA is precipitated, but about 1% remains in fat in a dissolved form or in the form of
thin suspension. It can also be introduced into fat in ethyl alcohol or acetic acid followed
by their removal by heating under vacuum.
NDGA imparts high stability to oxidation to neutral and weakly acidic products, does
not form coloration in the presence of iron. In some cases, it lends a product a slightly bitterish taste in long-time storage. NDGA is unstable to the action of high temperatures (in
broiling) and weak alkali.
A number of works note a high antioxidative efficiency of NDGA in stabilization of
lard, beef fat, bacon, carotene, vitamin A, cow butter.
NDGA is used together with synergists (ascorbyl palmitate; phosphoric, ascorbic and
citric acids) to increase the stability of lard, bacon and other products. Introduction of
thousandth fractions of a percent of NDGA to the fat part of bacon ensures a significant
antioxidative effect.
Only to a very minor extent, the antioxidative efficiency of NDGA is transferred to the
product into which NDGA-containing fat is added. It inhibits very well the oxidation in
waterfat systems, especially in the presence of synergists. In this case, it inhibits the
56
0.15
1
0.10
2
0.05
12
16
20
24
Time, h
28
32
36
40
Figure 1.14 Kinetic curves of oxidation of pork fat at 90C): 1, no antioxidant; 2, with 1% tocopherol; 3, with 0.1% tocopherol.
development of oxidative spoilage catalyzed by meat and blood pigments and their
derivatives.
The toxicological study of NDGA has shown that LD50 for mice is within the limits
of 20004000; for rats, 20005000; for guinea pigs, 830 mg/kg body weight.
Chronic experiments carried out in limited quantities have not led to more or less unequivocal results, which does not make it possible to give a toxicological evaluation for
NDGA and at the same time to set a permissible daily dose for man.
Tocopherols (vitamin E). By their chemical structure, they are derivatives of 6-oxychroman.
CH3
CH8
HO
CH3
CH2(CH2CH2CHCH2)2CH2CH2CHCH3
CH3
CH3
CH3
-Tocopherol (5,7,8-trimethyl tocol)

Tocopherols are widespread in nature.
Besides -tocopherol, other tocopherols have been isolated from natural sources:
-tocopherol (5,8-dimethyl tocol), -tocopherol (7,8-dimethyl tocol), -tocopherol
(8-methyl tocol) etc.
Vitamin E is a rather stable compound. It is stable to the action of high temperatures,
prolonged boiling in water, but is decomposed by UV light and some oxidants.
Vitamin E is soluble in oils and fat solvents.
Tocopherols are natural antioxidants of fats, apparently, preventing the formation of
peroxides in the living organism.
Fats isolated from the animal organism or from plants is the stronger to rancidification,
the more tocopherols they contain.
Animal fats contain 0.23 mg% of tocopherols; in vegetable fats, they are 90280
mg%, i.e., the almost optimal concentrations. Therefore, tocopherols stabilize animal fats
well and are inefficient for vegetable oils.
CHAPTER 1
57
The antioxidative efficiency of tocopherols is higher at low concentrations. Their introduction into fats at too high concentrations not only fails to enhance the antioxidative
effect, but in some cases leads to an adverse change of organoleptic parameters.
The increase of the stability of pork rendered fat, into which a 0.1% concentrate of vitamin E obtained by the method of molecular distillation from soybean oil was added, is
indicated by the data presented in Fig. 1.14.
Tocopherol isomers are not equivalent by their antioxidative efficiency, and it is not
proportional to their vitamin activity. For pork fat, the most efficient antioxidant is -tocopherol, but -tocopherol is also successfully used for this purpose.
Feeding animals with tocopherols also increases the stability of fat and fatty meat to
oxidation. However, only a minor part of tocopherol is preserved in fat.
Tocopherols were found to stabilize fats present in baked and fried products.
A large number of works deal with stabilization of fats by various compositions of
plant origin, which contain vitamin E (extracts of vitamins from wheat, a petroleum-ether
extract from maize grains, oil of wheat and maize seedlings).
Soybean flour, maize and barley flour, rice bran, rye and pea flour, flour from cotton
seeds, cocoa seeds, oats flour possess antioxidative properties.
Oats have been found recently to contain aliphatic alcohol-esterified 3,4-dioxycinnamoyl (caffeoyl), which possesses an antioxidative activity. The following esters were
isolated: 1-caffeoyl glycerol, 1-palmitoyl 2,3-dicaffeoyl glycerol and 1,2,3-tricaffeoyl glycerol. Their antioxidative activity in oats oil is similar to the activity of propyl gallate and
BOT.
Besides these antioxidants, many other substances and groups of substances have been
proposed, which possess antioxidative properties.
Eugenol and its derivatives possess good antioxidative properties with respect to soybean oil and citrus ether oils. The raw material for eugenol is ether oil of colluria and basil
oil. Sesamol attributed to the group of phenols (3,4-methylene dioxypenol) was obtained
from the unsaponifiable shelf fungus of gingili oil. By the efficiency of action in lard, it is
not inferior to nordihydroguaiaretic acid.
The antioxidative properties of 2,4,5-trioxyphenons have been studied. Antioxidants
of this type were proposed for fats, carotene and other products, as well as for preparing
feeds with fat for poultry and cattle. Ethoxyquine (2,2,4-trimethyl-6-ethoxy-1,2-dihydroquinolin) was proposed as a better feed antioxidant for protection of carotene of dried alfalfa
and carotene and vitamin A in mixed feeds. In the USA, it is permitted to be added into
poultry feed. Butyloxytolyene can also be used for inhibition of oxidation of animal fats
added into feeds, or to be added into feeds in a finely ground form.
Conidendrin is an antioxidant belonging to the group of polyphenols; it occurs in resinous trees. By its antioxidative efficiency for lard, it is close to nordihydroguaiaretic acid.
Guaiacum resin has been used for many years in some countries (USA, Austria, Canada
etc.). It also inhibits the oxidation of fats in dehydrated pork and frozen meat.
The antioxidative efficiency of tannins has been confirmed by patent applications and
research work. Many natural spices possess antioxidative properties; they slow down rancidification of fats, including in chopped frozen pork and beef.
The antioxidative properties of many kinds of spices (cloves, rosemary, sage, ginger,
black pepper etc.) have been found. The lipid fractions of tomatoes and carrots possess antioxidative properties.
The antioxidative properties of some substances belonging to the group of flavonoids
(quercitin, dihydroquercitin, pomiferin, catechin) have been studied. Upon addition of 0.1%
58
1.000
TBA numbers
0.900
0.800
1
0.700
0.600
2
0.500
3
4
0.400
0.300
10
20
30
40
50
Time, days
60
70
80
Figure 1.15 Dependence of the amount of oxidation products reacting with TBA on storage time of
sausages stabilized by (concentration of antioxidants, 0.02%): 1, control; 2, butyloxyanisol; 3, ascorbic acid; 4, sodium gentisate; 5, gentisic acid.
each of quercitin and propyl gallate to fats, the antioxidative effect was the same. Quercitin
inhibits the oxidation of pork fat in the presence of copper(II) no less satisfactorily than butyloxytoluene, owing to the ability of flavonoids to form complexes with heavy metals.
Crystalline amino hexose reductons obtained from hexoses and secondary amines
were found to have a high antioxidative activity in various animal fats.
Smoking fluids were found to possess rather strong antioxidative properties due to the
content of phenols in them.
In the recent years, gentisic acid (2,5-dioxybenzoic acid) and its sodium salt were
again proposed as antioxidants of lard and other edible fats. The efficiency of these substances in the inhibition of oxidation of lard is the same as that of butyloxyanisol. They inhibit the oxidative processes in unsalted frozen bacon and sausages. The comparative
evaluation of gentisic acid, sodium gentisate, ascorbic acid and butyloxyanisol are presented in Fig. 1.15.
Esters of sorbic acid propyl, allyl, butyl, isoamyl, hexyl, nonyl and decyl were proposed as substances inhibiting the oxidation of hydrogenated whale blubber. It is seen in
Fig. 1.16 that each of the esters studied possesses an ability to increase the stability of hydrogenated whale blubber in storage. There are yet no data as to whether these compounds
can be considered as antioxidants or should be attributed to synergists.
Frequently, additives possessing the properties of synergists are introduced into antioxidative compositions. Many of them are metal deactivators.
Some acids and their derivatives. Citric acid. Many works note the positive effect
of citric acid on the stability of fats and oils in storage. Citric acid forms soluble complex
compounds with metal ions. Application of this acid is made difficult by the fact that it is
not soluble in fats and is to be introduced into fats in propylene glycol or ethyl alcohol.
Therefore, frequently fat-soluble esters of citric acid are used, e.g., isopropyl citrate, stearyl
citrate. These esters are used independently or with phenolic antioxidants. Besides citric
CHAPTER 1
59
0.10
1
0.08
0.06
0.04
2
5
0.02
6
8
3
4
7
0
5
10
15
Time, days
25
Figure 1.16 Change of the peroxide numbers in hydrogenated whale blubber during its storage at
room temperature: 1, control; upon addition of: 2, 0.02% propyl ester of sorbic acid; 3, 0.02% allyl
ester; 4, 0.02% butyl ester; 5, 0.02% isoamyl ester; 6, 0.02% hexyl ester; 7, 0.02% nonyl ester; 8,
0.02% decyl ester.
acid, it is recommended to use oxalic, malonic, maleic, fumaric and other organic acids, as
well as mineral acids phosphoric and sulfuric.
Ascorbic acid and its derivatives Ascorbic acid (vitamin C) is a crystalline compound readily soluble in water.
Ascorbic acid and its dehydro derivative form a redox system, which can donate and
accept hydrogen atoms.
In the recent years, ascorbic acid and its stereoisomer D-iso-ascorbic acid became
widespread in food industry as synergist antioxidants:
HO
HO
HO
CH2OH
Ascorbic acid
HO
HO
OH
CH2OH
D-iso-ascorbic acid
60
Ascorbic acid is an oxidation inhibitor for lard and other fats. Together with -tocopherol, it has a very strong inhibitory effect. Besides, ascorbic acid can retard oxidative
changes of muscle tissue and blood pigments. There are indications that sometimes ascorbic
acid contributes to oxidation, e.g., when it is in contact with animal fat, in which the content
of tocopherol is insignificant.
Contrary to true antioxidants, which inhibit oxidation processes even at advanced
stages, ascorbic acid in similar cases not only fails to inhibit the development of oxidation
but even accelerates it. By the example of animal fats, it was shown that addition of ascorbic
acid at the stage of oxidation, when the peroxide number was higher than 0.05 (% iodine),
has a catalytic action. Ascorbic acid is recommended to be used for stabilization of those
fats, which contain natural or added antioxidants. Owing to its solubility in water, ascorbic
acid is used for inhibition of oxidative processes in emulsions of fats and oils, and its sodium
salt
O
HO
NaO
HO
CH2
OH
for inhibition of oxidation in packaged meat.

In introduction of both substances with food, LD50 for rats, mice and other animals
was found to be >5000 mg/kg body weight.
D-iso-ascorbic acid (3-keto-D-glucofuranolactone, erythorbic acid), which possesses
no vitamin C activity, found use as an oxidation inhibitor in emulsions of fats and oils, as
well as meat and meat products.
The sodium salt of erythorbic acid is used for treatment of fatback before smoking. It
retards oxidation and contributes to the development and fixation of a reddish tint.
A 1% content of erythorbic acid in food, which is equivalent to 500 mg/kg body weight
(rats) does not lead to any significant toxic effect.
Esters of ascorbic acid with high-molecular-mass fatty acids. Of special interest are
fat-soluble derivatives of ascorbic acid: esters with aliphatic acids palmitic, stearic, myristinic, and others.
Esters of ascorbic acid do not impart fats with undesirable smell, taste and colour.
Ascorbyl palmitate is a white or yellow-white powder with a smell similar to that of citrus
fruits. The melting temperature of ascorbyl palmitate is 112113C:
OH OH
O
OH
CH
CH
CH2
CO(CH2)14
CH3.
Ascorbyl palmitate and other synthetic esters increase the stability of fats and oils to
oxidation. They are very efficient in vegetable oils; their synergist action manifests itself
well with phospholipids and -tocopherol.
The antioxidant efficiency of ascorbyl palmitate in pork fat containing natural inhibi-
CHAPTER 1
61
tors is close to the efficiency of butyloxyanisol. The combined application of ascorbyl

palmitate and butyloxyanisol is especially efficient.
The presence of ascorbyl palmitate in butyloxyanisol-stabilized beef fat retards the appearance of a greenish tint in it during refrigerator storage.
There have been no reports of acute toxicity of ascorbyl palmitate in the literature. A
0.25% content of this substance in daily diet, equivalent to 125 mg/kg body weight, has no
noticeable toxic effect on rats.
Many amino acids possess an ability to retard the oxidative spoilage of edible fats. Histidin and arginin inhibit well the oxidation of edible fat. They exhibit a significant synergism with phenolic antioxidants -tocopherol, nordihydroguaiaretic acid and gallic acid
ethers.
Phosphatides are widespread in nature. In the literature, there are often contradictory
data on phosphatides as inhibitors of oxidation of fats and oils. This is, apparently, due to
the fact that phosphatides are a complex mixture of plant or animal phospholipids. Besides,
they include unsaturated fatty acids, which are readily oxidized when they get phosphatides.
Lecithin was one of the first antioxidants of edible fats to be used.
There are indications that phosphatides alone in the absence of phenolic-type antioxidants weakly increase the stability of lard.
Some works indicate that a minor addition of commercial soy lecithin succeeded in
retarding the oxidation of lard, cotton oil and other fats, as well as vitamin A.
However, cases are known when storage of products with a lecithin addition led to
their darkening and unpleasant smell.
The lecithin and kephalin fractions of soybean, sunflower and flax phosphatides have
almost the same efficiency in stabilization of sunflower oil.
Kolamin a constituent part of kephalin has an inhibitory action on the oxidation of
some fats. There are recommendations on the application of ascorbic acid together with
kolamin for stabilizing fats and preserving vitamin A in them.
Mixtures of carbohydrates and phosphatides for stabilization of lard, bacon and other
products have been patented.
Addition of lecithin does not prevent uncooked smoked sausages from oxidative spoilage and deteriorates their taste. The synergic action of phosphatides is dealt with in a large
number of works.
It has been found that thiodipropionic and thiodiacetic acids are capable of inhibiting
oxidation.
S
CH2
CH2
COOH
CH2
CH2
COOH
Thiodipropionic acid
Thiodipropionic acid was proposed as a stabilizer of oxidation of fats and oils. This
acid in combination with butyloxyanisol exhibits a significant synergism. Its LD50 in
studies on mice was found to be 2000; in rats, it was 3000 mg/kg body weight (perorally).
For such derivatives of thiodipropionic acid as dilauryl thiodipropionate and distearyl thiodipropionate, which are also used as inhibitors of oxidation of fats and food products, LD50
for mice was >2000 mg/kg; and for rats, >2500 mg/kg body weight. A 3% content of these
substances in the diet, which is equivalent to 1500 mg/kg body weight per day, has no
noticeable toxic effect.
In a number of countries, thiodipropionic acid is permitted for addition to edible fats.
62
Nevertheless, it has not found widespread use, as mercaptans or other sulfur-containing

products with an unpleasant smell can form during its decomposition.
Tetraalkyl tiuram disulfides are recommended as substances inhibiting the oxidation
processes in edible fats. This group of compounds includes tetraethyl tiuram disulfide
(TETD) or antabus:
CH3
CH2
CH3
CH2
C
S
CH2
CH3
CH2
CH3
The application of these preparations for increasing the stability of fats and oils has
been patented.
Besides, such sulfo compounds as thiourea, thiouracyl, cystin were studied as stabilizers of fats, fatback and other fat-containing products together with a rice-bran concentrate.
Phosphates. The salts of phosphoric acid have long been proposed to be used to increase the stability of fats and fat-containing products to oxidation.
Polyphosphates belong to a very small number of oxidation inhibitors, which exhibit
their action in the presence of water. They inhibit oxidation even in the presence of heme
pigments.
Table 1.7 presents a comparative assessment of the antioxidative efficiency of various
polyphosphates added into chopped pork meat. For the assessment, the reaction with
2-thiobarbituric acid (TBA) was used; the results are expressed in units of optical density
at a wavelength of 538 m.
Table 1.7
Added phosphate (0.5% of the weight of a meat
product)
No additives, control
Sodium tripolyphosphate
Sodium hexametapolyphosphate
Sodium tetrapyrophosphate
Orthophosphate
Optical density
before storage
one-week storage at
4.4C
1.200
0.192
0.168
0.176
1.200
5.500
0.334
0.270
0.255
5.450
Tripolyphosphate, hexametaphosphate and tetrapyrophosphate are efficient additives

for pork. Their efficiency increases at the addition of ascorbic acid.
Polyposphates in combination with ascorbic acid were found to play a positive role in
inhibition of oxidation in boiled meat.
Studies of the antioxidative action of polyphosphates on meat products subjected to
brining have found that polyphosphates contribute to the preservation of their coloration
and retard the oxidation of fat.
For inhibiting the oxidative spoilage of fat in bacon and sausage products, it is recommended to add polyphosphates into cover brines and syringe brines.
A significant antioxidant efficiency of action of a mixture of tripolyphosphate with sodium ascorbinate on roasted beef slices was established. Beef slices were immersed into a
solution containing 1% tripolyphosphate (Na5P3O10) and 0.27% sodium ascorbinate. The
effect of this treatment on the change of oxidation products reacting with 2-thiobarbituric
63
CHAPTER 1
acid (TBA) and the organoleptic parameters of the roasted beef slices during their storage
in a refrigerator and in a freezing chamber is seen from the data presented in Table 1.8.
Treatment of poultry carcasses with solutions of phosphates provides for the inhibition
of the oxidative processes in fat. Phosphates also decrease the losses of meat fluid in the
culinary treatment of the carcass. Depending on the size, the carcass is immersed into a 6%
phosphate solution for 624 h or into a 15% solution for 1.24 h.
Binding of traces of variable-valence metals is ever more recommended to be done by
using some salts of ethylene diamine tetraacetic acid (EDTA). The use of these compounds
in combination with antioxidants considerably increases the stability of lard and other food
products to oxidation.
Table 1.8
Storage
temperature,
C
1
26
Storage time,
days
1
4
7
11
18
11
31
45
81
164
Controls
Tested samples
TBA number smell, score** TBA number

11.5
15.2
19.5
21.1
21.2
3.5
2.3
3.2
4.9
4.1
2.5
2.6
1.9
2.7
2.4
2.2
3.5
0.3
0.4
0.3
0.3
0.3
0.2
0.2
0.2
0.2
0.2
smell, score*
5.6
5.3
4.7
5.4
5.5
5.9
5.8
* *Score 6 indicates the absence of smell, score 1, a strong rancid odour.
1.4.9 Comparative efficiency, methods of treatment and admissible concentrations

of antioxidants
A number of original works give a comparative evaluation of many antioxidants, synergists
and metal deactivators as applied to various fats and model systems, a major part of which
is dealt with in monographs. As as example, Fig. 1.17 compares the efficiencies of several
inhibitors of oxidation of pork rendered fat. As this kind of fat contains little natural inhibitors tocopherols addition of one synergist is the least efficient.
The most suitable inhibitors of animal rendered fats are phenolic antioxidants, preferably with addition of a synergist.
The choice of an antioxidant or an antioxidant mixture becomes much more complicated if fat is a component of a food product, because in this case it is in contact with moisture and various food components. If there is water in the system, the antioxidant should be
relatively soluble in fat and water. Water-insoluble inhibitors are more suitable for dry
fat-containing products.
When using antioxidants, a matter of importance is the moment of their introduction
into fat, so that to inhibit the development of the chain reaction of oxidation as soon as possible. Antioxidants can be introduced into raw materials before rendering, before settling
or draining off the fat into barrels. Below, we present the results of model experiments.
64
0.20
0.16
0.12
0.08
0.04
12
Time, h
16
20
24
Figure 1.17 Kinetic curves of accumulation of peroxides at a temperature of 110C during the oxidation of pork pat in the presence of 0.01% antioxidant: 1, no antioxidant; 2, ascorbyl palmitate; 3,
dodecyl gallate; 4, octyl gallate; 5, butyloxytolyene; 6, butyloxyanisol; 7, propyl gallate.
Point of introduction of 0.01% BOA
Induction period, h
Before rendering
Before settling
10.0
11.8
After settling
10.5
As seen, the greatest effect is achieved at the introduction of BOA into fat before settling and the lowest effect before rendering, which can be explained by adsorption of the
antioxidant by proteins of connective tissue.
Therefore in rendering fat in kettles the antioxidant should be introduced before settling.
For fats produced in automatic fat-rendering units (e.g., Titan), antioxidants can be introduced only at one point of the technological process before draining off into barrels.
Pork fat or another animal fat is accumulated in the receiver. After filling the receiver,
the supply of fat to it is stopped. Fat (35 kg, temperature usually 80C) is poured from the
receiver into a small vessel, into which the antioxidant or antioxidative mixture is added;
the contents are mixed to dissolution, poured back into the receiver and mixed with the
entire bulk for 10 min, after which fat is drained off into barrels.
The surface treatment of slabs of meat and other products is performed by sprinkling
with solutions or suspensions of antioxidants or by immersion into them, but in some case
it is better to fine spray a solid antioxidant. If a product should be soaked, it is kept for a
long time in a solution of an antioxidant or the antioxidant is introduced into tissues by a
syringe.
Pieces of fatback can be treated by rubbing the antioxidant together with salt in dry
salting, or by adding the antioxidant in solution into the brine in brine salting.
CHAPTER 1
65
Dehydrated products are usually treated with solutions or a suspension of an antioxidant before drying.
Into rendered fats and chopped products, antioxidants and antioxidative compositions
are also introduced in propylene glycol or in mono- or diglycerides; volatile solvents
alcohol or acetic acid can also be used; afterwards they are removed by a combined action
of temperature and vacuum. Salt, glucose and spices can also be used as antioxidant
carriers.
Some Western companies manufacture ready-made antioxidant compositions in
solutions.
The number of countries, in which the use of some antioxidants and synergists is permitted, increases. Recently, the Committee on Food Additives (FAO/WHO) determined the
limits of unconditionally and conditionally permissible daily doses of antioxidants for man.
The largest unconditionally permissible should not be considered as the maximum value, which can be permitted from the point of view of toxicity of a food additive. Therefore,
the Committee found it expedient to set the limits of conditionally permissible daily doses
so that experts in each country could make a final decision on the permissibility of the doses
within the limits conditional for this or that food additive with consideration of special requirements of their own country, groups of population, kinds of food into which additives
would be introduced, methods of their treatment, consumed amount of this food and other
peculiarities.
For some substances, only conditionally permissible doses are given due to the
absence of sufficient scientific data required for the toxicological evaluation of those
substances.
1.4.10 Methods for identification of antioxidants
The following methods are proposed for a quantitative determination of antioxidants, synergists and metal deactivators, as well as their mixtures: polarographic, colorimetric, spectrophotometric (in the visible, ultraviolet and infrared regions of the spectrum),
chromatographic (paper, gas and thin-layer chromatography) and other methods.
Polarographic methods and methods of determination in the infrared region of the
spectrum are not many and found no wide use.
Of considerably greater interest for practical purposes are spectrophotometric methods
of determining antioxidants in the ultraviolet region of the spectrum.
UV spectrophotometry is used for determining butyloxyanisol and butyloxytoluene in
edible fats.
In the presence of PG, BOA, NDGA, citric acid and monoisopropyl citrate, more than
93% butyloxytoluene was determined. Spectrophotometric curves of BOT and other inhibitors are given in Fig. 1.18.
Based on thorough studies of the spectrophotometric method of determining butyloxyanisol, higher and lower gallates in edible fats and oils, the authors consider it the simplest
and most reliable for quantitative determination.
Light absorption is measured at several wavelengths after extraction of antioxidants
by 72% ethyl alcohol. This method also makes it possible to determine the content of ascorbic acid in the presence of the above antioxidants.
A method of determining ethoxyquine in feeds from the absorption in the UV region
of the spectrum has been proposed.
Determination of ethoxyquine is based on its extraction with 0.5N HCl from the sol-
66
50
Absorptivity
40
30
20
3
10
4
5
0
240
260
280
, m
300
320
Figure 1.18 UV absorption spectra of antioxidants and synergists: 1, propyl gallate; 2, butyloxyanisol; 3, nordihydroguaiaretic acid; 4, butyloxytolyene; 5, citric acid.
vent and the measurement of the optical density of the solution at a wavelength of 296 m
(Fig. 1.19).
Other spectrophotometric methods of determining antioxidants in the UV region of the
spectrum have been also described.
Colorimetric methods, as spectrophotometric methods in the visible region of the spectrum, are used the most frequently for quantitative determination of antioxidants in edible
fats.
For carrying out the colour reaction, antioxidants are extracted from fat by a suitable
solvent or are distilled with superheated steam (in determining butyloxytolyene).
For quantitative determination of a number of antioxidants: butyloxyanisol, butyloxytoluene, gallic acid ethers, nordihydroguaiaretic acid, tocopherols and others, use was
made of redox reactions. The colour reaction is performed with ,-dipyridyl or potassium
ferricyanide. These colorimetric methods are nonspecific.
A reagent 2,6-dichloroquinone chlorimide is widely used for antioxidant determination; this reagent is specific for butyloxyanisol.
Using 2,6-dichloroquinone chlorimide, the content of butyloxyanisol in the presence
of butyloxytoluene can be determined.
A spectrophotometric method was developed for quantitative determination of gallates. Determination of propyl gallate is based on the colour reaction with the reagent ferrotartrate in the presence of an aqueous solution of sodium acetate and the measurement of
the coloration at a wavelength of 530 m with respect to water. When determining octyl
CHAPTER 1
67
1.0
1
0.9
0.8
Optical density
0.7
0.6
0.5
2
0.4
0.3
3
0.2
0.1
280
300
350
, m
Figure 1.19 UV absorption spectra of a standard solution of ethoxyquine in 0.5N HCl: 1, 0.0112
mg/ml; 2, 0,0056 mg/ml; 3, 0,0028 mg/ml.
and dodecyl gallates, the optical density of the solutions at 550 m with respect to isoamyl
alcohol is measured.
A simple and fast method of determining gallates is based on their isolation from fat
with a 95% alcohol and the determination of the amount of gallates in the extract by
measuring the coloration formed with Mohrs salt, at 580 m.
Recently, a complexometric method of determining antioxidants was developed. Mercury acetate proved the best precipitation agent of gallates. This method yielded good results in determination of gallates soluble in water. At the determination of butyloxyanisol
by the complexometric method the author obtained more reliable data than in the determination by the colorimetric method.
Chromatographic methods make it possible to detect comparatively easily and in many
cases to determine quantitatively several substances at once, if an antioxidant composition
was added into the product assayed.
Using paper chromatography, antioxidants butyloxyanisol and butyloxytoluene can be
separated in the presence of gallates and butyloxyanisol isomers. Three-valent ferrous sulfate or potassium ferricyanide are used as developers. This method enables detection of
0.001% gallate, 0.005% butyloxyanisol and 0.01% butyloxytolyene in pork fat.
When separating a large number of antioxidants in pork fat or margarine, the chromatogram is sprayed with one of the two developers: (i) a 1% alcohol solution of silver nitrate and after drying a 1% solution of ammonia; (ii) a 2% aqueous solution of borax and
after drying a 0.01% alcohol solution of 2,6-dichloroquinone chlorimide. The separation is
done on paper SS20443b or Whatman No 1.
68
Paper chromatography is used for separation of tocopherols over a period of several

years.
Using paper chromatography, the content of tocopherols in natural oils is determined.
In one-dimensional chromatography, paper is impregnated with zinc carbonate; in twodimensional chromatography, with paraffin. As a developer, ,-dipyridyl is used.
The method makes it possible to separate and determine -, -, -, -, and -tocopherols.
The literature gives results of separating methyl, ethyl, propyl, octyl, dodecyl gallates;
nordihydroguaiaretic acid, butyloxyanisol and butyloxytoluene using descending paper
chromatography. The antioxidants are isolated by 78% ethanol from a solution of fat in
petroleum ether; the extracts are evaporated to dryness and dissolved in ethyl acetate. For
their distribution, a mixture of chloroform with acetic acid (99:1) is used at a saturation of
the chamber with 50% acetic acid. All antioxidants separate well, besides butyloxyanisol
and butyloxytolyene, which have very close values of Rf.
Butyloxyanisol and butyloxytolyene can be separated most suitably by the method of
chromatography on Mitchell paper.
Thin-layer chromatography has found wide use in determination of food additive
owing to the exceptional speed of the analysis with all the other advantages of the chromatographic methods preserved.
Mixtures of pure antioxidants can be easily and quickly separated using thin layer
chromatography on kieselguhr. 2,6-Dichloroquinone chlorimide and diazotized sulfanilic
acid are used as developers. The method is very sensitive and reliable.
A method of quantitative determination of butyloxyanisol, butyloxytolyene, propyl
gallate and nordihydroguaiaretic acid in lard using two-dimensional thin layer chromatography has been described. Antioxidants are extracted with 80% ethyl alcohol and acetonitrile from a solution of lard in n-hexane. Stains are separated using benzene and acetonitrile. The quantitative determination is performed colorimetrically after extracting stains
from the plate.
This method determines the following amounts of antioxidants: BOA, 98101%;
BOT, 96101%; PG, 90101%; NDGA, 8298%. The method enables efficient separation
of butyloxyanisol isomers.
A method was proposed for determining nordihydroguaiaretic acid, propyl gallate,
ascorbyl palmitate, butyloxyanisol and butyloxytolyene in a thin layer on polyamide powder. A mixture of methanol, acetone and water at 3:1:1 or 6:1:3 ratios is used as solvents.
Identification is performed with diazotized sulfanilic acid or phosphoric-molybdic acid.
Ascorbyl palmitate in the presence of other antioxidants can be determined even if it
is present in fats in the amount of 0.0010.002%. Ascorbyl palmitate extracted from fat is
treated with a solution of the sodium salt of 2,6-dichlorophenol indophenol in the presence
of trichloroacetic acid, heated at 70C with a solution of 2,4-dinitrophenyl hydrazine in sulfuric acid. The reaction products formed are extracted with ethylacetate, separated on a thin
layer of silica gel in a chloroformethylacetate (1:1) system. The brick-red band of the
2,4-dinitrophenyl hydrazine derivative of the dehydro form of ascorbic acid taken from the
plate is eluted; the intensity of coloration of the solution is determined photometrically at
520525 m.
Thin layer chromatography can be used to separate methyl, ethyl, propyl, butyl, octyl
and dodecyl esters of gallic acid. A 10% acetylated cellulose is used as the stationary phase;
the solvent is a four-component system of a solution of Shell Soil A, n-propyl alcohol,
glacial acetic acid and formic acid at ratios of 45:6:3:6 (v/v).
CHAPTER 1
0.6
Detector signal, mV
69
0.5
1
0.4
0.3
0.2
0.1
0
10
5
Time, min
Figure 1.20 Chromatogram of a standard solution in petroleum ether: 1, butyloxyanisol; 2, butyloxytolyene.
Thin layer chromatography on polyamide was applied in determination of flavonoids,

glucosides and fat-soluble vitamins.
A number of gallic acid ethers, butyloxyanisol, butyloxytolyene, sesamol and others
were analyzed on a starch-bound polyamide layer in a methanol/acetone/water solvent
(60:20:20).
On a thin layer of polyamide, the Rf values of a large number of antioxidants (methyl,
ethyl, propyl, butyl, octyl, dodecyl gallates; butyloxyanisol, butyloxytolyene, sesamol, nordihydroguaiaretic acid, ascorbyl palmitate) with various solvents (methanolacetone
water, 60:20:20 and light petroleum etherbenzeneacetic aciddimethylformamide,
10:10:5:0.25) were determined.
The development of gas chromatography provided for the possibility of its use in the
field of antioxidant determination.
A method using gas-liquid chromatography has been developed for separation and
quantitative determination of butyloxyanisol, butyloxytolyene and ethoxyquine in samples
soluble in water and hydrocarbons. In combined occurrence of all of these antioxidants,
they are determined at a temperature of 188C on a column (1520.6 or 0.3 cm) filled with
20% silicon SE-30 on refractory brick (6080 mesh) at a helium flow rate of 185 ml/min;
detection, by heat conductance.
To determine traces of BOA, BOT and ethoxyquine, it is recommended to perform
chromatography at 185C on a column filled with 20% silicon SE-30 on chromosorb W at
a gas flow rate of 175 ml/min. An ionization detector is used.
For a quantitative determination of butyloxytolyene and butyloxyanisol in dehydrated
potato granules, a fast method of gas-liquid chromatography using a flame ionization
detector has been proposed. Figure 1.20 shows a chromatogram obtained in determination
of a mixture of both antioxidants.
70
A combination of rapid extraction with a gas-chromatographic assay enabled determination of traces of butyloxytolyene and butyloxyanisol in potato granules, vegetable oils
and packaging materials. The use of a column with a mixture of silicon SE-30 and Tween
80 at 150C provided a possibility of complete separation of assayed substances from interfering impurities. 3,5-Di-tert-butyl-4-oxyanisol was used as an internal standard.
A method of determining butyloxyanisol and butyloxytolyene on a gas chromatograph
with temperature programming and use of 3,5-dibutyloxyanisol as an internal standard has
been described. A chromatograph equipped with a catharometer was applied. Initial temperature of the column, 125C; final temperature, 190C; programming rate, 11 deg/min.
All existing methods of determining antioxidants, besides gas-liquid chromatography,
are low-sensitive at antioxidant concentrations below 1 mg%.
2
2.1
Polymer Packaging
Materials for Preservation
of Foodstuffs
Food polymers
One of the most important high-molecular-mass compounds is at present the class of polymers. As compared with common substances, such as, e.g., water (molecular mass, 18),
benzene (molecular mass, 78), chalk (molecular mass, 100), the values of polymers
molecular masses vary within the range of tens of thousands up to millions. In polymers,
their giant molecules are built from consecutively bound groups of atoms forming a long
chain, which contains sometimes hundreds of thousands repeating structural units: elements, links. The word polymer means many parts and is derived from the Greek words
polys meaning many and meros meaning parts. An example of a polymer consisting of atoms linked by chemical forces into a chain is plastic sulfur. As is known, it is produced by pouring molten sulfur into cold water. The structure of polymer sulfur is
S S S S . In this
represented by a chain of atoms linked by chemical bonds:
state, the properties of sulfur differ from the properties of common crystalline sulfur. They
resemble rubberlike rather than solid bodies. For most polymers, the repeating elements of
the structure are usually small groups of atoms. One of the simplest (from the point of view
of its chemical structure) and widespread polymers polyethylene has the following
structure: CH2 CH2 CH2 CH2 CH2 ... .
Polyethylene is obtained by attaching molecules of ethylene CH2 CH2 to one
another. By means of corresponding catalyst and conditions, the double bonds are opened
and chains are formed from consecutively attached groups of CH2 CH2 . The initial
molecule, from which the polymer is formed, is called monomer. The word monomer
is derived from the Greek word monos meaning single. The number of monomer units
forming the chain molecule of the polymer is called the degree of polymerization. Another
widespread polymer, polypropylene, has a close structure:
...CH2
CH
CH3
CH2
CH
CH3
CH2
CH
CH3
It is obtained by attaching molecules of propylene CH2
CH2
CH
...
CH3
CH to one another.
CH3
As polyvinyl chloride ... CH2 CHCl CH2 CHCl CH2 CHCl ... obtained
by polymerization of vinyl chloride CH2 CHCl , polyethylene pertains to large-scale
72
products.
...
CH2
Large-scale polymers include synthetic rubbers (polyisoprene

C CH CH2 , butadiene ... CH2 CH CH CH2 ... , and others),
CH3
polystyrene ... CH2
CH
CH2
... , cellulose hydrate and esters, as well as poly-
CH
mers, which are used in contact with foods. Among polymer materials suitable for contact
with food products, of special importance are linear polyesters, whose links contain aromatic and aliphatic groups, e.g., polyethylene terephthalate or polyethylene glycol terephthalate ...OCH2
CH2OOC
CO
... .
This is a crystallizable polymer. Its polymerization rate is maximal at 180190C. It

does not crystallize below 97C. Crystallites of polyethylene terephthalate melt at 256C.
If the melt is rapidly cooled, it has no time to get crystallized and will be in a glass-transition
state. The temperature at which it begins to pass from the glass-transition to rubber-like
state is 81C. If, however, the polymer has time to get partially crystallized (at a slower
cooling), its glass-transition temperature increases. Thus, for instance, at the crystallinity
rate of 65% the glass-transition temperature increases up to 120C.
Films from polyethylene glycol terephthalate are 5 to 6 times stronger than oriented
films from polyethylene, possess a lower vapour and water permeability and a larger oxygen and light resistance.
The breaking strain of this film is 175 MPa; relative elongation, 5070%; lowtemperature resistance, 160C; water absorption, 0.5%; melting temperature, 250C; temperature of the total strength loss, 248C.
O
If the main chain of the macromolecule contains amide groups C NH , then the
polymer belongs to the class of polymer compounds under the general name polyamides;
in a general form, their chemical structure can be expressed by the general formula
...
C
O
NH
R'
NH
...
where R and R are meant to be atomic groups ( CH2 )n and (CH2)m. Films from polyamides in combination with films from other materials have recently found use in packaging of meat products.
Along with the required performance properties, such as chemical durability, a certain
level of the physicochemical, physicomechanical and technologocal properties, polymer
materials used in direct contact with foods should also meet high hygienic requirements.
Therefore, in accordance with the law, polymer materials can be used in contact with a
given type of food products only after a corresponding permission from the sanitaryepidemiological bodies. Goods from polymers are subject to thorough organoleptic,
sanitary-chemical and toxicological studies.
Polymers are produced not only by chemical methods. They are widespread in nature
in the form of cellulose, starch, natural rubber, silk and various resins. Not only many kinds
of natural polymers can be reproduced by chemical methods and synthetic polymers
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developed (e.g., synthetic rubber), but also new polymer substances required for the economy can be created. Chemical methods can also be used to change the chemical nature of
a natural polymer, e.g., cellulose, by imparting it with the required properties. As a rule,
natural, synthetic and chemically changed natural polymers are used not in pure form, but
in various combinations both between themselves and with various substances added into
the polymer composition to impart it with properties required.
To date, there is a tendency not to expand the range of large-scale polymers used as
the basis for production and processing of plastics, but to search for rational ways of using
traditional polymers. This search proves the most productive in physicochemical, chemical
and physical modification of polymers or in combining various polymers and other materials in constructions, which optimally combine the properties of a component and the final
complex of the properties of material or article.
The simplest variant is a mixture of two or several polymers, which gives the required
combination of performance properties.
When choosing a polymer for fabricating an article, one should proceed from the purpose of the article and conditions of its use. Herewith, one should be based on the values of
the characteristics, which determine the performance of the article, e.g., the value of breaking strain at the sterilization temperature or the strength of an adhesion seam in heat sealing
etc. These characteristics should correlate with conditions, under which the article would
be operated, e.g., the value of strength should not go below a given level under all performance conditions. The successful fabrication of an article from polymers is possible only
if the characteristic properties of the plastics are taken into account depending on the operational conditions and methods of processing.
When choosing polymers, it is necessary to use their resources to a maximum, so that
an article not only conforms to its purpose but its fabrication from a chosen plastic is economically more expedient than fabrication from another material. The chosen polymer and
other ingredients of a composition should conform to the sanitary-hygienic conditions.
Most polymer compositions used to produce plastics can include besides a polymer
binder hardeners, plasticizers, fillers, dyes, pore formers, lubricating agents and other
components. Each of the components of a polymer composition performs its specific
function.
Plasticizers are usually introduced into plastics to increase the plasticity of a composition and of a plastic produced from it. This change of properties (physical modification)
contributes to an easier processing of the plastics into articles, increases their low temperature resistance, decreases the elasticity modulus. Introduction of plasticizers into a composition facilitates the mixing of a polymer with other ingredients, decreases the
temperature of processing a plastic into articles. In some cases, besides the above functions
plasticizers also impart plastics with such properties as, e.g., noncombustibility, increases
their heat resistance and light permanence.
Both low- and high-molecular-mass compounds can serve as plasticizers. The requirements they should meet are as follows: the ability to match with polymers to form an operationally stable system, low volatility; absence of colour, smell; the plasticizing action
should be preserved at the lowest operational temperatures; chemical stability should be no
less than in polymer components.
In some cases, additional requirements should also be met, such as an almost complete
absence of extractability from the polymer with liquid media, oils, solvents, detergents,
food products.
The most important plasticizers include esters of aromatic and aliphatic carboxylic
74
acids and phosphoric acid, epoxidized compounds, polyesters, esters of glycols and monocarboxylic acids.
Fillers of plastics are solid and gaseous substances, whose introduction makes plastics
stronger, less deformable and less shrinkable, or makes them to acquire other useful properties, such are incombustibility, larger friction coefficient, electrical conductivity etc. In
some cases, fillers do not improve the operational properties but, being a cheaper and more
available part of the plastics, reduce their cost. Fillers, which significantly improve the
operational properties of plastics are usually called active.
The content of fillers in plastics can change within broad limits and is usually 4550%
in terms of polymer weight. In high-filled plastics, the content of filler can exceed the polymer content severalfold.
Of undoubted interest are the current works on production of high-filled thermoplastics directly in the synthesis process. The idea is to use the catalyst applied onto the carrier as a filler in the polymer composition. Thus, the filled composition is produced directly
in the reactor, which not only makes the mixing process simpler, easier and less energyintensive, but contributes to a stronger bonding between the components. Such materials
developed by academician N.S. Enikopolov et al. were given the name of norplastics.
The most widespread fillers are solid; they are divided into powdery and fibrous. In
some cases, such fillers as, e.g., graphite, glass, various metals etc., are used both as powders and fibres. Active fibrous fillers are called reinforcing fillers.
The general requirements imposed on fillers are primarily their ability to mix with
polymer to yield a given degree of homogeneity, the ability to be wetted by the polymer
melt or solution, the stability of the properties in storage of the filler, processing and use of
the plastic.
When using powdery fillers, the process engineer should solve a number of problems,
such as to determine the optimal size of particles, the concentration of filler and the desirable structure of the polymerfiller system. In the latter case, it is desirable to determine
which type of structures (a more or less uniform distribution of particles in the bulk of the
polymer composite, or formation of chain structures consisting of filler particles, or else,
e.g., formation of a three-dimensional network from the chain structures etc.) is the most
expedient for achieving a given set of properties.
It follows from the above that polymer materials are used in fabrication of articles not
as individual substances but as a polymer composition, a mixture of various polymer ingredients, which confer a required shape upon the article and then fix this shape by various
technological techniques.
A great diversity of polymer types and polymer compositions makes it possible to
choose those the combinations of properties of which correspond to the conditions of operation of an article. Especially specific are operational conditions of polymer materials
used for packaging of foods. Packaging is reduced to not only providing the possibility of
prepackaging and transporting the food products, but to protecting them from the impact of
the environment, pathogenic bacteria, preserving the nutritive value of a product, increasing
its expiry date and many other aspects. Thus, a polymer packaging is active with respect to
a food product. However, this activity can be not only useful but also harmful.
This is due to the fact that polymer material is a complex composition, which, besides
a polymer, i.e., a high-molecular-mass compound, includes many low-molecular-mass
chemical compounds.
As a rule, additives and low-molecular-mass impurities are chemically not bound to
the polymer. Under certain conditions, these substances can pass (migrate or diffuse) into
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the contacting medium: air, water, foodstuffs. This creates a potential hazard for man when
using polymer materials as food packaging, because migrating substances can be toxic and
have adverse effects on the human organism. Of special importance is that, getting into the
human organism in small concentrations but acting for a long time, they can evoke no fast
and acute diseases, but act slowly and sometimes not manifesting themselves for years.
Therefore, prevention of such pathological phenomena becomes the most important
hygienic and social problem.
This problem is being solved by a common effort of physicians, chemists and process
engineers. At present, physicians listen to a course of lectures on polymers, and process engineers study the possible consequences of incorrect use of polymer materials and methods
of developing practically harmless polymer articles.
The hazardous action of polymer articles is usually determined by the toxicity of lowmolecular-mass substances present in them, but not by the polymer itself, which is practically insoluble in water and other food media. Therefore, two criteria determine the harmfulness of a polymer material: the toxicity of low-molecular-mass substances present in a
polymer or forming in it, and the amount of these substances passing into the contacting
medium. The certificate of toxicity, i.e., the extent of harmfullness for man, of chemical
substances is issued after toxicological studies; and the chemical composition, amount and
character of migration of individual substances from polymer materials are studied in the
course of sanitary and chemical tests.
In view of the importance of this problem, besides a certain set of physicochemical and
physicomechanical properties, polymer materials intended for contact with foods should
also satisfy hygienic requirements: the formulation of a polymer material should not include
substances possessing a toxicity, but only those substances that are permitted by the Ministry of Health bodies and are present in a corresponding list; articles from a polymer material in contact with food products should not change their organoleptic properties (i.e.,
taste and smell) and should not evolve low-molecular-mass chemical substances in amounts
exceeding admissible levels, i.e., in amounts, which can have a harmful effect on humans
when taken up with food; at the impact of food media, the appearance of the articles should
not change. Physico-hygienic, physiologo-hygienic and microbiological studies can be also
necessary in some cases.
2.2
Hygienic characteristics of packaging materials components
Preliminary information on the hygienic characteristic of substances introduced into a polymer composition can be obtained based on the physicochemical properties solubility in
various media, volatility etc. However, ultimately the possibility of using this or that chemical substance in polymer materials can be decided upon only based on the data obtained in
experiments on animals. The aim of toxicological studies is to reveal the toxic action of
low-molecular-mass substances, evolved from polymer materials into the environment, on
the animal organism. The currently accepted scheme of toxicological studies is two-stage.
The first to be studied are the toxic properties of separate components, which are either initial substances for producing a polymer or are introduced into it subsequently to impart it
with certain properties. In each particular case, the need for the toxicological evaluation of
substances is determined based on the formulation of polymer material and the results of
the sanitary and chemical analysis. This toxicological evaluation is to establish the norms
of evolution of these low-molecular-mass components into the environment air, water,
food products or model media imitating them. If, as the result of a toxicological evaluation,
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any of the additives is found to be practically nontoxic, no norms of evolution for it are established, and its use is permitted in all-purpose plastics without any obligatory control of
its evolution.
The second stage of the toxicological evaluation is to study the toxic action of all polymer material as a whole depending on its assumed application. This type of toxicological
research is to be carried out either when the evolution of separate components is close to
the established norms but the combined action of several components is anticipated to be
stronger, or when not all substances evolved from the plastic have been identified. It is especially important in this case to establish the amount of substances capable of evoking a
pathological effect.
Proceeding from the degree of the risk of possible pathogenic effects on the organism
to develop, taking into account the biological activity and extent of migration from polymer
materials, various additives can be divided into admissible, whose use for food brands of
polymer materials is permitted, and inadmissible.
The first group includes compounds, which do not change the organoleptic properties
of products, and also those whose harmlessness has been proven by many years of practice.
This group includes most major compounds used in production of polymer materials:
monomers, plasticizers, dyes. However, their use is regulated by hygienic norms the admissible amount of migration (AAM) (e.g., for such monomers as styrene, epichlorohydrin,
formaldehyde) or by standardization of their content in a polymer composition on the level providing for the harmlessness for foods.
The group of inadmissible compounds includes those the use of which in production
of food-purpose polymer materials is totally banned.
This group incorporates compounds, which possess a high toxicity and pose a significant threat in the case of migration into the environment (e.g., arsenic and lead compounds).
Based on the results of hygienic studies, the maximally admissible daily dose (Dm) is
established.
This coefficient is a major parameter for the calculation of the AAM for a given substance in the food brands of polymer materials.
Based on the results of the toxicological experiment of determining Dm and AAM, the
health bodies make a decision on the admissibility of using the substance studied in food
brands of polymer materials.
Let us dwell on the evaluation of the biological activity of compounds used the most
in production of polymer materials: monomers, catalysts, initiators, stabilizers, plasticizers.
Monomers. When producing polystyrene, the initial monomer is styrene (vinyl benzene) a liquid with a characteristic smell, which boils at 146C. The norm of the admissible amount of migration of styrene from polystyrene articles is 0.01 mg/l.
Epychlorohydrin is a colourless transparent liquid with a specific irritating smell. Possesses a high biological effect, which to a large extent is explained by the presence of chlorine-containing groups in the molecule. AAM of epychlorohydrin is 0.1 mg/l.
Vinyl chloride is a colourless gas without a smell; boils at 13.8C. AAM of vinyl chloride is 0.01 mg/l.
Most polymerization catalysts are totally incorporated into the final product. The residue of the inorganic compounds in the polymer can be characterized by the ash content.
Thus, the ash content of polyethylene intended for contact with foodstuffs should not exceed 0.02%. The presence of even insignificant amounts of catalysts in the finished article
may lead to a faster ageing of polymer material.
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Polymerization initiators are capable of decomposition during the heating to form free
radicals. Usually, oxygen-organic and -inorganic peroxides, hydroperoxides and diazo
compounds are used as initiators. Most of these substances possess an irritating action, have
an effect on the nervous system. Peroxide degradation products are also biologically active.
The content of polymerization initiators and products of their degradation in finished polymer materials should not exceed 0.2%.
Stabilizers contribute to the long-term preservation of the properties of plastics. Stabilizers enter into a chemical interaction with polymer. They readily diffuse from it into
contacting media. The proximity of the mechanisms determining the efficiency of stabilizers to the phenomena occurring in a living organism points to their biological activity.
Widespread heat stabilizers are stearates of metals calcium, zinc borate, lead etc. Calcium
and zinc stearates, as well as complex stabilizers, proved to be practically nontoxic substances. At the same time, stearates of cadmium, barium, lead possess a high toxicity.
For stabilization of PVC materials contacting with foodstuffs, epoxidized soybean oil
is used, which is a low-toxic compound. However, its introduction to the polymer composition in excess amounts may enhance migration of the other ingredients.
Plasticizers. All in all, 2000 various plasticizers are known; however, in production of
materials contacting with food products, a limited number is used: glycerol; paraffin oil;
ethanolamines; esters of phthalic, sebacinic, adipic and citric acids; as well as lowmolecular-mass polyesters. In the opinion of some investigators, esters of sebacinic and citric acids, as well as stearic acid and its salts (calcium and zinc stearates) can be considered
to be practically nontoxic plasticizers.
Glycerol, triacetin, castor oil, mono-, di- and triethanolamines and their salts are also
attributed to nontoxic plasticizers. Of great importance are acetyl tributyl citrate and ethylhexyl phenyl phosphate, which are used to produce films intended for packaging of food
products. Both plasticizers are low-toxic, possess a high water, oil and low-temperature resistance as well as insignificant volatility.
Fillers. Silicon dioxide, chalk, cellulose, wood veneer, titanium dioxide etc. are used
as fillers. For the most part, they are nontoxic.
Solvents. Organic solvents toluene, benzene, ethylacetate, hexane, petrol, methylene
chloride etc. are used in polymerization or polycondensation in solution. Certain amounts
of these solvents can remain in fabricated polymer materials both after the main process
operations and after some auxiliary operations. Chloroorganic and aromatic compounds
and alcohols can remain in the material owing to incomplete drying.
Migration of solvents into contacting media can have an impact on their taste and
smell, and also lend them toxic properties. Information on the toxicity of particular solvents
can be found in reference books PDK Vrednykh Veshchestv (=MPC of Harmful Substances) (in Russian) (Leningrad, Khimiya Publishers, 1975) and Vrednye Veshchestva v
Promyshlennosti (=Harmful Substances in Industries) (in Russian) ed. by N.V. Lazarev
(Leningrad, Khimiya Publishers, 1971).
Dyes. Synthetic or natural dyes soluble in most common solvents, as well as pigments
of organic and inorganic origin are used for colouring plastics. The dyes are usually insoluble. Migration of dyes can have a general toxic action during its penetration through the
skin, as well as in the stomach during its intake with water or with food products.
Various aminoanthraquinone and azo dyes are capable of evoking disturbances of the
functional state of the liver, kidneys, the central nervous system; to disturb redox processes
in the organism. A characteristic feature of most dyes is a low toxicity at a single introduction into the organism in large doses and the ability to cause intoxication during the chronic
78
intake of small doses.

As for inorganic dyes, their biological activity depends on the element occurring in the
compound. A general toxic action is characteristic of strontium- and chromium-based dyes.
Iron- and titanium-based dyes are practically harmless. To guarantee the harmfulness of
using coloured articles, the AAM for dyes is set to be with the safety margin of 1001000.
In operation of polymer materials, they age, i.e., their physicochemical and physicomechanical properties change under the action of external conditions. Ageing of polymers
is due to the degradation reactions owing to the rupture of the molecular chain. As the result
of the degradation, articles get deformed, crack and in some cases break. Some degradation
processes are accompanied with a change of the appearance of the articles, staining, yellowing, blooming, warpage etc.
Degradation of polymers usually occurs under the action of chemical agents (water,
alcohols, acids, oxygen, ozone etc.) or under the action of physical impacts (heat, light, ionizing radiation, mechanical energy etc.). Polymers can also be degraded during their processing owing to the violation of the technological regime. All these processes are
invariably associated with the evolution of harmful chemical substances degradation
products from plastics into the environment.
Decomposition of polyethylene is accompanied with evolution of such substances as
formaldehyde, acetaldehyde, acids, unsaturated hydrocarbons, low-molecular-mass oligomers; in strongly pronounced decomposition, H2O and CO2 can evolve. Besides the above,
acetone, methyl alcohol and other alcohols are found among the degradation products of
polypropylene.
The most toxic are formaldehyde its AAM was set to be 0.1 mg/l and methyl alcohol (AAM, 1.0 mg/l).
Polystyrene in degradation evolves styrene, -methyl styrene, ethyl benzene and other
aromatic hydrocarbons, benzaldehyde, benzophenone and other aromatic aldehydes and
ketones. Aldehydes, alcohols, hydrogen chloride, chlorinated hydrocarbons, unsaturated
hydrocarbons are formed as the result of the degradation of PVC.
Ageing of methylacrylate is accompanied by the evolution of methyl alcohol, MMA,
methacrylic acid, unsaturated hydrocarbons. The AAM of MMA is 0.25 mg/l.
Amino plastics are degraded to form aldehydes (formaldehydes), ammonia; phenoplastics, to form phenol (AAM, 0.001 mg/l), aldehydes; epoxy resins evolve epichlorohydrin (AAM, 0.7 mg/l), phenol, chlorinated hydrocarbons, aromatic hydrocarbons. To
predict the potential hazard of plastics used for contact with foodstuffs, it is necessary to
have a real idea of the chemical nature of substances evolving from them, the level of their
migration and toxicological characteristics.
To establish the correspondence of the finished article to the hygienic requirements,
special studies should be carried out. They are based on modelling the real conditions under
which polymer materials would be used, followed by the determination of the organoleptic
properties of the contacting media and the level of migration of the chemical compounds.
In an ideal case, migrating substances should be determined directly in food products.
However, the compositions of food products are rather complex, so in most cases it is
impossible to determine particular chemical compounds in them. For instance, milk is a
complex chemically and biologically active system, which includes protein, fat, plasma;
these, in turn, consist of amino acids, casein, albumin etc. The presence of these substances
not only disturbs the determination of separate compounds migrating from plastics, but is
also capable of changing the initial shape of these substances, i.e., to enter into interaction
with them. Nevertheless, a number of highly sensitive assays for determining separate low-
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molecular-mass substances in food products (e.g., solvents, plasticizers, monomers in sunflower oil, milk, curd, cheese) have been developed to date; still, sanitary-chemical studies
are mainly carried out on model solutions, which simulate particular kinds of products by
the most characteristic features.
Solutions of some salts, acids, alcohols serve as model media to simulate the extractability of various food products. In all cases, water is used as one of the model solutions as
the most universal and convenient medium for organoleptic studies and the determination
of the amount of chemical substances migrating from plastics.
Different countries use various sets of model media, which reflect more or less completely the character of major food products. An essential criterion in choosing a model medium is to simulate the factors, which contribute to or prevent the migration of chemical
substances: the consistence of a product, its pH and composition of the salts; the content of
water, fat or alcohol. The greatest attention is paid to liquid and fatty products.
The requirements to plastics used for prepackaging solid food products are less stringent. In some countries, they are permitted to be used without special studies.
In the Russian Federation, 9 model media are used; in the USA, 8; in France, 13; in
Czech Republic and Italy, 6; in Germany, 4. There are certain differences in the composition of model media simulating the same food products, especially of fats, which are proposed to be replaced in tests by olive or sunflower oil, heptane, hexane, diethyl ester.
It is known that aggressivity of food products with respect to polymer materials depends to a certain extent on the content of moisture in them. Therefore, the approaches to
the studies of articles intended for contact with food products of a moisture content of above
15% and below 15% are different.
Almost all model media include water, so for simplicity water-containing products are
simulated by water; fat-containing products, by sunflower or other vegetable oil. As the result of accumulation of experimental data, the principles of choosing simulators of food
products are being reconsidered at present.
The conditions of modelling polymer tests in this country have been accepted to depend upon real conditions of their practical use with some exaggeration.
The specific surface of specimens of a material or articles should correspond to real
operating conditions.
The sanitary-chemical study is preceded by organoleptic studies. Their aim is to reveal
the possibility of transferring a foreign smell and flavour to food products, which are in contact with a polymer material. The organoleptic parameters are determined by tasting and
are expressed in points of smell intensity. Changes of the organoleptic properties of food
products and model solutions contacting with articles studied are due to the transition of
polymer components into them. In this connection, the data obtained in the organoleptic
studies are one of the most important limiting parameters in the sanitary-chemical study of
articles from polymer materials. If the organoleptic examination reveals a change of smell
and taste of a food product or a model medium as the result of a contact with polymer material, this is the reason for banning this material for packaging foodstuffs.
The subsequent sanitary-chemical studies isolate both the total amount of substances
that passed into model media from the polymer composition, and separate components.
Their qualitative composition is determined, i.e., chemical substances are identified and the
character of their migration is defined. The total amount of low-molecular-mass substances
that pass into the media is determined by the so called integral methods. They include the
methods of oxidizability, brominability, dry residue of the extracts. However, neither of the
methods gives the complete idea of all substances migrating into model media. In particular,
80
the oxidizability shows the total content of (organic and inorganic) reducers (in solution)
capable of oxidation under conditions of the experiment, and characterizes the resistance
of the material to water. The brominability testifies to the presence (in extracts) of substances capable of adding bromine, e.g., unsaturated compounds, phenol. The dry residue obtained by evaporation of the extracts at 100105C contains no volatile substances, whose
boiling temperature is lower than these temperatures.
Therefore, major information in sanitary-chemical studies is obtained using the methods that make it possible to determine the migrating substances in a differentiated manner.
These methods include specific chemical reactions, which make use of the ability of
each individual compound to enter into interaction with certain reagents. Usually, such reactions are used, which yield coloured compounds absorbing light in the visible region of
the spectrum. Such a feature of these compounds makes it possible to register the intensity
of the coloration on a photoelectrocolorimeter type of instruments, and, therefore, to determine the concentration of an analyzed substance with greater accuracy.
Such instrumental methods as gas-liquid and thin-layer chromatography, spectroscopy
in the ultraviolet and infrared regions, mass spectrometry, spectrography are also widely
used.
Much attention is paid at present to the elucidation of the regularities of migration of
individual supramolecular components, which is especially important for packagings and
containers for long-term use. In a general case, the intensity of migration is affected by the
physicochemical impact of polymer and medium, the composition and technology of producing and reprocessing a polymer, duration of contact of the product and the packaging.
The migration ability of particular components is described using the diffusion equation,
which gives a possibility of predicting the migration process at different operating conditions. Migration of monomers is well described by the diffusion equations, as in this case
the determining factor is the solubility of the monomer in the polymer.
In a number of cases, migration processes of additives are described by two parameters: D (diffusion coefficient) and S (solubility). When an additive in the model medium is
not very small, migration is determined by diffusion of the polymer additive and changes
proportionally to time raised to the power of 1/2. When additives are very small, the rate of
migration changes linearly.
In a number of cases, the migration process is described taking account of several factors (concentration of a component, temperature of the medium, time of contact), by making
up the regression equation. Mathematical models of migration of this or that component are
being developed.
The chemical nature of the model medium has a significant effect on the character of
migration. It has been found that water, weak solutions of acids and salts evoke a surface
cracking of PE at elevated temperatures, which leads to accelerated migration of lowmolecular-mass substances from these materials. In this connection, the use of such a material as PE should be limited in time at temperatures higher than 60C due to possible
cracking. The amount of migrated substances (solvents, products of heat-oxidation decomposition) often does not exceed the admissible level of migration. However, it deteriorates
the organoleptic properties of food media, which is also inadmissible from the hygienic
point of view.
An insignificant swelling in fats or fat-simulating media is not always a sufficient reason for recommending a material as a packaging for fat. In a number of cases, the determining factor is oxygen permeability of the polymer film, because an increased oxygen
permeability leads to a rancidity of the packaged fat-containing product, as well as to a
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decrease of vitamins in it. Besides, one should pay attention to the fat solubility of polymers low-molecular-mass ingredients: plasticizers, stabilizers, dyes. Only consideration of
all the above factors together enables a conclusion of the expediency of using a particular
material in contact with fat. Owing to a change of its composition, the same polymer can
be used in different applications. One of the oldest polymer materials cellophane has
been widely used in the recent years as a packaging for foodstuffs (owing to its low hydrophilicity and gas permeability due to the application of a lacquer coating on the surface of
the film). This material can be heat sealed, so cellophane can be used as casings for sausages
and cheeses. But new problems have arisen: removal of the residual solvent in the lacquer,
especially from the adhesive layer, the purpose of which is to create a strong bonding of the
coating and the film. If the coating is formed directly on a product, one should take account
of the diffusion of the solvent not only in the air but also in the product. Thus, when applying
a latex coating on a cheese, the residual content of the solvents and monomers is controlled
both in the coating and in the cheese. The sanitary-chemical properties can be improved and
the range of application of the material could be expanded not only by changing the composition of the polymer material, but also by varying particular parameters of the technological process. For this purpose, the technological process is to be optimized with
consideration of definite sanitary-chemical parameters of significance for a given material.
This approach was used to modify the process of producing a combined material based on
polyethylene and cellophane. Besides the major technological parameters, the mathematical model of the process comprised the organoleptic parameter, which is the determining
parameter in this case, and the extent of oxidation of the polyethylene coating surface.
Mathematical treatment of the data made it possible to choose the temperature of PE extrusion on cellophane, at which the organoleptic and other sanitary-chemical parameters of the
material satisfy the generally accepted hygienic norms. The sanitary-chemical properties
often become a determining factor in deciding which of the materials is in this case the best.
The criterion of choosing the material has been developed, which takes into consideration the sanitary-chemical parameters. This criterion is the ratio of the aggregate of the useful properties to the total costs of all the life cycle, which adds up from the expenses for
development, production and operation. This or that hygienic parameter (e.g., oxidizability,
content of solvents, temperature at which a smell emerges) is assigned a certain numerical
value in the abstract scale (1 or 0) and the sum of values for one and the other material is
calculated. For instance, LDPE and HDPE are compared with respect to oxidizability (less
for HDPE), number of solvents (available for HDPE), migration of 3,4-benzpyrene (less in
HDPE), smell (appears in HDPE at a higher temperature). At the same costs, the preferred
material should be HDPE, whose complex parameters of the hygienic properties are 20%
higher than those of LDPE.
Owing to the studies carried out in the recent years, the quality of many polymer materials was significantly improved.
The major way of achieving this are:
increase of the purity of initial raw materials
introduction of nontoxic additives into the composition
selection of the formulations of polymer compositions, which ensure a sufficient
chemical stability of materials
choice of optimal polymer-processing regimes, which prevent the thermooxidative
degradation of material
application of coatings, preventing migration of low-molecular-mass substances, on
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the surface of material

use of additional technological techniques improving the hygienic properties of materials (vacuum treatment, heat treatment, washing etc.).
It is very important that the technological protocol be strictly observed: ingredients of
the composition should not be replaced by others; raw materials should be of the extent of
purification required to produce a hygienically flawless material. The article obtained
should be used only for the intended purpose within the temperaturetime limits required.
The permit issued by the Ministry of Health stipulates the operating conditions of material
or fabricated packagings, and the violation of these recommendations is fraught with
serious consequences for human health.
Having obtained the results of the sanitary-chemical study, the hygienists make a conclusion of the possibility or impossibility of using the polymer material in contact with given products. If it can be used, the operating conditions are stipulated, i.e., the temperature
regime and time interval, as well as specifically the kind of a food product. The same polymer can be suitable for one product and can not be used in contact with another product.
This is explainable by the chemical nature and physical structure of both the polymer itself
and additions in its composition. Such a widespread material as polyethylene is broadly
used for contact with water-containing products, but on a limited scale with fat-containing
materials. And such a polymer as polyamide is intended for fatty products and can not contact with water. It should be noted that there are many ways to modify polymers: impart
them with water resistance or, vice versa, water solubility, fat resistance, gas impenetrability etc. Due to the latter, materials not used previously for certain products can withstand a
contact with them without changing their properties and the properties of the product. Thus,
for instance, the higher homologs of polyolefins possess an increased fat resistance; application of lacquers on cellophane imparts it with water resistance, while coating polyethylene with foil makes it gas-impermeable.
Unsatisfactory sanitary-chemical parameters are a signal for process engineers, who
correct the production process for polymer articles, change the composition of polymer material, choosing such additives, which would not migrate during the contact of the packaging with the contents. When developing new polymer materials, the technological process
should be optimized with account for the hygienic requirements, and this is a guarantee of
the safety of using polymer materials for food packaging.
At present, all regulatory documents for polymers intended for contact with food products include compulsory hygienic parameters, in accordance with which the material is controlled at the stage of its final fabrication.
2.3
Methods of packaging foodstuffs
To preserve a product, it should be packaged in good condition. If it was getting spoiled,

the very perfect packaging would not restore its original properties. Contrarywise, favourable conditions for accelerated spoilage of the product can develop in the packaging. Thus,
for instance, each variety of fruits and vegetables has its most favourable harvest time.
Fruits and vegetables picked up too early do not reach their normal size. Their green
pulp has a grass acidic taste. The coloration and aroma of these fruits and vegetables are
weakly expressed. If prematurely picked fruits and vegetables are put into storage, they
droop and brown faster.
On the contrary, fruits and vegetables harvested too late are infected with various
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diseases and fungal rots. They are susceptible to damage, cold injury, development of floury
texture, have a tendency of rapid overripeness, loss of gustatory properties and vendibility.
On the strength of the above reasons, it is inappropriate to preserve fruits picked later than
the admissible harvesting time. They should be delivered to the consumer as soon as
possible.
The optimal time of harvesting many varieties of apples could be determined by their
colour. Thus, for long-term storage of many varieties of apples they should be picked when
they have a greenish-yellowish coloration with predominant green colour. Fruits intended
for mid-term storage have yellow-green colour, and totally yellowed fruits are not to be
stored.
The strength of attachment of fruits to the fruiting branch is also an indicator of their
ripeness. Overripe fruits are detached by a weak touch.
Experts determine the optimal time of picking fruits by the colour of seeds, content of
sugar and acid in them, taste and density of fruits and vegetables, content of starch etc.
Any damage (punctures, injuries, damage caused by codling moths and scabs, absence
of fruitstalk) are undesirable in putting fruits into storage. In accordance with the State Standards, only highest and first grade fruits are put into long-time storage. Though harvested
fruits and vegetables receive neither water nor nutrients, they absorb oxygen, evolve carbon
dioxide, water, heat and various volatile organic substances. This physiological process is
generally called respiration. The respiration intensity can also serve one of subjective parameters of ripening, ageing and possible duration of product storage. To make clearer how
the respiration intensity change data are used in such cases, consider an example of storing
apples at various temperatures. First of all, let us mention that it is customary to divide the
change of respiration intensity in the fruit ripening period into three phases. The first is characterized by a low level of respiration. The second is characterized by an increased intensity
of respiration. An increase of respiration intensity implies that fruits have ripened. Subsequently, ageing and spoilage of products shall follow. Spoilage begins the sooner the more
intensive the respiration process is. As is usual, the rate of reversible chemical reactions can
be regulated by either changing the temperature or by changing the concentration of final
products in the reaction medium. Therefore, by decreasing the temperature to some limits
or by changing (modifying) the atmosphere, in which the biologically active products are
stored, we can extend the time during which they achieve optimal properties, i.e., extend
the storage time and improve the quality of the products.
Fresh fruits and vegetables are valuable foodstuffs, one of the major sources of providing the human organism with vitamins, mineral salts, organic acids, biologically active
substances essential for life. The output of these products increases each year; however,
their consumption is obviously of seasonal character.
Partly, the problem of long-time storage is solved by using special chambers and storage facilities at a relatively low temperature of refrigerating chambers with artificial refrigeration.
However, storage of fruits and vegetables in refrigerators has a number of disadvantages: losses are still high; storage is possible only to January or February, only some varieties preserve the food merits in the spring period, when the human organism has a special
need for vitamins; too low temperatures cause irreversible biochemical processes in fruits.
Therefore, it is necessary to use advanced methods of storage. One of the promising
methods of storing fresh agricultural produce, which makes it possible to preserve consumer properties for a long period of time is to develop a gas medium, characterized by an increased content of carbon dioxide and a decreased oxygen content.
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This method is widely used abroad. However, construction of such chambers is associated with difficulties of their air-tight sealing, development of special gas mixtures etc.
Development of a modified atmosphere is possible only in storage of fruits and vegetables in polymer films with a given gas, vapour and water permeability by natural accumulation of carbon dioxide and increasing the content of oxygen in respiration of fruits and
vegetables. Harvested fruits and vegetables continue to grow, they absorb oxygen, evolve
carbon dioxide, heat and volatile organic substances. This physiological process of respiration is described in a simplified way by the equation: C6H12O6 + 6O2 = 6CO2 + 6H2O +
674 kcal. However, the respiration process proceeds according to this scheme only if there
is a free access of oxygen, and oxidation proceeds up to the final products. During the storage in a packaging little permeable for air, the access of oxygen to the product is hampered
and oxidation can proceed not to the end, which results in the emergence of visible signs of
the physiological disorder in the metabolism. Therefore, one of the main requirements to
polymer films for storage of fresh agricultural produce is absolute gas permeability.
However, an excessively high gas permeability makes the film little suitable for packaging fruits, because in such films it is impossible to create an atmosphere with an increased
content of CO2 and decreased content of O2. In films with low gas permeability, free oxygen present in the packaging is consumed for respiration over a short period of time, and
the concentration of CO2 may increase up to the limits dangerous for fruits and vegetables
(more than 610%). Therefore, such films are also unsuitable for packaging fruits and vegetables.
Many polymer films possess a sufficient gas permeability, a selectivity of permeability, the extent of which depends not only on the chemical nature of a film, but also on its
thickness, temperature conditions, partial pressure of the gases and other factors. Films
from high-pressure polyethylene (up to 60 m thick) are used in practice; they possess a
certain permeability for CO2 and O2, weak vapour and water permeability and such important properties as high elasticity, strength, chemical inertness, resistance to external factors,
heat sealability etc.
The idea of using film containers with gas-exchange membranes is a further development of the method of storing fruits and vegetables in polymer packagings.
French scientists proposed and realized in practice a method of regulating the composition of the atmosphere in storage of fruits. The method is based on using the selective permeability of silicon elastomer (polysiloxane) for various gases.
The method comprises four steps: storage of fruits using diffusion exchangers, which
are located outside the storage chamber; storage of fruits using diffusion exchangers located
inside the storage chamber using gas-permeable walls from films (for very large premises);
storage of fruits using small storage tanks with windows closed off with a silicon film (soft
containers from polyethylene, of 5001000 kg holding capacity).
One of the technically simplest variants of using the selective permeability of film materials for regulating the gas composition of the atmosphere are soft polyethylene containers.
Fruits are put into storage in these containers in the same way as in common boxes.
Containers are equipped with inserts (windows) from silicon elastomer. The amount of elastomer is the same as in the diffusion exchanger.
After putting boxes with fruits into the container, its top is tightly fastened, after which
the exchange with the outer atmosphere is predominantly through the silicon window.
Diffusion of gases through the window is a function of the partial gas pressure differential on both sides of the membrane, of the type of cloth used in the film and of the thick-
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ness of the coating of the cloth with silicon elastomer.

The choice of siloxane elastomer to be applied on the cloth is determined by the unique
properties of this material: the gas permeability of polydimethylsiloxane (PDMS) is 1520
times as high as that of natural rubber, which has the highest permeability of all-hydrocarbon elastomers.
By their gas solubility, both these rubbers are close, and a higher gas permeability of
PDMS as compared with natural rubber is explained by a considerable increase of the rate
of gas diffusion. This is also confirmed by the fact that the diffusion coefficient is largely
determined by the nature and structure of polymers, whereas the values of the solubility coefficient depend mainly on the nature of diffusing gas or vapour.
Storage of fruits in containers has a number of advantages: there is no need to seal the
premises, and products are stored at a temperature of +2 up to +7C. Therefore, containers
could be used both in artificially refrigerated and noncooled fruit storages. These features
of the container method of storage make it rather promising, in particular, for a broad use
in collective farms and state-owned farms.
The size of containers could be diverse. However, in each case, for a given area of the
membrane, there is a dependence between the weight of stored apples, storage temperature
and a given content of O2 and CO2 in the container. The violation of this dependence can
leads to unfavourable results of storage. Putting fruits for storage should be done as soon
as possible after harvesting.
Successful storage of food products can be ensured only at a correct choice and maintenance of the main factors of storage (temperature, relative humidity, composition of the
atmosphere) not only for fruits of each species and variety, but even for fruits of the same
variety depending on the growth conditions, picking time and duration of storage.
Provision of required temperature and humidity conditions of storage is done rather
successfully by constructing refrigerating chambers. However, even in perfect refrigerating
storage facilities the losses of fruit-and-vegetable produce are considerable, its vendibility
qualities and nutritive value are significantly decreased, all due to premature overripening,
ageing and damage caused by physiological and parasitic diseases.
Creation of a modified gas medium using selectively permeable film materials (SPFM)
deserves special attention, as this method of storage does not require constructing expensive
sealed storage facilities or reconstructing the existing refrigerating chambers. The method
can be also successfully used under conditions of noncooled storages (warehouses, cellars).
Additional expenses for polymer materials are not large and are totally paid off due to the
significant improvement of the quality of fruit-and-vegetable produce and a decrease of natural depletion of weight and losses. The use of this method makes it possible to put the produce for storage in a modified gas medium directly where it is harvested.
A container design has been developed, which enables a secure protection of the membrane from mechanical impacts and its multiple use. The design makes it possible to carry
out tests of storing fresh agricultural raw materials using SPFM and to perform calculations
of the feasibility of this method as compared with the existing method of refrigerator storage
in open standard boxes and containers. When preparing SPFM for applying onto the base
of polymethylsiloxane composition, the so called spread coating method was used.
Package inserts with membranes and filters from SPFM are operated under conditions
of fruit and vegetable storages without the light; the temperature in storages is +2 up to
+7C. If refrigerator chambers are used for storage, the temperature is decreased to 0 to
2C. The further decrease of temperature leads to irreversible cold damage of the fruits
burns, scalds etc. Relative humidity in package inserts is maintained at a high level
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(9599%), which in violations of storage technology leads to the condensation of moisture

on the walls. During the preparation of the membranes, their pasting, as well as in subsequent operation of package inserts, SPFM can be subjected to deformations and mechanical
damage. However, the main requirements to this type of materials is the high level of gas
permeability and the selectivity of permeability with respect to various gases, mainly to oxygen and carbon dioxide.
SPFM are used for long-time storage of fruits and vegetables not independently but as
membranes. The design of vegetable and fruit containers can be different, which depends
on the kind of produce, charge volume and other factors, but they are fabricated mainly from
a food-grade polyethylene film 80200 m thick.
When fabricating package inserts with membranes, and subsequently gas-selective
heat diffusion devices (CSHD) the main problem was to join the gas-selective membrane
with polyethylene and polystyrene, because these materials are of different chemical nature.
Bonding of the membrane to polyethylene was done by two techniques pasting and
heat sealing; bonding to polystyrene was performed by pasting using intermediate materials. As polyethylene packages with membranes are operated under conditions of high relative humidity (9599%) and even of moisture condensation of the walls of the container,
studies were carried out to determine the strength of pasting with adhesive sealant VGO-1
after holding the specimens in water. A prolonged holding in water proved not to have any
noticeable effect on the strength of pasting.
The second technique suitable for bonding a membrane from SPFM to polyethylene
is heat sealing, which consists of the following. A membrane with round holes 35 mm in
diameter along the perimeter with 5-mm spaces between the holes is put onto a polyethylene
package insert with a window in it. A polyethylene-film covering also with a window in it
is put on top of the membrane. They are pressed by a plate heated up to a temperature of
about 130C. Under the action of temperature and pressure, the fused polyethylene of the
covering is sealed through the holes to the material of the insert. The covering is slightly
larger than the membrane, owing to which the material of the membrane is sealed to the
polyethylene package.
The heat sealing method requires less hand labour as compared with the pasting method. Almost all operations can be mechanized. Besides, raw stuff and materials are saved
there are no expenses for undercollar cloth and adhesive sealant; additional expenses for
polyethylene coverings are insignificant.
Initially, tests of storage of fruit-and-vegetable produce were carried out using containers and package inserts with membranes fixed by the above methods. The design of the
package inserts is such that the membrane was located in one of the side walls of a container.
However, the use of such packages on a commercial scale is difficult due to the complexity of their fabrication, difficulty of using mechanized automated lines.
Poor removal of biological heat of the respiration of fruit-and-vegetable produce in
large-volume containers (300-100 kg) leads to the increase of the temperature gradient in
the bulk of the produce.
All these necessitated a further improvement of the method. However, for storage of
small batches of fresh agricultural produce, as well as for special purposes, e.g., for equipping deepwater ships, expeditions, the method of storage in small packages with membranes remains acceptable.
Placement of a gas-selective membrane in the inner cavity of the device made it possible to protect it reliably from mechanical damage and ensure its multiple use. The design
of GSD enabled introduction of the membrane directly into the bulk of stored produce.
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The method of creating a modified gas medium by means of gas-selective devices using a hose polyethylene film is economical, simple and accessible for practical use in nonhermetic storages of all types.
A gas-selective device has the shape of a funnel with shanks and blades, whose inner
cavity has gas-selective elements. The body of the device was fabricated from a food-grade
shock-proof polystyrene sheet 2.53 mm thick by the method of vacuum molding or pressure casting from granulated polystyrene. The gas-exchange section of the device is perforated.
The device is universal and can be used with hose polyethylene film in all kinds of fruit
and vegetable containers manufactured by domestic industry.
During the storage, it is necessary to check daily the temperature regime in the storage
facilities and to sample and analyze the gases in sampled packages in two days for the first
six days and then once a month. Such kinds of produce as garlic, bulb onion and carrot are
stored at a temperature of 01C, and other kinds of produce, at 34C. At a stabilized regime of the atmosphere in a packaging with produce in the visually normal state, the duration of storage is determined by the necessity related to the produce sales time. The
maximum storage time is 79 months. Storage can be terminated in the case of deterioration of the quality of fruits, as well as at a decrease of the oxygen content below 2% or at
an increase of the carbon dioxide content above 67%.
Activated charcoal absorbs ethers evolved in respiration of fruits, aldehydes and acids,
the formation of which is associated with the disturbance of their metabolism, the biochemical and mechanical injuries of tissues, and ethylene which causes accelerated ripening of
fruits. In storage, fruits are subjected to microbial spoilage, one of the major means of controlling which is to use substances suppressing the development of microorganisms.
Gathering the harvest into
polymer containers with GSHD
Stockpiling
Modular storage
Sales of produce
Sorbic acid is the most efficient of acid antiseptics; it is absolutely tasteless and has no
smell. Its salts (e.g., potassium or sodium sorbate) as aqueous or aqueous-alcoholic solutions are as efficient. Introduction of activated charcoal and any antimicrobial preparation
into the packaging makes it possible to remove excess ethylene and volatiles evolved by
fruits, and also to inhibit the processes of microbial spoilage. For this purpose, a porous hydrophilic material treated with a suspension of the antiseptic and activated charcoal is
placed at the point of fixation of the membrane, as the most suitable place; it is placed from
the inner side of the membrane facing the fruits. Papers of sufficient strength, e.g., kraft,
cloth, paperboard etc. can be used as a hydrophilic porous material. The suspension can be
applied by spraying, immersion or passing between rolls. When carrying out the works, cotton calico impregnated by immersion into a suspension of activated charcoal and sorbic acid
in acetone was used as a porous hydrophilic material. After drying, a gasket was cut from
this material. The size of the gasket was equal to the size of the gas-selective membrane
used. The gasket was placed from the inner side of the membrane. In the case of using the
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gas-selective device for storage, the gasket was placed between the membrane and perforated wall of the GSD. The gasket was fixed the way the membrane was fixed, by adhesive
sealant VGO-1. Storage was performed in unsealed facilities at a temperature of 13C.
Analyses established the food components of fruits to be better preserved in storage in
a modified atmosphere than in a common atmosphere. Noticeable changes were observed
to occur in the content of total sugar, pectins and tannins. The development of an anaerobic
exchange is indicated by the amount of alcohol and acetaldehyde. Under conditions of a
modified atmosphere, accumulation of alcohol and acetaldehyde was observed to be insignificant, owing to which apples stored under these conditions had no physiological diseases.
The economic effect of storing apples in containers with GSD is due not only to the lower
expenses for storage, but mainly due to the increased vendibility of apples.
The recommendation to store food products of only good quality refers not exceptionally to the storage of fruits and vegetables. It is equally valid with respect to other products:
meat, dairy, fish etc.
The meat of a just-killed animal usually has a glossy surface, dark red colour and rubberlike consistency.
After cooking, green meat is usually coarse and is difficult to chew. The smell of such
a meat is weakly expressed due to the absence of aromatic substances. Usually, this meat
is said to be tasteless. Therefore, fresh meat should be subjected to maturation, during which
it becomes tender, juicy and aromatic. Herewith, under the action of enzymes there occur
autolysis, degradation of proteins to polypeptides and amino acids, and breakdown of the
carbohydrate system of the muscle tissue to simpler substances. This leads to the accumulation of lactic and phosphoric acids in the musculature and a shift of the reaction of the
medium to the acidic side. The pH values of the meat vary between 5.6 and 6.0. Part of tightly bound water passes to loosely bound water. Only after biochemical changes in maturation, meat acquires a tender consistency, becomes juicy, and has an expressed aroma and
taste.
The maturation time depends on the quality, integrity and assumed use of meat. The
course of the maturation process also depends on temperature, kind of animal, its age, sex,
on management and feeding conditions prior to slaughtering and its condition during the
slaughtering.
At present, carcasses, half-carcasses or quarters are first cooled for 2448 h at a temperature of 0C and relative humidity of 8590% and air conditioning. At a low air velocity, the temperature inside the meat should be from + to +2C. Herewith, a dried up layer
is formed on the surface of meat. After that, the carcasses are hung up and held in a refrigerator approximately at a temperature of +2C and 85% relative humidity. Air velocity
should be such that to prevent unnecessary losses of mass at these temperature and humidity
regimes. At a higher temperature, meat becomes more tender and matures faster. During
the maturation, it is necessary to observe hygienic conditions and, as far as possible, to
avoid temperature variations of more than 1C.
Under the above described conditions, beef matures in 814 days; pork, about 3 days;
veal and mutton, 37 days.
Losses of mass in maturation of meat according to the described method are rather significant. They differ depending on the species of animal, its age and the properties of meat,
and make 2.55% on average. Dressing losses owing to the removal of dried and
dark-brown parts of carcass surface (facings) are to be added to losses of mass after maturaion. The dressing losses are, as a rule, 1.52%. Thus, the total losses reach 47%, and
in hanging of individual slabs of meat, even 12%.
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After maturation, meat should be consumed as soon as possible; otherwise, it is difficult to prevent further losses.Veal and pork do not withstand a long-time storage at the given
temperature regimes. The storage time of meat at a temperature of 0 up to 2C in a refrigerator can be increased significantly owing to the introduction of 1015% carbon dioxide.
The above described method of preserving the quality of meat by its hanging and cooling is widely used, e.g., in Germany.
In Germany, a special composition was developed, which makes it possible to preserve
meat fresh for five days even at a temperature of 35C. According to the proposed method,
a freshly slaughtered carcass is immersed for 10 sec into a solution of maize starch, cooking
salt, sugar and fruit acid. Experimental checks found this composition to prevent the activity
of salmonella, which cause food poisoning.
For more long-time preservation of the quality of meat, it is kept in frozen state. Deep
freezing is considered to be the best method of meat preservation. Freezing at a temperature
of 40C and strong air motion with high humidity, followed by storage at 18C in the
dark guarantees the preservation of the quality of cattle meat for 1012 and of pork for 46
months; when stored in the dark at 30C, cattle meat is preserved for 2224 months; and
pork, 1315 months without the change of quality. During the storage in a frozen form, the
losses of vitamins, especially vitamin B, are slowed down.
If unpackaged meat is stored in the frozen form, then in storage from 18 up to 20C,
relative humidity of about 90% and good air conditioning, the losses of mass of meat are
considerable.
In freezing, the losses of mass of cattle meat are from 1 up to 2%; and of pork, from 1
up to 1.6%. The losses of mass after 3 months of storage in the frozen form reach, as a rule,
2.23.2% in cattle meat, and in pork, 1.52.0%. The losses strongly vary and depend first
of all on the kind of meat, as well as on temperature and duration of freezing. During the
freezing in a frozen form, meat not only loses its mass but is subjected to other changes,
including the denaturation of proteins and oxidation of fats. These processes also depend
on temperature and time, as well as, in this case, on the action of light; herewith, the
short-range region of the spectrum is especially efficient. The freezing conditions are also
significant for the above processes. In deep freezing, the changes of products are little tangible, because a thin structure of crystals is formed, and, owing to their small growth rate,
a smaller amount of water contained in the cells passes into the intercellular space. At
non-deep freezing, water contained mainly in the intercellular space freezes. Herewith, a
small amount of large crystals is formed, which grow at a large rate, and the muscle tissue
loses much water, and connective tissue is broken. The longer the freezing process is, the
more time it takes for water to diffuse from the muscle fibres or cell protoplasm owing to
the osmosis. The protein being in solution gets denatured owing to a change of the concentration. Water permeability of the cell wall changes. These changes are largely irreversible,
and in the subsequent thawing the meat looses a large amount of cell sap, which contains
nutritive and flavouring substances.
Freezing of meat by liquid nitrogen (196C) is the fastest method of freezing, which
finds an ever wider application in Western practice. Due to evaporation of liquid nitrogen,
this type of freezing prevents the structural changes better, as the result of which the freshness and flavour of meat are preserved till thawing even after long-term storage. Colourless,
tasteless nitrogen changes neither the smell nor the taste nor the colour of meat. It does not
enter into chemical interaction with the product. Owing to an extremely large temperature
difference, the freezing lasts only several minutes.
Technically developed countries use the newest achievements in meat industry and
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avoid losses of mass by means of storing and freezing meat in polymer films. The basic requirements are reduced to the above mentioned sanitary-hygienic norms, which should be
observed in storage of meat.
Besides banning polymer films, from which ingredients of the polymer composition
can migrate into meat, a number of requirements are imposed upon films. They should possess the following properties: protect meat from harmful external effects; not to change the
taste and smell of meat; prevent the loss of flavour; possess a high mechanical strength, as
well as the capability of non-penetration of microorganisms; not to lose the operating properties with temperature changes; possess the required water and vapour permeability and
have the given values of gas impermeability and fat resistance; possess a flexibility and acquire the shape of the packaged product; packaging into the film should be easy and economical not only manually, but also in automatic machines; films should be transparent and
easily printable. Besides, they should be sufficiently cheap so that the economy from reducing the losses exceeds the packaging costs.
The main requirements of foodstuffs hygiene, as well as the technical requirements are
satisfied with respect to polystyrene films, combined polyesterpolyethylene films, as well
as certain polyamidepolyethylene combined films and other films.
Polyester films have a number of advantages. Their mechanical strength is so high that
a thin film can not be torn by hand. Polyester films can be used for fabricating vacuum packagings. They preserve their operating characteristics within admissible limits in the temperature range from 200C up to +255C. This means that foodstuffs packaged into polyester
films can be sterilized by boiling in water or by steam heated up to 120C. Products packaged into polyester films can be scalded, boiled, steamed, stewed, grilled, dried. Along with
this, these films can be used in freezing products by liquid nitrogen down to a temperature
of 196C. As polyester films possess a certain rigidity, air bubbles are inevitable in polyester packages. The film should adhere tightly to meat along the entire surface, otherwise
air cavities with a high relative humidity emerge.
Polyester films belong to a few artificial packaging films, which have an insignificant
permeability for carbon dioxide.
Many polymer film materials are characterized by the dependence of gas permeability
on humidity. Thus, the oxygen permeability of combined (polyamide/polyethylene) films
with an increased relative humidity increases. The oxygen permeability of polyester films
is absolutely not affected.
Packaging of cattle meat into water-, vapour- and gas-impermeable films for maturation and cold storage has significant advantages. Thus, for instance, the quality of meat can
be preserved especially completely during the storage in a refrigerator if the package is
filled with a gas of a certain composition: a mixture of 8590% nitrogen and 16-10% carbon dioxide. This composition favours the storage of meat at a temperature of 0 to +2C.
Nitrogen serves as an inert gas medium. Carbon dioxide evolved in maturation of meat begins to act, preventing the spoilage at a low temperature and a weak concentration of CO2
only in several weeks.
A favourable effect of carbon dioxide is based on the inhibition of the development of
microorganisms. A possible change of coloration due to the microbial metabolism is slower
in this case.
The concentration of carbon dioxide greater than 1015% is undesirable, because the
further increase of the concentration is accompanied by an increase of CO2 diffusion
through the packaging film, owing to which only a limited part of carbon dioxide will be
absorbed by meat fluid.
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Application of polyethylene terephthalate (polyester) films for meat packaging makes

it possible to avoid the use of nitrogen. Meat can be separated from bones and cut into slabs
from a quarter carcass of a temperature plus 12C and pH 6.2 immediately after cooling.
This should be done if possible in 24 days after slaughtering.
Meat of only good quality should be used for storage in films.
Cutting and packaging should be performed in facilities with a temperature of plus
812C for 2040 min. Therefore, it is important that prepackaging and packaging premises be near refrigerators.
Meat of 3 up to 10 kg weight can be packaged into polyester thermosetting packages,
as well as packages from combined films, one of the layers of which is a polyester film.
Thermosetting films are those that shrink at a short heating up to a temperature of plus
685C.
Films acquire this property as the result of a preliminary biaxial stretching. After the
action of the deforming force is removed, the resultant structure of the films becomes unstable. Transition to the stable structure after the external mechanical action is removed can
be delayed either by keeping the film frozen under the operating conditions, so that it is
in a glass-transition state, or else the structure of the film formed in the process of orientation is fixed by rare crosslinks, which link the chain macromolecules into a three-dimensional network. If this system is warmed up, the rare crosslinks would not withstand the
tendency of breaking down the segments of chain macromolecules under the action of the
heat development of microorganisms on the surface of meat. Simultaneously, the danger of
deterioration of the quality of meat (appearance, smell and taste) is decreased. Application
of absorbing pads contributes to the increase of storage time and improvement of the quality
of meat.
Herewith, it should be taken into account that, with a pad for absorbing meat fluid, the
loss of mass is approximately 0.8%. Addition of absorbing material should correspond to
the expected loss.
Packaging into films is also recommended for storing frozen meat. This prevents its
loss of mass, change of coloration etc. In this case, its aroma, vitamins and nutritive value
are preserved. In impermeable films, packaged slabs of frozen meat preserve their useful
properties longer. While packaging into dense films is acceptable for maturation and refrigerated storage of only cattle meat and, on a limited scale, of veal, packaging of frozen meat
into impermeable films is suitable for all kinds of meat. For meat to be well preserved in a
packaging, its quality should be perfect. Meat should be packaged into a proper film with
all rules observed, quickly frozen and properly stored (23 weeks at 02C, maturation and
storage).
Meat of cattle should be matured prior to freezing; the maturation process is almost
stopped by freezing, and thawed meat matures worse due to the known structural and biochemical changes. At room temperature, such meat remains hard for a long time. Good maturation before freezing is required, first and foremost, for slabs of meat intended for
cooking.
Packaging of meat in water-, vapour- and gas-impermeable packages from polyester
films or from polyester combined films for maturation, as well as for storage in frozen condition is an especially effective technique for preserving the nutrients and reducing the losses. Meat matured and stored in packages, as compared with that matured and stored without
packaging, has the following advantages: it is protected from contamination and microbes,
drying, oxidation, discoloration, loss of aroma. Besides, its storage time and quality increase. Such a meat has a greater nutritive value, it is more succulent and tender, and has a
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better aroma. Storage of packaged meat allows a stronger circulation of air in the refrigerator.
Losses of mass in maturation and storage of meat in a refrigerator are restricted to exudation and make 12.5% on average, whereas in usual maturation and storage without a
film they reach 47%.
Due to the use of respective film packages, losses in maturation and storage of meat
can be decreased by two thirds on average with simultaneously better maturation and increased storage time. Meat in impermeable film packages shows no considerable losses of
mass not only during the freezing, but also in storage.
Dressing of carcasses, as well as cutting of meat and its processes can be more rational
and with a relatively smaller labour input.
Storage and transportation of packaged meat in stacked boxes or dispatch in cases increase the labour productivity, make it possible to use the premises more rationally and increase the load-carrying capacity of vehicles by almost 22%.
Packaging of frozen meat into vacuumed packages enables hygienic lossless thawing
in a bath with cold water, which is economic from the point of view of time and energy expenses.
Based on modern achievements of polymer chemistry, synthetic films and materials
on their basis have been created, the use of which for protection of meat and meat products
from spoilage in combination with artificial cold make it possible to significantly reduce
normal wastage and ensure the sanitary well-being of a product.
Fabrication of meat and meat products in a packaged form contributes to the solution
of an important social problem economy of socially useful labour during the sale and consumption of prepackaged products on the market, in catering trade and in housekeeping.
Unfreezing of products in microwave ovens takes only several minutes, so meals should be
prepared in such ovens in packages from polyester films of the type of SP-2.
When using polymer packagings for meat and meat products, the effect of external factors vacuum or modified atmosphere with a low content of oxygen in the packaging on
the complex multicomponent biological system can vary depending on its state, which is
determined by the character of the physicochemical and biochemical processes in muscle
and fatty tissue.
The need to solve the problem of increasing the duration of refrigerator storage of
chilled meat invariably increases as the technological processes of meat production are improved.
Apart from the general increase of meat production, volumes of stored meat in chilled
state increase, the assortment of semifinished meat and meat products becomes broader.
Storage in chilled state using film materials makes it possible to preserve the food nutritive value of products, to decrease losses of mass, to improve the sanitary state of products
and sites of their production, storage and sale.
At present, great attention is paid to novel methods of storing chilled meat, which are
based on vacuumizing and use of modified atmosphere. This required the development of
novel film materials, which possess an increased gas, vapour and moisture permeability;
special equipment and qualified personnel.
From the practice of storing fresh agricultural raw materials and ripening of cheeses,
it is known that the gas composition inside polymer packagings can be modified using film
materials, which possess a selective permeability for carbon dioxide, oxygen, nitrogen and
other gases.
Selectively permeable film materials (SPFM) are used as membrane inserts of soft
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polymer containers.
Changes of the gas composition in packages occur in accordance with the generally
known gas diffusion law, whose driving power is the difference of partial pressures of the
gases on both sides of the material. Owing to this, gas is transferred from the zone with a
high partial pressure to that with a lower partial pressure up to a point of a certain equilibrium.
The rate of the onset of an equilibrium state of the gas phase inside a packaging depends on the selectivity of material of the insert; the rate is assessed by the ratio of the
amount of one gas to that of the other, which pass per unit of time through a unit of 1 atm.
Thus, prerequisites are established for studying the possibility of using gas selective
materials for storage and transportation of chilled meat.
Some of the products, for instance, dry kissels, concentrates of first and second courses, desserts, dry beverages (coffee, cocoa, etc.), freeze-dried food products, etc. readily absorb moisture. Even small amounts of moisture, oxygen and light cause spoilage of
freeze-dried products, instant coffee, babys formulas. These products are well preserved
in vapour-, gas- and light-impermeable packaging, best of all, under conditions of deep vacuum or in an inert gas atmosphere. Dry food products may disturb the integrity of a packaging. Therefore, the requirements to their strength characteristics should be more stringent.
Thus, during the packaging of cereal concentrates into lacquered cellophane the layer of lacquer is damaged by particles of a cereal.
In vacuum packaging, the mechanical impact of a dry product on the material is noticeably increased, which leads to the necessity of using multilayer films based on polyethylene terephthalate. Modern weighing-and-packaging machines exert a considerable
mechanical impact on polymer film materials. This equipment is intended to be used at high
speeds (their performance often exceeds 100 packagings per minute). Packaging material
for this equipment should be strong, have a smooth surface and low friction coefficient. In
most cases, the use of soft, low-strength polymer film materials is inadmissible on modern
weighing-and-packaging equipment. Materials should be sufficiently strong, such as combined materials from paper, aluminium foil, cellophane, polypropylene, polyethylene
terephthalate etc. In a number of cases, e.g., in packaging cloves, cinnamon, coriander, laurel leaf powder, food concentrates, instant coffee etc., a high air tightness is required. Attention should be paid to the fact that a high initial humidity of a product at its airtight
packaging leads to the condensation of moisture on the inner side of the packaging and the
development of mold. Therefore, before packaging, one should be sure that the concentrates
are sterile or else to add a preservative. Thus, it is recommended to add about 0.02% of sorbic acid to kissel concentrates. The maximum admissible moisture content for instant coffee
is 67%.
Packaging of food concentrates into paper or cellophane with a polyethylene coating
enables increasing their shelf lives 1.5-fold, and packaging into combined materials based
on aluminium foil, more than 2-fold as compared with packaging into parchment or imitation parchment paper. The shelf lives of some milk concentrates, such as coffee with milk,
cocoa with milk, cocoa with cream, coffee with cream and scalded cream in paper or cellophane with a polyethylene coating increase twofold as compared with those in imitation
parchment or in labelling paper.
At present, products with a high content of fat store well in combined packaging materials based on paper, cellophane, aluminium foil with a grease-resistant coating based on
copolymers of vinyl chloride with vinylidene chloride, ethylene with vinyl acetate. These
coatings are applied as a melt and water emulsions latexes. Fatty products store well in
94
containers from cellulose derivatives ethrols. Food concentrates of the first and second
courses are well stored in combined materials based on aluminium foil. Herewith, it is recommended to add into the fat-containing concentrate of a food product an oxidation-preventing substance, e.g., dodecyl gallate (up to 0.01% of the weight of fat).
Application of paper with a coating from polyethylene (viscotene) or cellophane with
a polyethylene coating (PC-2, PC-3, PC-4) instead of imitation parchment makes it possible
to increase the shelf life of milk concentrates from 34 up to 68 months. For packaging
of dry products from potato, the following are successfully used: for semifinished crackers,
a polyethylene film and paper with the polyethylene coating; for roasted crackers, PC-2
film; for potato crisps, a film from a mixture of different grades of polyethylene, PC-2, etc.
For packaging of dried potato with a moisture content of 68%, four-layer kraft paper bags
with a double polyethylene coating were successfully used. In this packaging, the product
was stored up to 6 months without losing its edibility characteristics. Freeze-dried fruits,
berries, purees and other products store well in glass and tin cans. However, this kind of
containers have drawbacks: they are brittle, unsuitable for transportation (glass containers),
they corrode (tin cans), their weight is large (sometimes exceeding the weight of the contents nine times). Therefore, more advanced containers for these products are made from
polymer films, e.g., lavsanpolyethylene (SP22), films based on aluminium foil plied up
with polypropylene or a mixture of certain brands of polyethylene (steralkon, lamister, folgoplen), polyethylenepaperfoil, etc. Materials based on foil with application of a polyethylene film or SP-2 film possess the best protective properties.
As food products degrade, there occurs decomposition of vitamin C. The better a container is, the slower the decomposition of ascorbic acid proceeds. The efficiency of the protective properties of containers could be judged by the change of coloration of products in
storage, as well as by the change of the composition of aromatic compounds present in the
food product.
Airtight packaging of food concentrates can be done into packages from polymer and
combined materials on packaging lines. For this purpose, both Russian equipment (e.g., of
the type of the KMKh-75 automatic machine) and Western equipment (e.g., of the company
Hassia GmbH) are used.
Granular food products, e.g., corn flakes and dry breakfasts, are packaged into rectangular boxes from chrom-ersatz paperboard (240250 g/m2) with the inner package insert
from thin paper (4070 g/m2) coated with polyethylene. This line is manufactured by the
Swedish company Cristiagren.
The tendency of manufacturing food products both in this country and abroad is that
products of a high degree of preparedness become more widespread. In particular, frozen
ready-prepared meals, semifinished products, fruit-and-vegetable juices, etc., are offered
for sale in increasing amounts. Packaging of food products intended for freezing can be carried out by various methods. Thus, for instance, trays fabricated from an aluminium alloy
with several divisions are used for this purpose. The inner surface of the trays was covered
with a corrosion-resistant lacquer; its upper surface was finished with lacquered aluminium
foil, which was sealed to the lips of the tray. For packaging of frozen products, containers
from polymer materials are used, sometimes in combination with traditional materials. Attempts are made to fabricate containers withholding the sterilization by boiling followed by
warming-up in hot water. Packages from a polyethylene terephthalate film plied with a
polyethylene film are used for this purpose the most. A package fabricated from such a material (e.g., from SP-2 film) is transparent, which makes it possible to see its contents. The
main requirements to the material for packaging frozen ready-prepared meals are as
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follows: its use should be permitted by the State Sanitary Inspection for contact with a given
concrete product under concrete conditions of storage, transportation, sale and use; it should
be sufficiently processable and economical, airtight, strong and elastic.
For a material not to become brittle at a deep freezing to minus 5060C or refrigerator
storage at minus 2030C, it should be sufficiently elastic. Besides, packaging material intended for prepackaging frozen ready-to-eat meals should withstand rapid defrostation and
warming-up of the packaged product in boiling water.
As the packaged food product is protected by polymer material, it proves to be possible
to use for its freezing the most progressive method of contact freezing. This method is performed in contact plate freezers or in refrigeration brines. The packaging prevents the product from spoilage by burns. Slowing-down of the chemical reactions at low temperatures
enables the use of polyolefins, such as polyethylene and polypropylene, in contact with fatty
products.
Frozen ready-prepared meals, as a rule, are packaged either into packages from
single-layer or multi-layer polymer materials, or else into boxes of various designs with
thermoplastic coatings.
Type of food product
Dried fruits and vegetables

Corn products (popcorn, cornflakes), oat diet products,
kissels, dried potato puree and
other dry products containing
no fat
Potato fried in oil (chips,
crackers)
Food concentrates (first and
second courses) containing
no more than 1015% fat
Food concentrates containing
more than 15% fat
Milk concentrates (based on

coffee, cocoa)
Instant coffee
Spices and food additives
Recommended kinds of packing materials

Non-long-term storage
Long-term storage,
stringent storage conditions
Polyethylene-coated kraft paper

Polyethylene-coated cellophane
Polyethylene-coated paper and
paperboard
Polyethylene film
Polyethylene-coated polyester
(lavsan)
Polyethylene-coated aluminium
foil (lacquered on the outside)
Lacquered cellophane
Fat-resistant copolymer-coated
paper
Polyethylene-coated paper.
Lacquered aluminium foil with

fat-resistant copolymer coating
Lacquer aluminium foil,

paper polyethylene
Lacquer paper, aluminium
foil polyethylene
Fat-resistant copolymer-coated Lacquer aluminium foil,
paper and paperboard
paper fat-resistant copolymer
Fat-resistant copolymer-coated coating
cellophane
Lacquer paper, aluminium
foil fat-resistant copolymer
coating
Polyethylene-coated cellophane Cellophane aluminium
foil polyethylene
Cellophane aluminium foil Cellophane aluminium
polyethylene
foil polyethylene
Lacquered cellophane
Cellophane aluminium foil
Polyethylene-coated cellophane polyethylene
Cellophane aluminium
foil copolymer coating
(of the type of CVC)
96
(continued)
Type of food product
Recommended kinds of packing materials

Non-long-term storage
Freeze-dried food products

(humidity 23%)
Polyethylene-coated lavsan
Cellophane aluminium foil
polyethylene
Long-term storage,
stringent storage conditions
Lavsan aluminium foil
polyethylene
Polyethylene lavsan
adhesive lavsan polyethylene; polyethylene lavsan
adhesive fluoroplastic
polyethylene; lavsan aluminium foil polyethylene
aluminium foil polyethylene
Packages from polyethylene terephthalatepolyethylene SP-2 are characterized by the

range of working temperatures from 70 up to +120C. Ready-prepared meals are frozen
at these temperatures at a temperature of minus 6070C, and unfreezing and warming-up
can be performed directly in the package. It takes the customer a minimal time to prepare
the frozen product for consumption. If the frozen product, e.g., the first or second course,
is to be consumed in the hot state, its preparation would take a maximum of 12 min or less
if a microwave oven is used. If the frozen meal is to be consumed in the cold state, e.g., it
is a dessert, then its preparation requires about 1 min. After the preparation, the product can
be put from the package into dinnerware by cutting one of the sides of the package.
Frozen meals can be packaged into films either from high-density polyethylene or
from a mixture of low- and high-density polyethylenes. These films withstand sterilization
in boiling water at 120 and even 130C, they are more transparent and more resistant to fats.
Films from polypropylene are well heat-sealable. Films from polyethylene terephthalate are
characterized by even better protective properties. They withstand the action of low (minus
4460C) temperatures and boiling in water at 130C, are low-permeable for vapours and
gases; are characterized by a good resistance to attrition and impact loads. Their disadvantage is poor heat sealability, which in practice makes impossible the use of these films on
automatic packaging lines. Therefore, the polyethylene terephthalate or, as it is often called,
polyester film is plied with a film from polyethylene or polypropylene. The polyethylene
terephthalate film provides for such properties of the material as strength, resistance to attrition, gas impermeability.
The inner layer from polyethylene or polypropylene ensures the heat sealability of the
material. Its disadvantage is that it is in short supply and expensive.
As we mentioned above, storage of the most biologically active products or in prolonged storage times of food products requires that packaging material has a combination
of high protective properties and light permeability. In these cases, multilayer polymer film
materials are successfully used, one layer in which is aluminium foil.
Such a type of packaging material, e.g., for packaging infants food, was developed at
the Moscow Technological Institute of Meat and Dairy Industry together with workers of
from the Paper-and-Packaging Plant of the Ministry for Meat and Dairy Industry. It was
called folgoplen. Cellophane from an unreeling roll is fed to the plying rolls of a Werner
and Pfleider line. Before the bands of cellophane and aluminium foil are pressed together
by the rolls, a thin layer of polyethylene melt is to be put between them on the cellophane
surface. This thin layer is to paste cellophane and foil together. This operation produces a
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three-layer (cellophanelow-density polyethylenefoil) film. This material is made heat

sealable by applying a polyethylene melt on the foil. The layers of polyethylene melt applied from above are not pressed one to another until the polyethylene melt hardens. Therefore, to provide for a sufficiently good adhesion of the layers one to another, the
polyethylene melt is applied at a high temperature of the order of 270C. At this temperature, intensive oxidation of polyethylene is initiated. The active centres formed in polyethylene molecules are capable of interacting with the packaged product, causing undesirable
chemical reactions, which lead to spoilage of the packaged product. An example of these
reactions is the rancidification of fat. To avoid such phenomena, one more layer of polyethylene is applied on the surface of the oxidized polyethylene layer at a temperature sufficient for it to melt but insufficient to be oxidized.
To increase the strength of adhesion at as low temperature as possible, the surface of
films is treated by a corona electric discharge.
Besides folgoplen, other light-impermeable materials with high protective properties
are polyethylenefoilpaperpolyethylene, cellophanefoilpolyethylene and others.
As for boxes from paperboard, chrom-ersatz or dense paper coated with a layer of thermoplastic polymer, the following combinations are the most recognized: the outer layer
paraffinepaperthermoplast; paper can be replaced by chrom-ersatz. The material consisting of paraffinepaperaluminium foilthermoplast is widespread. In all combinations
considered, the inner layer is a thermoplast, which is polyethylene or polyvinyl chloride,
polyisoprene hydrochloride, saran (copolymer of vinyl chloride CH2=CHCl with vinylidene chloride CH2=CCl2), compositions of copolymers with paraffine.
Great importance is attached to the expansion of production of ready-prepared meals,
including frozen stuff. To date, many frozen ready-to-eat meals are manufactured, such as
meat balls in red sauce, stewed beef, beef goulash, minced beefsteak, kidneys in red sauce,
stewed pork. Two portions of these meals are packaged into paperboard boxes 1207050
mm in size. A similar packaging for four portions is also used. In this case, the paperboard
box is 1809050 mm in size. Inside, boxes are layered with lacquered cellophane. The
packaged product is frozen in fast freezers at temperatures of minus 3040C for 23 h.
Within this time, the temperature in the bulk of the product reaches 18C. At approximately this temperature, ready-to-eat meals are stored in refrigeration chambers for up to one
year. Frozen meals are transported at temperatures not higher than 15C. In trading networks, they are stored at a temperature of 18C. In five months of storage at minus
1820C, frozen ready-to-eat meals, packaged into a paperboard box with an insert from
lacquered cellophane and heat sealed, lose from 1 up to 3% of their initial weight.
Frozen fruit juices preserve well their valuable nutritive properties in polymer containers. Being packaged into bags from the polyethylenecellophane film PC-2, frozen fruit
juices preserved their taste, colour, flavour, vitamin content for three years of refrigeration
storage at a temperature of minus 1820C. These results were obtained in storage of frozen
apple, grape, tomato, cherry, black-currant etc. juices. Similar results were obtained in storage of these juices in packages from paper with a polyethylene coating and from multilayer
film material (cellophanealuminium foilpolyethylene).
Commercial production of frozen juices tomato, apple and grape in Tetra Pack
packages was introduced. The packaging material was paper with a polyethylene coating
on one side and with a thin layer of paraffine on the other side. This material was first sterilized by irradiation by a bactericidal lamp, and then was converted into a hose by wrapping
and heat sealing the longitudinal seam. Sterilized fruit juice was fed to the hose thus obtained. The transverse sealable elements form a chain of tetrahedral packages cut from the
98
hose. The cut tetrahedra are put into transport containers. After packaging, the juices are
immediately frozen in fast freezers. The freezing takes 3.54 h.
The described freezing method, in contrast with thermal preservation of, e.g., tomato
juice, enables preserving a major part of vitamin C, whereas the microbiological characteristics (bacterial content) in storage of frozen juices at 18C for one year do not change in
practice. Frozen juices are defrosted in the package. If the unfreezing is done in the air, its
duration is 56 h; in flowing water, it lasts 1.01.5 h. Unfrozen (defrosted) juices are stored
in the package in different ways depending on the conditions: at room temperature, no more
than 24 h after defrosting; in a domestic refrigerator, for up to one week; and in refrigeration
cabinets of trading networks (at a temperature of 8C), for up to two months.
Automatic lines similar to those described enable packaging of spreads (jams, creams,
concentrated fruit-and-vegetable juices) also in packages from polymer and combined materials of the type of PC-2. Packages from paper with a polyethylene coating are also used;
sometimes, even simply from polyethylene.
Concentrated and natural juices, sauces, syrups, fluid food concentrates in general are
at present packaged either into paper or paperboard containers with a polymer coating, or
else in bottles or canisters from polymer materials. Fluid preserved products are successfully packaged into rectangular and tetrahedral containers. The prepackaging of natural and
concentrated juices into these containers, which are characterized by a high airtightness, is
similar to that of long-storage milk into tetra packs. Such packaging lines (Tetra Pack Aceptic) were developed by the Swedish company Tetra Pack and found wide use not only for
packaging milk but also for aceptic filling of fruit-and-vegetable juices and other fluid food
products.
A combination of paraffinepaperaluminium foilpolyethylene is used as a material
for packaging fruit-and-vegetable juices. This material is passed as a band through a bath
with a hydrogen-peroxide solution and is used to form a continuous tube with the continuous sealable seam. The inner surface of the tube is warmed up by an infrared source to eliminate the remaining hydrogen peroxide and for additional sterilization. A food product is
fed to the sterilized tube. Naturally, the bottom of the tube is sealed by the transverse seam.
The transverse sealable seams are implemented by means of sealable elements, as the tube
is filled with a food product. The continuous chain of tetrahedra formed in this way is cut
into separate packagings.
The packaging material used for these purposes it consists of the outer layer of paraffine or lacquer, then paper, aluminium foil and the inner layer of polyethylene is characterized by the capability of being heat-sealed and forming airtight packagings. It protects
well the packaged product from microorganisms, light, oxygen, air; and prevents the loss
of moisture. In such a packaging, it is possible to store natural or concentrated
fruit-and-vegetable juice under usual conditions for up to one year.
Polymer materials characterized by a high gas impermeability are also used for storage
of sterilized food products. In this case, the bactericidal action of gaseous chlorine, formaldehyde, propylene oxide, ethylene oxide and other gaseous substances is used. In preservation of food products in polymer packagings, it is natural to use only hygienically
harmless gaseous ethylene oxide and propylene oxide, as well as a mixture consisting of
60% ethylene oxide and 40% carbon dioxide. Under usual conditions, inhibition of the microflora in such a gas mixture takes 46 h. To provide for the safety (to exclude the possibility of explosion), mixtures of ethylene oxide or propylene oxide (no more than 17%) with
such inert gases as nitrogen, carbon dioxide, freon, etc. are used. The process is accelerated
by increasing the pressure of the gases up to 68 kgf/cm2. The thickness of the walls of the
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polymer packaging should not exceed 60 m.

Sterilization of food products by gaseous substances can be done not necessarily in
polymer packagings with good gas permeability. If a product is packaged in an airtight
package from polymer material with low gas permeability, the polymer package is vacuumized, filled with a bactericidal mixture of gases and sealed. In this case, the materials
used are based on foil, such as cellophanealuminium foilpolyethylene,
cellophanepolyethylene. The absence up to the present of domestic packaging materials
of the type of lavsanfoilpolyethylene mixtures, lavsanpolyethylene, etc. is due to the
lack of supply of polyethylene terephthalate. Its high cost as compared with cellophane is
compensated by the adaptability of the packaging process and a high quality of the packaging.
The specific properties of these materials are especially pronounced in packaging thermally preserved food products. This preservation can be performed both at 100C and at a
higher temperature. In the former case, the treatment process is called pasteurization; in the
latter, sterilization of the food product. In thermal preservation, the polymer packaging material should be temperature-resistant. At a temperature higher than 100C, an increased
pressure is created inside the packaging, so special attention should be paid to the ability of
the material to form strong seams and to preserve airtightness of the packaging within the
entire range of working temperatures.
In practice, there is no individual polymer film, from which one could fabricate a package suitable for thermal preservation of food products in it. This is due to the fact that, as a
rule, heat-resistant polymer materials poorly yield to heat sealing. Besides, there are a number of other reasons, such as unsatisfactory sanitary-hygienic properties, strong deformation or thermosetting; high gas, vapour and aroma permeability, owing to which polymer
materials are used for the considered method in combination with other polymer materials
or with aluminium foil. In such combinations, high-density polyethylene and its mixtures,
polypropylene, polyamide, polyethylene terephthalate etc. are used for thermal preservation of food products in packages.
The most widespread combinations of individual films in combined film materials for
packages suitable for thermal preservation of food products are as follows.
Polyethylene terephthalatelow-density polyethylene is suitable for thermal preservation at a temperature not higher than 105C and for packaging products containing no
more than 30% fat. If, instead of LDPE, a mixture of low- and high- (or medium-) density
polyethylenes is used, then the combination of polyethylene terephthalate and polyethylene
withstands sterilization at a temperature of 120C. The material described above but reinforced with the central layer of aluminium foil was found to be good in long-time storage
of sterilized products. In the recent decade, the most advanced material for storage of food
products proved to be a combination of polymer lacquerplastic aluminium
foiladhesivepolypropylene. As a rule, this material is used for fabrication of containers/packagings by the deep draw extrusion method. The polypropylene film in particular
cases can be used for sterilization of food products in the heat treatment up to 130C and
as an individual film. However, owing to its high oxygen permeability, the film from
polypropylene can not be used for storage of products sensitive to the action of oxygen, and
such products are numerous.
For sterilization of food products with a high content of fat at a heat treatment up to
130C the French company Organico manufactures a film material from polyamide under
the tradename of Rilsan. For heat treatment of any food products by heating up to 130C,
a film from polytrifluorochloroethylene can be used.
100
An example of the thermal preservation of food products in packages from a polymer

material is a method of pasteurization of dried fruits: plums, cherries with increased
moisture content of up to 30%. This method was developed in the Moldavian Research
Institute of Food Industry. Hermetically sealed into packages from polyethylene or
polyethylenecellophane film PC-2, dried fruits (200-gram portions) are passed through a
tunnel convection drier. The total time of holding a package in the drier is 12 h at a temperature, which provides for the warming-up of the product up to 8085C. At this temperature the product is pasteurized, which enables preserving products with up to 30% moisture
for no less than one year.
Above, we have already attracted the readers attention to the fact that in the described
methods of preservation special attention should be paid to the strength of sealed seams and
to the prevention of the loss of airtightness of the packaging owing to the increase of pressure inside the package. Research has shown that the strength of sealed seams should be no
less than 80% of the strength of the base material. The maximal strength of the heat seal is
provided for at its width of 56 mm, and in the case of thermoshrink materials it should be
even smaller. At the width of 120 mm, the strength of the seal seam decreases owing to
the setting of the material and the emergence of internal stresses, which contribute to its
breakdown. To compensate for the pressure emerging inside the package at the thermal sterilization in an autoclave or in a sterilization vessel, a counterpressure is created and maintained. During the sterilization of the products in packages from polymer materials, a
pressure exceeding that emerging inside the package is maintained in the autoclave. Otherwise, packages inflate. As the autoclave begins to be cooled, the heat carrier cools down
quicker than the content of the package. Owing to this, the difference of pressures in the
package and outside it can prove to be larger than the value the package can withstand without breaking down. To avoid the disturbance of airtightness of packages, special attention
should be paid to the maximally possible elimination of air from packages prior to their sealing.
Sterilization studies of such products as tomato pulp and collops in polymer packages
showed an advantage of the steam-air method of thermal sterilization over the water method, because it is easier to maintain the set parameters of the process in the former case. The
external pressure in the course of the process should be 0.20.3 atm higher than the internal
pressure. At a temperature of 100C, the counterpressure should be of the order of 1.251.3
atm. At a higher temperature, excess pressure is increased by 0.3 atm for each 5C. In sterilization by this method at 100C of fruit juices, at 117C of liver sausage and at 121C of
green beans and soup from champignons, the best results were obtained for films from
polypropylene and polyamide. The sterilization process took 1530 min. The quality of the
products was preserved for 6 months. Until now, heat treatment of food products in packages from polymer materials has been considered. However, thermal preservation of food
products in polymer containers can also be successful.
Herewith, thermal preservation of such fruit-and-vegetable products as juices, compots, confiture, jam can be done at a temperature not higher than 100C. Packaging of these
products into polymer containers is sufficiently easy. In some cases, the product heated up
to the required temperature is poured into containers, and in other cases the packaged product is heated in containers at a temperature of 80100C. The described method of sterilizing food products in polymer containers is characterized by some features. As rigid and
semi-rigid containers are readily deformed both at excess internal and at excess external
pressure, the success of the process depends on the correct choice of the regime of application and removal of the counterpressure.
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Fabrication of polymer containers is accompanied by the emergence of the so-called

internal stresses. Under the action of these stresses, a nonuniform shrinkage develops during the heating of containers. The shrinkage is avoided by the correct choice of the regimes
of application and extent of counterpressure. This choice is required in transition from one
type of polymer containers to another, as well as in changing the sterilization regime. The
use of vacuumizing of the packaging should be specially accounted for. Shrinkage and the
related change of shape of the polymer containers are eliminated by warming the containers
before filling them. Thus, for instance, cups from high-density polyethylene or from
polypropylene should be warmed before filling for 30 min at a temperature 510C higher
than the sterilization temperature, i.e., for HDPE at 110C and for polypropylene at 130C.
The sterilization regime in such cups is characterized by a maximal temperature of
120125C.
Rigid polymer containers are closed either by metal or polymer lids. When using metal
lids, the sealing of polymer containers is done by mechanical methods similar to those used
in the case of tin or glass containers. These methods include vacuumizing. When using
polymer lids, the sealing is done by heating, and vacuum is created either by special means
or due to a decrease of volume of the product during its cooling. In sterilization of food
products in polymer packages with metal lids, it is recommended to use the following values of counterpressure: at the sterilization temperature of 105C, counterpressure of 0.7
atm; at 112113C, 0.8 atm; at 116117C, 0.9 atm; at 129C, 1.0 atm.
In the recent decade, another widespread method of sterilizing food products has been
sterilization by radiation. This method imposes special requirements on polymer materials,
such as resistance to ionizing radiation within the limits of the doses used in preservation;
absence of harmful substances emerging in this method of sterilization; absence of foreign
taste and smell. Tests have shown that in sterilization of food products by gamma rays from
a cobalt source at doses common for preservation of food products (0.55.0 Mrad), the major characteristics of a number of polymer materials do not undergo noticeable changes.
Such materials include, for instance, films from polyethylene, polypropylene, polyamide,
polyethylene terephthalate. The characteristics of strength, gas and vapour permeability,
as well as specific characteristics mentioned above remain within the normal limits. Such
films as from polyvinyl chloride, from copolymers of vinyl chloride with vinylidene chloride, from polyisoprene hydrochloride have a foreign smell when irradiated even by the doses of 0.10.2 Mrad. The most resistant to radiation sterilization of food products are
considered to be cellophane lacquered with nitrocellulose lacquer, nonlacquered cellophane, polyethylene terephthalate and polyamide films.
At the radiation impact on multilayer polymer and combined materials, the endurance
of the least-resistant components increased about 1.5-fold. A foreign smell emerging in irradiation of polyethylene is due to the evolution of gaseous products: carbon dioxide, hydrogen, ethylene, propane, butane. In irradiation of polyethylene terephthalate, the evolved
gases were carbon dioxide, nitrogen, oxygen, water vapours and other volatiles. Irradiation
of films from copolymer of vinyl chloride and vinylidene chloride yielded a number of gaseous products with a sharp smell: chlorine, hydrogen chloride, hydrocarbons and some carcinogenic products.
In domestic practice, good results were obtained in radiation preservation of a number
of fresh fruits and vegetables, raw meat, meat culinary products, poultry and other food
products in polymer packagings. As a rule, products were subjected to small radiation doses
(0.51.2 Mrad). The most promising in this respect proved to be films of the type of PC,
paper with a polyethylene coating, polyethylene terephthalate films. In this case we mean
102
domestic polymer materials, to which we should also add lacquered cellophane suitable for
this kind of sterilization of products not containing a large amount of moisture. Polyamide
films of the type of rilsan and nylon showed good characteristics. Of special interest are the
results of radiation treatment (0.6 Mrad) of beef meat packaged into cellophane with a polyethylene coating. Meat treated in this way had no foreign smell and stored well under room
conditions for up to two weeks. Pork at the same method of preservation stored for up to
three weeks. Hens and ducks, at a slightly large irradiation dose (1.0 Mrad), stored under
room conditions for up to one month. Meat culinary products irradiated with 0.8 Mrad
stored in this packaging for up to four months.
The described method of storage is also applicable for fish and fish products. Irradiation by a dose of 1.0 Mrad at a temperature of 05C made it possible to store unfrozen
herring for 60 days, fresh pike for 60 days, unfrozen cod for 120 days, fried fish for 60 days,
fish in tomato sauce and in vegetable marinade for 365 days.
With the rise of production and due to the appearance of polymer materials exceeding
the traditional materials (wood, tin, cardboard, paper, glass, natural cotton fibres, tarpaulins
etc.) fish industry came across the problem of using these advanced materials as packaging
and containers for transportation and storage of fish products; consumer containers for
packaging and sales of various fish products, including culinary products.
To provide for the introduction of new materials in fish industry, R&D and process
design units were organized to carry out work in the following directions:
research into polymer materials satisfying the physicomechanical and sanitaryhygienic requirements to packagings and containers for fish products and to synthetic fibres
for fishing nets and tackles
development of polymer containers designs
mechanization of prepackaging/packaging of fish products into polymer containers
R&D works for the organization of enterprises and plants for production of polymer
containers.
These measures made it possible to organize production of polyethylene boxes of
1025 litres in capacity; polyethylene barrels of 50 litres in capacity; small packages with
overprinting; inserts, bags and packages for whale meat, salt fish, frozen fish; 1.5-litre polyethylene cans with overprinting; polyethylene cans of 0.10.4 litres; trays from polyvinyl
chloride.
Production of goods in small packages was increased. For processing of marketable
fish products, new fish-processing complexes were put into operation for production of fish
delicacies in places of consumption.
For packaging of products into consumer containers, use is made of polymer films,
cartons and combined materials based on paperboard, paper, foil with a polymer coating.
The use of polymer materials for packaging, transportation and storage of fish products
makes it possible to free traditional materials woods, white tin, aluminium, glass, etc. This
decreases the costs and consumption of materials in production of containers/packagings.
For instance, production of a 50-litre barrel from polyethylene for packaging cod liver oil
requires three times as less materials as compared with 10-litre glass flasks.
New combined packaging materials used in fish industry are aluminium foil polypropylene (of the type of steralkon) and aluminium foil coated with heat sealable lacquers.
The steralkon packaging is strong, light, glossy; makes it possible to produce solid-drawn
cans of various configurations, which possess airtightness and enable sterilization of the
CHAPTER 2
103
product. There are several lines manufacturing these cans for fish industry.
Domestic industry assimilated the filling and closing equipment operated on polyvinyl
chloride and polystyrene (cases of packagings) and aluminium foil with heat sealable
lacquer (lids of packagings).
104
3
3.1
Combined Packaging
Materials Using Cellulose
and Its Derivatives
Internal stresses in coatings using cellulose
Polymer coatings find wide use for protection and decorative finishing of traditional materials (metal, woods, glass, paper, etc.), as well as in the development of plied and combined
materials of various purposes.
In developing the physicochemical bases for production of these materials, of great importance is to study the effect of structural transformations on the properties of polymer systems in their transition from the liquid to the solid state. A peculiar feature of this transition
for polymer coatings is that their formation mechanism passes the stage of gelation and is
accompanied with a sharp inhibition of relaxation processes, which lead to the emergence
of internal stresses (BH).
Studies of the durability of polymer coatings have established that their service life is
largely determined by BH, capable of inducing the spontaneous exfoliation and decomposition of polymer coatings on rigid and elastic supports. Therefore, of great scientific and
applied importance is to develop the physicochemical ways of decreasing BH. This problem is topical in developing packaging materials for food products, as they affect the protective properties of packagings.
Usually, low-molecular-mass plasticizers are used for this purpose. Their mechanism
of action is related to the weakening of intermolecular interaction between structural elements and to the increase of their mobility, which leads to the relaxation of stresses. This
effect is also achieved in the formation of polymer coatings under more mild conditions,
e.g., at (relatively) low temperatures. However, the use of these regularities for monitoring
structure formation in polymer systems is not always efficient, as, along with the decrease
of BH, the physicomechanical, adhesion, thermophysical, dielectric and other properties
are considerably worsened in this case.
In this connection, it is important to decrease BH not during the weakening but during
the intensification of intermolecular interaction between the structural elements. This
would also make possible a considerable improvement of the performance properties. This
effect is achieved by forming a three-dimensional network from supramolecular components available in the liquid system before the onset of its solidification due to the emergence of local bonds, whose strength is commensurable with the energy of thermal motion.
The appropriateness of forming such a network ensues from the new views of the mechanism of BH in polymer systems. The regularities establishing the interaction between the
106
character of structural transformations in liquid systems and the incompleteness of relaxation processes were the basis for developing new physicochemical views of the ways to
decrease BH in polymer coatings, based on the development of an ordered thixotropic
structure in film formers and fixing it in ready-prepared products. This is the essence of the
phenomenon of a decrease of BH.
Thixotropy is one of the forms of gelation: such a gel is transformed into a fluid at a
weak mechanical impact, e.g., in mixing, and in a quiescent state a network again emerges
in the fluid; the peculiar feature of the network is that overstresses in it rapidly relax, which
enables formation of products with higher performance characteristics. The effect of a thixotropic decrease of BH is universal and is observed during the formation of polymer coatings, adhesive layers, filled and reinforced systems from monomer and oligomer
compositions, solutions and dispersions of polymers of different chemical composition.
However, not all polymers are readily transformed into thixotropic gels, so new
methods of creating them in various film-forming systems were developed. This is achieved
by introducing special additives to liquid systems. In some cases, these are oligomers forming bridges between supramolecular structures; in other cases, polymers creating a threedimensional network in monomers, oligomers, dispersions and solutions of polymers.
For polymer dispersions with large particles, universal modifiers are efficient: first
they break particles into more fine structural elements, and then crosslink them into a
three-dimensional network. The role of these modifiers can be played by monomers and oligomers, polymer electrolytes adsorbed by particles of dispersions, surfactants.
The gel formation mechanism was studied by various physicochemical methods:
infrared spectroscopy, high-resolution nuclear magnetic resonance, electron paramagnetic
resonance, scanning and transmission electron microscopy; rheological, thermophysical,
physicomechanical etc. methods.
The phenomenon of a thixotropic decrease of BH does not depend on the method by
which the thixotropic structure is created; it can be produced as the result of adding poor
solvents, branched oligomers, crosslinking agents, structuring systems, surfactants, dispersants.
In many cases, it is much more convenient to work with thixotropic systems than with
liquid or solid systems. They are processable, impregnate fibrous materials less and do not
bleed on paper, which is important in printing production and other industries.
The development of a thixotropic structure makes it possible not only to considerably
improve the performance characteristics of polymer coatings. In a number of cases, it enables the complete exclusion of low-molecular-mass plasticizers (readily dropping out in
the process of ageing and, thus, sharply decreasing the durability of the coating) from the
formulation of rigid-chain polymers. The authors used the phenomenon of a thixotropic decrease of BH to develop elastic polymer coatings based on nitrocellulose (NC) with high
physicomechanical properties. Usually, plasticizers are used for this purpose in polymer
coatings from NC, in particular, castor oil, which is in short supply, at a 1:1 ratio. Grafting
of other polymers to NC does not exclude plasticizers, either. NC was modified by polyurethane oligomers with a 0.30.5 ratio of the isocyanate and hydroxyl groups. The extent
of oligomer branching was regulated by introduction of different amounts of triol. Figure
3.1 presents the kinetics of BH changes during the formation and ageing of polymer coatings. It is seen that significant BH emerge in polymer coatings from nonplasticized NC.
Introduction of castor oil at a ratio of 1:1 decreases BH by an order of magnitude. However,
the properties of such polymer coatings are unstable, which is indicated by a sharp increase
of BH during the thermal ageing of polymer coatings. A significant decrease of stresses is
107
in, MPa
CHAPTER 3
1.0
0.6
2
3
4
5
0.2
12
40
Time, h
80
120
Figure 3.1 Kinetics of the buildup of internal stresses during the formation and thermal ageing of
polymer coatings from a 10% solution of NC in butyl acetate: initial (1), plasticized by castor oil (2),
modified by weakly (3), medium (4) and strongly (5) branched oligomer.
observed as a thixotropic structure is created in polymer coatings by means of highly

branched oligomers. Polymer coatings from such systems are distinguished by good physicomechanical properties (see Table 3.1) before and after the ageing.
Table 3.1
Additive
Polyurethane oligomer,
weakly branched
strongly branched
medium branched
Castor oil
NCO/OH
Content of
additive,
weight
fraction
Tensile strength,
MPa
Breaking elongation,
%
before
ageing
after
ageing
before
ageing
after
ageing
0.3
0.5
0.5
0.3
0.4
0.5
0.0
0.1
0.3
0.5
0.7
90
90
110
90
90
90
100
100
100
100
100
24.0
28.1
8.5
28.6
32.4
43.7
0.06
2.0
7.6
8.7
10.0
23.4
28.0
8.8
29.3
31.5
39.2
0.03
3.3
8.3
10.0
15.0
48
80
91
60
60
20
640
247
95
76
48
50
81
96
60
60
22
600
213
88
72
41
90
100
110
16.7
14.7
14.6
13.1
11.8
60
51
68
30
50
Polymer coatings from NC are characterized by an inhomogeneous globular structure.

The globular morphology of the structural elements is preserved in the presence of castor
108
Figure 3.2 Structure of polymer coatings from initial NC (a) and NC modified by a thixotropic
additive (b).
oil. The character of structure formation is changed significantly in the development of a

thixotropic structure, which is also indicated by the change of the rheological properties. It
is seen that solutions of initial NC and polyurethane oligomers represent weakly-structured
or Newton-type systems. Their modification by castor oil and weakly branched oligomers
does not change the character of the rheological curves. Formation of a thixotropic structure
is observed in a solution of NC in the presence of a highly branched oligomer. The cause
of this phenomenon was shown by the method of IRS to be related to the formation of hydrogen bonds between hydroxyl groups of NC and the modifier.
These regularities were used to produce a thixotropic structure in solutions of polymers of different chemical composition with the view to improve the properties of polymer
coatings: polyurethanes, polyester amidourethanes, chlorinated rubbers, nairites and chlorinated nairites, block copolymers (Fig. 3.2) .
Depending on the purpose of polymer coatings, the thixotropic structure can be formed
by choosing the nature of solvent; introducing a surfactant with a definite structure of mol4
1
2
log
4
3
1
0
1
log p
Figure 3.3 Dependence of viscosity on shearing stress for 10% solutions of the initial components
(a) and modified NC (b): a, for strongly (1), medium (2), weakly (3) branched oligomers and initial
NC (4); b, for NC modified by weakly (1), medium (2), strongly (3) branched oligomer and castor
oil (5).
CHAPTER 3
109
ecules, bifunctional compounds of polymers forming a network skeleton on solutions of the

base polymer, monomer or oligomer (Fig. 3.3).
3.2
Moisture-resistant packaging materials based on cellophane
3.2.1 Justification of the composition of the coating

Compositions based on modified cellulose became widespread in food industry as packaging materials. This is due to the fact that packaging of food products into polymer materials
significantly extends their shelf life, reduces losses in transportation and its costs. Besides,
most film materials are transparent, they colour well and take up ink printing, which enables
presenting a packaging in a good marketable state.
One of the most widespread film polymer materials is hydrated cellulose film, cellophane. It has such valuable properties as a high mechanical strength, gas impermeability,
grease resistance and transparency. However, it also has a number of drawbacks, which significantly restrict its applications. In an elementary link, the hydrated cellulose macromolecule has three hydroxyl groups, which is the cause of a large affinity of cellophane to water.
H
C
CH2OH
OH
OH
H
H
OH
OH
C
H
CH2OH
H
C
A film from hydrated cellulose contains up to 12% of water and about 11% of glycerol.
Its thickness is from 20 up to 50 m and its mass is 30100 g. To make cellophane hydrophobic, films are lacquered with a layer of 24 m cellulose ester or a synthetic polymer.
Swelling in water for 1 h by about 50%, cellophane loses its mechanical strength twofold. Besides, not being a thermoplast (and degrading when heated up to 170180C), cellophane is not capable of heat sealing, which makes impossible its use for vacuum
packaging. Various currently used modifications of cellophane are devoid of its major
drawbacks. Until recently, the basic coating for cellophane was nitrocellulose. However,
these coatings have a comparatively low adhesion to hydrated cellulose (especially in a humid atmosphere); low heat sealability, grease and oil resistance; become more vapour- and
moisture-permeable upon application of labels.
Lacquered cellophane used in Russia, by the company Meyer, also has nitrocellulose
as the base for the coating. Along with the general drawbacks characteristic of cellophane
with such a kind of coatings, cellophane by Meyer also has the following drawbacks. The
lacquer composition is multi-component (over 10 components), many of the components
have not been disclosed by the company and are not manufactured by Russian industries.
Domestic research yielded a moisture-resistant, heat-sealable cellophane with a coating based on domestic raw materials; optimal processes for it have been worked out.
To develop moisture-resistant heat-sealable cellophane, thermoplastic polymers with
high parameters of moisture resistance were used as modifiers: copolymers of vinylidene
110
chloride and vinyl chloride, epoxy oligomers with molecular masses from 600 up to 3000
and various compositions on their basis.
Tables 3.23.6 present the properties of modifying polymers.
Table 3.2 Properties of films from copolymers of vinylidene chloride with acrylonitrile at ratios
of 80:20 and 60:40.
Ratio of monomers in initial mixture

(vinylidene:acrylonitrile)
Content of nitrogen in copolymer, %
Content of acrylonitrile, wt. %
Characteristic viscosity in cyclohexanone
Gas permeability of 25-m film, ml/645 cm2 /24 h/atm
for N2
for O2
for CO2
F-218
F-220
80:20
6.1
23.1
0.95
60:40
1.2
42.4
1.87
0.084
0.710
1.770
0.422
3.420
7.910
Table 3.3 Basic properties of resin Saran F-120 (copolymer with a high content of vinylidene
chloride and low content of acrylonitrile).
Properties
Grades of different viscosity
Viscosity limits, cp
Specific weight at 25C
Refractive index at 25C
Tensile strength, MPa
Elongation, %
Moisture permeability of films, g/dm2 24 h at 37C
Permeability of toluene vapours, g/dm2 24 h
210 3 Pas
10 3 Pa h
180220
1.60
1.580
56
8
0.023
0.0403
10120
1.60
1.580
70.3
8
0.023
0.0403
Table 3.4 Properties of films from copolymers of vinyl chloride, vinylidene chloride, and from
epoxy oligomers.
Water
resistance
Oil/grease
resistance
80100
excellent
good
100150
excellent
excellent
2000
115160
excellent
excellent
excellent
unstable
Gas permeability
Heat
for O2, 10 6 g
sealability
mm/244 m2 cmN temperature,
at 21C, 0% rel.
C
humidity
Material
Water
permeability,
g mm/244 m2
cm Hg at 25C
Copolymer of
vinylidene chloride
with vinyl acetate
Copolymer of
vinylidene chloride
with vinyl chloride
Epoxy oligomers
Low-density polyethylene
0.20
0.01
0.06
111
CHAPTER 3
Table 3.5 Characteristics of copolymers.

Name of polymer
Relative humidity
Content of C, %
Copolymer of vinylidene chloride with

acrylonitrile at a ratio of 80:20 [SVN-80]
60:40 [SVN-60]
Copolymer of vinylidene chloride with
vinyl chloride at a ratio of 60:40 [SVKh-40]
Copolymer of vinyl chloride with vinyl
acetate [VKh+VA]
1.59
57.98
2.49
1.29
50.88
Table 3.6 Characteristics of epoxy oligomers.

Epoxy
grade
ED-5
ED-15
E-40
Mol. mass
Epoxy
value,
%
1620
57
1820
12
10
710
18
54
910
67
24
60
7080
150
10
6
3
30
18
9
600
E-41
E-44
E-49
900
1500
2500
3000
Viscosity*, Amount of hardener Melting Elasticity

sec
per 100 g of
temperaby the
oligomer
ture (ring
NIILK
and ball
scale**
hardener adduct
test),
No 1
C
25 by
Ubbelode
7280
8590
105
Solvents
510
ketones
ketones
toluene
150
150
540
acetates
ketones
ketones,
ethyl
cellosolve
*of a 40% solution in cellosolve, as measured by a VZ-4 viscosimeter.

**NIILK = Nauchno-Issledovatelsky Institut Lakov i Krasok = Research Institute of Lacquers and
Paints
Polyvinylidene chloride is a very strong and robust material with exceptionally good
water resistance, it has a high softening point, as well as a limited compatibility and solubility. Copolymers of vinylidene chloride with such monomers as acrylonitrile or vinyl
chloride have a slightly lower water resistance and chemical resistance than polyvinylidene
chloride; however, they possess a good solubility and compatibility. These copolymers are
applicable for production of coatings, films, sheets and plastics.
Table 3.7 presents the properties of films from copolymer SVN-80 produced by casting from solution in methyl ethyl ketone.
Table 3.7 Properties of CVN-80 films (thickness, 70 m).
Tensile strength,
MPa
Relative
elongation,
%
Vapour / moisture
permeability,
g/dm2 (48 h)
Air permeability,
cm3 cm/cm2 sec atm
20
280
0.035
0.04010 8
Swelling in water,
% (24 h)
112
3.2.2 Copolymer-based coatings

O
Copolymers having in their composition the polar groups Cl ; C N C
and
CH3
others were used as coatings for cellophane.
The 5% solutions of these copolymers in a mixture of acetone and cyclohexane (1:1)
were used. Lacquering was done by dipping followed by drying in the air. The material obtained was tested for vapour and moisture permeability (Table 3.8) and swelling in water
(Table 3.9).
Table 3.8 Vapour/moisture permeability of cellophane lacquered with various copolymers.
Copolymer used as a coating for
cellophane
Thickness of coating, m
Vapour
Moisture
permeability, g/dm2 (48 h)
SVN-80
SVN-60
SVKh-40
VKh+VA
Common cellophane
5
5
4.5
4.5
0.72
2.50
0.45
4.00
17
0.82
2.00
0.65
16.00
25
As it follows from Table 3.8, the greatest effect in decreasing vapour and moisture permeability of cellophane was rendered by copolymers SVN-80 and SVKh-40.
Table 3.9 Kinetics of swelling in water of cellophane lacquered by various copolymers.
Copolymer used as a
coating for cellophane
SVN-80
SVN-60
SVKh-40
VKh+VA
Common cellophane
Thickness
of coating,
m
Weight increment, %
1h
2h
3h
5h
24 h
Film
peeling
time
5
5
4.5
4.5
17.0
25.0
60.0
48.0
70.0
29.0
32.5
75.0
75.0
34.5
38.0
78.0
34.5
45.0
80.0
60.0
70.0
85.0
48 h
24 h
20 min
2h
As it follows from Table 3.9, cellophane with a lacquered coating from SVN-80 possesses a lower degree of swelling in water in 24 h. The film of this copolymer peels off cellophane in 48 h, whereas the film SVKh-40, which also provides for a sufficiently low
vapour and moisture permeability of cellophane, peels off in 20 min of swelling in water.
Figure 3.4 presents the kinetics of swelling in water of common cellophane and cellophane lacquered with copolymers SVN-80 and SVN-60. Common cellophane swells in 1
h almost to a maximum, and then in 24 h the amount of absorbed moisture increases insignificantly. In the case of coating with lacquers, the swelling in 1 h decreases by about 5
times for the coating from SVN-80 and by about 3 times for the coating from SVN-60. In
only 24 h the swelling of lacquered cellophane reaches a maximum of 6070%.
Studies have shown that lacquered coating from copolymer SVN-80 is the most expedient material to be used as a hydrophobic coating for cellophane.
Various epoxy polymers with molecular masses from 600 up to 3000 were used to obtain water-resistant coatings for cellophane. Various solutions of epoxy oligomers (10, 15
CHAPTER 3
Weight increment, %
100
113
80
2
3
60
40
20
0
2
10 12 14 16 18 20 22
Swelling time, h
Figure 3.4 Kinetics of swelling in water of common cellophane and cellophane lacquered with
SVN: 1, common; 2, SVN-60; 3, SVN-80.
and 20%) in a mixture of acetone and cyclohexane (1:1) were prepared. Cellophane was
lacquered by dipping followed by drying in the air. The hardeners used were polyethylene
polyamine, hardener No 1 (a 50% solution of hexamethylene diamine in alcohol) and adduct. The materials produced were tested for vapour and moisture permeability and swelling in water (see Table 3.10, Figs. 3.53.8).
Table 3.10 Vapour/moisture permeability of cellophane with epoxy coatings.
Epoxy grade
Molecular mass
E-40
600
E-41
900
E-44
1500
E-49
3000
Concentration
of lacquer, %
Vapour
20
15
10
20
15
10
20
15
10
20
15
10
1.60
1.73
1.80
1.59
2.00
2.50
1.82
2.22
2.70
1.50
2.10
2.70
Moisture

1.45
1.70
1.63
1.40
1.80
2.08
1.45
1.80
2.60
1.45
2.04
2.96
Cellophane with coatings from epoxy oligomers possesses a good heat sealability.
However, it appears not possible to recommend epoxy coatings for cellophane, as thicker
coatings (~10 m) are required to achieve the required hydrophobic properties, which leads
to a considerable decrease of the elasticity of material on the whole and, besides, to cracking
and pitting of the coating, both in the sites of sealing and on the surface of the material in
comparatively small storage times.
Gas permeability, g/dm2 48 h
114
1
4
10
8
Moisture permeability, g/dm2
Figure 3.5 Dependence of vapour permeability of cellophane with coatings from various epoxy oligomers on the thickness of a coating.
E-49
E-40
E-41
E-44
2.5
10
7.5
Weight increment, %
Figure 3.6 Dependence of moisture permeability of cellophane with coatings from various epoxy
oligomers on the thickness of a coating.
E-40
E-44
E-49
40
30
20
10
0
0
10
20
15
Concentration of lacquer, %
Figure 3.7 Dependence of the swelling in water for 1 h of cellophane with various epoxy coatings
on the thickness of a coating.
CHAPTER 3
115
Swelling, %
50
40
30
E-40
E-41
E-44
E-49
20
10
1
24
Swelling time, h
Figure 3.8 Kinetics of the swelling in water of cellophane with an epoxy coating; concentration of
a lacquer, 20%.
3.2.3 Coatings based on lacquer compositions

With the aim to eliminate the drawbacks specific to copolymer coatings and those based on
epoxy polymers, works were carried out to develop and adjust lacquer compositions based
on SVN-80 and E-49 polymers imparting cellophane with the most hydrophobic properties as compared with other polymers studied.
Lacquer compositions were prepared as follows. Dry resin E-49 in the amount of 50,
30, 20, 10 and 5% of the weight of dry copolymer was added into a 3% solution of SVN-80
in a mixture of acetone and cyclohexanone (1:1). Cellophane was lacquered by dipping and
dried in the air. The coating produced had (depending on the amount of epoxy oligomer
added, see above) the following weight per 1 m2: 7.0 g, 5.0 g, 5.0 g, 5.0 g, 4.5 g.
If the specific weight of the coating is taken to be ~1 g/cm3, then the thickness of the
lacquer layer (on two sides) is equal, respectively, to 7 m, 5 m, 5 m, 5 m, 4.5 m. The
coating obtained was thin, elastic, transparent and was even along the thickness. Tables
3.11, 3.12 and Figs. 3.9, 3.10 present the data of the tests of produced material for vapour
and moisture permeability and swelling in water.
Table 3.11 Vapour and moisture permeability of cellophane lacquered with compositions from
SVN-80 and E-49.
Amount of epoxy E-49 in the
lacquer composition, %
Vapour
50
30
20
10
5
2.00
2.05
2.01
1.80
1.89
2.14
2.21
2.02
1.60
1.25
1618
2225
Nonlacquered cellophane
Moisture
Note

E-49 is introduced as a
percentage of the weight of
dry copolymer SVN-80.
Lacquer SVN-80, of 3%
concentration
Vapour / water permeability,

g/dm2
116
4
3
2
Water permeability
Vapour permeability
10
20
30
40
50
Amount of resin E-49, %
Weight increment, %
Figure 3.9 Dependence of the vapour/moisture permeability of lacquered cellophane on the composition.
60
1
50
20
2
10
10
20
30
40
50
Content of resin E-49 in the composition, %
Figure 3.10 Change of swelling of lacquered cellophane depending on the content of resin E-49 in
the lacquer composition. 1, Swelling in 24 h; 2, swelling in 1 h.
Table 3.12 Swelling kinetics of cellophane lacquered with compositions from SVN-80 and E-49.
Amount of epoxy E-49 in the lacquer
composition, %
Weight increment, %
1h
2h
3h
5h
24 h
50
12
15
21
26
50
30
11
15
20
26
48
20
9.5
14
20
26
47
10
9.0
14
19
24
47
11
20
23
30
53
68
68
71
75
80
5
Nonlacquered cellophane
Seam strength, g/25 cm
CHAPTER 3
117
160
140
120
100
80
60
40
20
110
130
150
170
230
190
210
Temperature, C
Figure 3.11 Dependence of the seam strength of the lacquered cellophane-based composition on
temperature.
As it follows from the presented tables and figures, an optimal amount of resin E-49
in the lacquer composition, providing for the best hydrophobic properties of cellophane, is
10% of the weight of copolymer. An increase of the concentration of E-49 in the lacquer
composition leads to a deterioration of the moisture resistance of cellophane, probably, due
to a reduction of compatibility of the resin with SVN-80. A decrease of the content of E-49
down to 5% and less leads to a decrease of adhesion of the coating to cellophane (peeling
of the lacquer film on the second day, as compared with five days for compositions with
10% of E-49 and more), which, in turn, causes a deterioration of the moisture resistance of
lacquered cellophane.
Table 3.13 Dependence of the heat-seal strength of lacquered cellophane on heat sealing
temperature.
Voltage at the heat sealing
device, volts
Sealing temperature, C
Seam strength,
g/25 cm
80
130
80
160
135
180
149
85
90
95
100
110
120
170
205
131
Cellophane lacquered with a composition from SVN-80+E-49 heat seals well. An optimal heat sealing temperature is 180C (see Fig. 3.11 and Table 3.13).
118
3.2.4 Design of heat sealed seams

The effect of temperature on the strength of various designs of seams was studied. Two designs of heat sealed seams are known to be available: butt sealed and lap sealed (Fig. 3.12).
The former work in exfoliation; the latter, in shear.
Butt sealed
Lap sealed
Figure 3.12 Types of heat sealed seams.
Breaking strength of seam, kg/cm
Studies of the temperature dependence of the strength of heat sealed seams of these
designs showed (Fig. 3.13) the strength of seams working in shearto exceed 40130 times
the strength of seams working in exfoliation. The character of the temperature dependence
is in both cases the same: with temperature increasing the strength of the seams decreases
monotonically, which is, probably, due to the increase of the number of coating-to-base
intermolecular bonds broken per unit of time under the action of heat motion.
6
4
20
40
60
80
100 120 140

Temperature, C
Figure 3.13 Effect of temperature on the heat-seal strength of lacquered cellophane in exfoliation
(1) and in shear (2).
Seams working in shear when loaded are feasible only for longitudinal seams of most
items; butt seams work in exfoliation, thus weakening the item on the whole. It is recommended to use tucked seams (Fig. 3.14) working in shear, as they present no problems in
processing.
The diagram for the adhesion breakdown of tucked seams and a dependence of their
strength on temperature are presented in Fig. 3.15.
As it follows from Figs. 3.133.15, the breakdown character of the seams of compared
designs and the shape of the breakdown adhesiogram is absolutely the same; the absolute
CHAPTER 3
119
Initial appearance
of sealed films
Tuck
Sealing
After loading
Breaking strength of seam,

kg/cm
Figure 3.14
4
3
2
1
20
Figure 3.15
40
60
80
100 120 140

Temperature, C
Effect of temperature on the strength of tucked seams.
values of the adhesion strength of the seams are also very close.
By the performance properties and breakdown mechanism, the recommended seam
design does not practically differ from the characteristics obtained in seam shear tests.
Thus, the most rational composition from the viewpoint of heat sealability and hydrophobicity of cellophane out of copolymers with epoxy resins studied as coatings is the
lacquer composition from copolymer SVN-80 and epoxy resin E-49 in the amount of 10%
of the weight of copolymer. Cellophane with this coating was called cellophane SVN-80.
As it follows from the data of Table 3.14, the composition of copolymers SVN-80 from
various test batches is sufficiently homogeneous by its main characteristics. Thus, the ultiTable 3.14 Chlorine content and characteristic viscosity of various test batches of copolymer
SVN-80.
Batch numbers
of SVN-80
Chlorine content,
%
Characteristic
viscosity, m2/sec
Note
266/1
56.50
1.22
267/1
55.72
1.20
267/5
55.77
1.11
The characteristic viscosity of

copolymers was determined from
0.5% solutions in cyclohexane at
T = 25C
270/5
56.85
1.27
120
Table 3.14 Chlorine content and characteristic viscosity of various test batches of copolymer
SVN-80.
Table 3.14 (continued)
Batch numbers
of SVN-80
Chlorine content,
%
Characteristic
viscosity, m2/sec
334/5
54.47
1.10
341/5
57.10
1.13
341/5
56.61
1.22
544/5
56.27
1.15
545/5
56.85
1.08
548/5
59.74
1.18
550/5
58.78
1.12
Note
mate difference in the characteristic viscosity is about 0.2, and in the content of chlorine
about 5%. For this reason, the properties of cellophane lacquered with copolymer SVN-80
in these test batches are also sufficiently homogeneous (see Table 3.15).
Table 3.15 Properties of cellophane lacquered with copolymer SVN-80 from various test batches.
SVN-80
batch nos
Vapour
Moisture
permeability, g/dm2
(48 h)
Swelling
in water,
%
(24 h)
Time to
peeling,
min
Seam
strength,
g/2.5 cm
266/1
0.16
0.17
30
50
200
267/1
0.18
0.16
35
60
200
267/5
0.11
0.13
30
50
150
270/5
0.12
0.17
30
60
150
334/5
0.10
0.10
30
60
150
341/5
0.12
0.13
35
60
200
541/5
0.17
0.19
25
50
110
544/5
0.17
0.20
35
60
100
545/5
0.18
0.20
35
60
110
548/5
0.20
0.25
35
60
120
550/5
0.14
0.17
30
60
150
Note
1. Cellophane was
lacquered with 5%
solutions of SVN-80 =
E-49 in cyclohexane
(viscosity, sec, by VZ-4
viscosimeter)
2. Tensile strength and
relative elongation of
cellophane lacquered
with SVN-80 was within
the limits of GOST (State
Standards) in all batches
studied
3. Time to peeling in
minutes was determined
by the method of GOST
7730-63
Thus, the studies conducted make it possible to conclude that the test batches of copolymer SVN-80 manufactured by the plant of the V.A. Kargin Institute of Chloroorganic
Products and Acrylates differ little from one another by their main characteristics, which
provides for the production of lacquered cellophane with sufficiently close values of the
major physicochemical and physicomechanical characteristics.
121
CHAPTER 3
3.2.5 Justification of the choice of solvent

The properties of the produced coating are known to depend largely on the quality of the
main film-forming material. However, a number of technological factors, the formulation
of the coating including, also have a significant effect on the properties of the film.
When developing the formulation of a lacquer coating, special attention should be paid
to the correct choice of the solvent for the film-forming polymer.
As it follows from the literature data, the most suitable solvents for copolymers of vinylidene chloride with acrylonitrile are ketones: methyl ethyl ketone, acetone, cyclohexanone, as well as 1,4-dioxane, dimethylformamide, mesityl oxide.
A number of solvents and solvent mixtures were tested in order to choose solvents for
the lacquer composition based on SVN-80. As expected, ketones proved to be the best; what
is more, acetones or aromatic hydrocarbons could replace 60% of ketones in the solvent
mixture. The composition would not dissolve in acetones only. The data on the choice of
solvents are given in Table 3.16.
Table 3.16 Solubility of the composition SVN-80+E-49 in various solvents (concentration was
taken in terms of three parts of SVN-80 plus 0.3 g E-49 for 100 ml solvent).
Solvents
Ratio
Solvent
boiling
temperature, C
in 1 h
in 24 h
Acetone
56
slight residue
total dissolution
Methyl ethyl ketone

Cyclohexanone
Ethyl acetate
80
156
75
total dissolution
slight residue
partial
dissolution
ditto
not dissolved
ditto
ditto
ditto
partial
dissolution
ditto
not dissolved
ditto
Butyl acetate
Ethyl cellosolve
Ethyl cellosolve
125
130140
78
Methyl ethyl ketone:

ethyl acetate
1:1
80
75

ethyl acetate
1:4
80
Dissolution
total dissolution
almost total
dissolution
total dissolution
75
ethyl acetate:
butyl acetate
80
75
125
incomplete dissolution, slight

residue

ethyl acetate:
butyl acetate:
cyclohexanone
1:2:1:1
80
75
125
156
almost total
dissolution

ethyl acetate:
80
75
1:1:3
total dissolution
total dissolution
Note
1. Dissolution
temperature,
1518C
2. Introduction
of butyl acetate
into the mixture
of solvents leads
to an opaque
coating on
cellophane
122
Table 3.16 Solubility of the composition SVN-80+E-49 in various solvents (concentration was
taken
terms(continued)
of three parts of SVN-80 plus 0.3 g E-49 for 100 ml solvent).
Tablein3.16
Solvents
butyl acetate:
acetone
Ratio
Solvent
boiling
temperature, C
3:2:3:2
Acetone:
cyclohexanone:
butyl acetate:
toluene
Dissolution
in 1 h
Note
in 24 h
125
56
56
156
125
ditto
1:1:2:1
To find a good solvent for SVN-80, we plotted the kinetics of its swelling in vapours
of such organic solvents as acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate and
some mixtures of these solvents. The data are given in Table 3.17.
Table 3.17
Solvents
Weight increment, % per hour
Acetone
Methyl ethyl ketone
Cyclohexanone
Ethyl acetate
Acetone:cyclohexanone =
1:1 (mixture No 1)
41.5
33.5
2.5
18.2
12.2
49.0
42
4.2
25.5
14.2
53.5
45.5
5.4
27
15.1
60
52.5
7.5
29
17.7
92.7 100
110
118 Swelling
86
95
98.5 temperature,
27.5
42
52
60
20C
33
33
33
33
32.2
43.2 57.0 64.0
20.5
22.9
42.7
Acetone:cyclohexanone:
15.1
butyl acetate: ethyl acetate
= 2:2:2:4 (mixture No 2)
Note
52.7
68.5
Weight increment, % per hour

Cyclohexanone
12
16
22
27
32
36
17.0
39.2
47.4
69.3
84.0
108
132
149.5
188
212
Swelling
temperature,
55C
In all solvents studied, except ethyl acetale, SVN-80 swells unrestrictedly. The extent
of its swelling in ethyl acetate vapours is 33%.
The swelling of SVN-80 in vapours of methyl ethyl ketone (without comparison with
its swelling in acetone) is characterized by the highest rate in the first 24 h.
The swelling rates of SVN-80 in vapours of all solvents studied (except ethyl acetate)
become approximately the same in 24 h (Fig. 3.16).
The SVN-80 swelling rate in acetone vapours is maximal. However, the use of acetone
as a solvent of SVN-80 is not expedient owing to its high volatility and, therefore, worse
conditions of film forming. The latter statement confirmed experimentally is consistent
with the literature data.
An increase of temperature leads to an intensification of the swelling process. Thus,
CHAPTER 3
123
130
2
110
Weight gain, %
3
90
4
5
6
70
50
30
10
8
16 24 48
56
64 72
80
88
96
Swelling time, h
Figure 3.16 Kinetics of swelling of copolymer SVN-80 in vapours of some organic solvents: 1,
cyclohexanone (T = 55C); 2, acetone; 3, methyl ethyl ketone; 4, mixture No 2; 5, mixture No 1; 6,
cyclohexanone; 7, ethyl acetate.
the swelling rate of SVN-80 in cyclohexanone at a temperature of 55C exceeds that in acetone at room temperature more than twofold.
As the result of the studies, and also because
the method of drying by infrared beams, as a more advanced method as compared
with convective drying, rules out the large duration of the drying process and the possibility
of insufficient drying of the coating
application of solvents with a high boiling temperature improves the film-forming
conditions, and the use of a mixture of solvent complicates the process at the stage of recuperation of the solvents
we believe that the use of cyclohexanone as a solvent of SVN-80 is the most expedient.
3.2.6 Wetting of hydrated cellulose film with some organic solvents and solutions of
SVN-80 on the basis of these solvents
As indicated by the results of recent studies, the value of adhesion is largely affected by the
wetting of substrate with a fluid adhesion-promoting agent. By conducting studies of the
wetting of a hydrated cellulose film with such organic solvents as cyclohexanone, acetone,
some mixtures of solvents, as well as solvents of SVN-80, we thought it possible to confirm
the choice of a solvent for SVN-80, i.e., to obtain the minimal values of the contact angle
of wetting ( ) and the time of its complete spreading (Tmax) for a good solvent for
SVN-80. The study conducted has shown that in the case of the above solvents we have an
ideal wetting of the base: is practically equal to zero, and the spreading of a drop of a
solvent is almost instantaneous. Based on these data, it was natural to assume that the affinity of the studied solvents to cellophane is almost the same, which was confirmed by the
124
study of the wetting of a nonpolar (paraffin) support by the same solvents. The data of the
study are summed up in Table 3.18.
Table 3.18 Contact angle of wetting of paraffin by some organic solvents.
Solvents
Acetone
Cyclohexanone
Mixture No 1
Mixture No 2
eq
37
40
43
40
As seen in the table, the values of in all four cases are rather close.
As the study of the wetting of cellophane by pure solvents gave us no possibility to
determine, which solvent is the best for SVN-80, we studied the wetting of cellophane by
solutions of SVN-80 on cyclohexanone and mixture No 1. Acetonic solutions of SVN-80
were not studied as solutions on a volatile solvent, which deteriorated film formation. The
purpose of this study also aimed at establishing the effect of the concentration of the solution on the wettability of the support. The results are presented in Tables 3.19 and 3.20 and
in Fig. 3.17.
Table 3.19 Contact angles of wetting of cellophane by solutions of SVN-80.
Contact angle of wetting, deg
T, sec
10
30
60
90
120
150
180
210
240
300
360
420
480
510
Solution of SVN-80 in cyclohexanone
Solution of SVN-80 in mixture No 1
20%
15%
10%
7.5%
5%
15%
10%
45
32
28
24
20
18
16.5
15.0
14.5
39
21
16.5
11.5
12.4
10.0
7.5
7.3
7.2
7.2
20
[75] 15
12
9
7
5
23
16
10
7
[135] 6
3.5
[15] 15
[25] 10
[35] 8.5
[40] 6.0
[50] 4.0
[60] 3.5
[90] 2.5
38
27
20
17
12
26
[25] 19
[35] 12
[45] 9
[55] 8
[110] 7
11
Table 3.20 Dependence of the contact angle of wetting and time of complete spreading on the
concentration of SVN-80 solutions.
Concentration
of solution,
%
20
15
eq, deg
Teq, min
SVN-80 in
cyclohexanone
SVN-80
in mixture 1
SVN-80 in
cyclohexanone
SVN-80
in mixture 1
15
7.5
11.0
5
4
CHAPTER 3
Table 3.20 Dependence of the contact angle of wetting and time of complete spreading on the
Table
3.20 (continued)
concentration
of SVN-80 solutions.
Concentration
of solution,
%
eq, deg
SVN-80 in
cyclohexanone
10
7.5
5
125
Teq, min
SVN-80
in mixture 1
4
3
2.5
SVN-80 in
cyclohexanone
7.0
3
2.5
1
SVN-80
in mixture 1
1
As it follows from Fig. 3.17, the rate of reaching eq is higher for the solution of
SVN-80 in mixture No 1. This is explainable by a decrease of the viscosity of the solution
at the addition of acetone to cyclohexanone. However, an increase of the rate of spreading
does not lead to an improvement of wetting. What is more, introduction of acetone worsens
the wettability of the solution. Indeed, if the value of eq in the case of the solution of
SVN-80 on cyclohexanone at a concentration of the solution of 15 and 10% is, respectively,
7.2 and 4.0, then for solutions of SVN-80 of the same concentration on a mixture of solutions, eq is 11 and 7.
Contact angle of wetting, deg
50
In cyclohexane
In mixture
40
30
20
10
10%
5%
1
10%
7.5%
3
15%
15%
5
6
Spreading time, min
Figure 3.17
This, we have shown that solutions prepared using a mixture of solvents have a worse
wettability as compared with solutions of cyclohexanone.
3.2.7 Working-out of an optimal process regime for producing cellophane SVN-80

The effect of drying time on the properties of lacquered cellophane was initially studied on
specimens obtained in the laboratory. Cellophane was lacquered by dipping*, dried in the
*3% solutions of SVN-80 and E-49 in a mixture of cyclohexanone:acetone (1:1) were used for the
coating.
126
air until tack-free, and then held at a temperature of 8085C for 15, 30, 45, 60 and 90 min.
It was noted that only the specimens dried for no more than 1520 min preserve their
elasticity; the others become brittle and, when allowed to swell in water, the lacquer film
in them exfoliates in several hours.
The initial variant of the pilot-plant lacquer installation for drying the coating made
use of the convective method. However, attempts to produce material with a desirable set
of properties failed: at comparatively low drying temperatures (70C) the coating peeled
off from cellophane swollen in water for 13 h; at higher drying temperatures, the coating
possessed a sufficiently good moisture resistance but was not heat sealable. Exfoliation of
the lacquer coating from cellophane swollen in water (in the case of its drying at low temperatures) can, probably, be explained by the presence of traces of solvent; the same is indicated by the opacity of lacquered cellophane in swelling. The inability of lacquered
cellophane dried at increased temperatures to be heat sealed is, probably, due to the
crosslinking of the polymer at these temperatures. At some intermediate temperatures there
is no crosslinking and no traces of solvent in the film; still, swelling in water for a short time
leads to exfoliation of the lacquer coating from cellophane.
Using the convective method, the coating is dried unevenly with respect to the thickness; the rate of diffusion of the solvent from the deep layers of the coating to the surface
layers is much smaller than the rate with which the solvent evaporates from the surface. As
the result, the surface layer dries up faster, and the solvent, which continues to diffuse to
the surface, disturbs the integrity of the coating. Micropores are produced, via which molecules of water during the swelling freely penetrate into the coating, to cellophane; its swelling exfoliation of the lacquer film occur. In the given case, these phenomena play an even
greater role owing to the fact that the solvent for the lacquer composition was a mixture of
acetone and cyclohexanone (1:1) with different boiling and evaporation temperatures.
On the other hand, the film-formation conditions are, probably, such that adhesion
forces are commensurable with internal stresses generated in the lacquer film in its formation, which can lead to rapid exfoliation of the coating in swelling.
In view of this, the convective method of drying the coating in the pilot-plant installation was replaced by a more advanced method of drying with infrared beams, which provide
for the heating of the lacquer layer along its thickness and an increased solvent diffusion
rate from the depth of the coating to the surface. Besides, IR drying removes the necessity
of using mixtures of solvents with different boiling temperatures. The high drying rates
in this method enable using cyclohexanone to produce a lacquer composition; cyclohexanone provides for good film-forming conditions and end material with an optimal set
of properties.
Preliminary works on IR drying of lacquered cellophane showed the appropriateness
of using this method of drying. Lacquered cellophane dried for 23 min by plate-type IR
radiators at an optimal distance of 5 cm between the film and the plates, at a supplied voltage
of 100 V (approximately, a temperature of 10120C corresponds to this voltage) swells
in water in 24 h up to 2023% as compared with 3540% for lacquered cellophane dried
by the convective method. The lacquered film does not peel off from cellophane swollen in
water for 5 days; the lacquered cellophane is heat sealable.
A technological scheme for producing lacquered cellophane was developed.
Cellophane from the unreeling device via the guiding rolls is fed to the lacquer bath,
where it is covered with lacquer on one or both sides as required, is then supplied to the
drying section, and after drying of the end material is supplied by a special tensioning
device to the reeling roll.
CHAPTER 3
3.3
127
Modification of cellulose diacetate for packaging materials
Films and consumer containers based on cellulose diacetate (CDA) are promising ecologically safe materials intended for contact with high fat-content spreads, confections and infants food products. Great importance of these materials for food industry and the diversity
of requirements imposed on them makes it necessary to develop new formulations of ethrols
with specific balanced sets of properties.
The possibility of targeted regulation of the properties of cellulose acetate compositions was studied. The aim of the studies was to obtain food-grade ethrols with a wide range
of plasticity properties, MFI (melt fluidity index), a wide interval between the yield temperature and breakdown temperature, a high tensile yield strength, a certain set of performance characteristics. Therefore, it was necessary to develop ethrol whose process
characteristics would enable its reprocessing into consumer containers by injection molding, by methods of blow molding and pressure forming.
We studied triacetine (TA)-placticized CDA with the content of combined acetic acid
of 55.8% and molecular mass of 45,000 (as determined from the viscosity of solutions in
acetone). Dibutyl esters of the general formula
C4H9
ROC (
CH2
)n C
where R =
CH2CH2
CH2CH2
]m
OC4H9,
or
CH2
CH
CH3
served as modifiers of the plasticizing system. Namely, they are dibutyl esters of polydiethylene glycol adipinate (PDEA), of polyethylene glycol cebacinate (PAC-22) and of
polypropylene glycol adipinate (PPA-4). The amount of modifier in the plasticizing system
of TA + oligoester was varied from 0.1 up to 10%; the amount of mixed plasticizer was
constant and equaled to 35% per 100% CDA. The ingredients were mixed in a high-speed
turbomixer at a temperature of 343 K; the mixing time of dry components was 8 min; of
dry components with liquids, 12 min. The mixture obtained was homogenized in an extruding-and-kneading machine at a melt temperature of 453 K at the outlet from the head of the
extruding machine. The straps obtained were cooled, cut into granules and used to form a
band 3540 m thick on an extruder with the orifice slit, at a temperature for the cylinder
zones of 438451468 K, orifice temperature of 468 K, temperature at the output 453 K.
Test specimens of corresponding sizes were cut from the band in longitudinal and transverse directions. Model thin films (20 m thick) from the CDA + TA + oligoester system
were prepared by hot pressing at 423 K and pressure of 12 MPa.
The phase transitions in plasticized compositions were determined by the refractometric method by finding the temperature dependence of the refractive index for thin (20 m)
films in an URL-1 refractometer at a continuous change of temperature at a rate of 1 K/min.
The glass transition temperature was determined by the thermomechanical method at a constant strain on a specimen (1.410 2 Pa) and a rate of 1 K/min and also refractometrically.
Preliminarily, the data obtained by both methods were shown to correspond one to the other.
The thermomechanical characteristics of the compositions were determined using a tensile
creep-measuring instrument according to State Standard GOST 18197-72 at a constant
strain (110 Pa) and heating rate of 5 K/min on specimens of 1.82.00.3)10 4 m.
128
The mechanical properties of model thin films were assessed on an N-2001 R-0.5 tensile tester at a strain rate of 0.3210 3 m/h with the automatic recording of the strain curve.
The mechanical indices of the extrusion films were determined at temperatures of 293 and
393 K on an Instron tensile tester according to GOST 14236-81 at a strain rate of 10 2 m/h
on specimens with the working area parameters of (5100.4)10 3 m.
The melt fluidity index MFI was determined by GOST 11645-73 on an IIRT instrument at a temperature of 463 K, load of 100 N, standard capillary of 0.948 mm in diameter
and 8 mm in length. The rheological properties of the material were studied on a capillary
constant-pressure viscosimeter at temperatures of 453, 463, 473 K and the rate of shear from
10 3 up to 10 4 s 1.
Due to the great importance of the performance stability at given temperatures in contact with biochemically active media during the development of plasticized compositions,
one should account for their thermodynamic stability. It provides for a long-time invariability of the properties not only in reprocessing, but also in long-term storage. In this connection, phase diagrams were obtained for triple CDA+TA+oligoester system of different
molecular nature (PDEA, PAC-22, PDEC, PPA-4), which made it possible to single out regions of homogeneity at various temperatures. Studies of the isothermal cross sections of
phase-equilibrium bulk diagrams have established that the homogeneity region for all systems studied expands with temperature increasing. Comparison of the phase diagrams of
the systems containing various-structure oligomers shows that an increase of the length of
aliphatic segments between ester groupings, which provide for the interaction with polar
groups of the polymer, leads to the deterioration of compatibility. Compatibility of the components of the CDA+TA+oligoester triple systems decreases in the sequence PPA-4 >
PAC-22 > PDEA. Analysis of the phase diagrams shows that at room temperature the systems comprising >57% of oligoester in the mixture are microheterogeneous.
By the example of the CDA+TA+oligoester systems, we considered the effect of oligoester on the efficiency of the plasticizing action of the TA+oligoester mixture with respect to CDA. For this purpose, we studied the concentration dependence of Tg and the
mechanical properties of the films. As the content of oligoester in the plasticizing system
increases, its plasticizing action rises. Herewith, addition of oligoester, which contains residues of molecules of sebacinic acid (up to 50% PAC-22), decreases Tg of the polymer to
a greater extent. Comparison of the phase diagrams and of the dependence Tg = f(Cm) shows
that interstructural plastification in the microheterogeneous system begins at the introduction of oligoesters. Therefore, a decrease of the extent of polarity of the components as the
result of the increase of the length of aliphatic fragments or a change of their branching in
the oligoester enhances the action of the second plasticizer, which plays the role of an interstructural lubricant leading to a large decrease of Tg.
When analysizing the data for the mechanical properties of model films from
three-component systems (Table 3.21), it is seen that the systems containing PDEA and
PPA-4 have the greatest breaking strength p; while the systems with PAC-22 are more
elastic (have a greater relative breaking elongation ). The studies conducted enabled singling out homogeneity regions for all systems studied. The regularities obtained were used
in developing food grades of ethrol with given rheological, strain-resistant and sanitary-chemical properties. Modified ethrols were fabricated by the traditional process.
The set of technological and performance properties of films fabricated from ethrol
compositions of various formulations (Table 3.22) was studied. In the general case, introduction of oligoester to an ethrol composition at the stage of its preparation significantly
(by an order of magnitude) decreases the effective viscosity of the melt, shifts Tg and Tm to
129
CHAPTER 3
the region of higher temperatures practically without changing the plasticity interval. As the
result of the decreased strength of the intermolecular bonds the deformability of the material
at increased temperatures increases. The obtained regularities were used when choosing the
optimal content of modifier in the plasticizing system to provide for a balanced set of technological and operational properties of ethrols of various purposes.
Table 3.21 Strength properties of CDA films plasticized by TA in a mixture with oligoesters
(15%).
Oligoester
TA:oligoester mass ratio
p, MPa
, %
3:1
1:1
1:3
3:1
3:1
5.6
4.2
8.7
7.1
4.1
4.5
13.0
6.0
4.5
12.0
PDEA
PDEA
PDEA
PPA-4
PAC-22
Comparative analysis of the rheological properties of base ethrol and ethrol modified
by PPA-4 showed that the optimal temperature of plasticizing material in an extruder was
438 K for the extrusion grade and 463 K for the blow-molding grade. These temperatures
provide for an intensive agitation of the melt at lower loads. It should be noted that MFI for
all modified compositions is much higher than the rated values. Such compositions can be
reprocessed at lower temperatures and smaller shear loads, which is confirmed by the data
obtained in reprocessing of modified compositions on industrial equipment.
Table 3.22 Process characteristics of modified ethrols.
p, MPa
Plasticizer and Melt viscosity,

its content, %
102, Pa s
TA (35)
TA(25)
PPA-4 (10)
TA (25)
PAC (25)
TA (25)
PDEA (10)
, %
at 293 K
at 393 K
at 293 K
at 393 K
24.0
3.5
60
40
2
4
48
42
100
140
5.2
45
20
140
5.8
45
30
130
Note: Polymer, CDA; plasticity range (Tpl Tg), 315 K.
The established anomalous dependence of the rheological, physicomechanical and

strain characteristics of modified ethrols suggests that the effect of strengthening of plasticized CDA at the introduction of small additions of oligoester is determined by structural
changes at the supramolecular level. An increase of the mobility of the structural elements
and the acceleration of relaxation processes in modified material provides for the formation
of a more homogeneous structure, which is confirmed by the data of electron-microscopy
analysis.
To determine the rational applications of packaging/container materials and consumer
containers on their basis, we determined the endurance and service time of articles in
130
contact with a product or a medium modelling this product (Table 3.23).

Table 3.23
Long-term strength of CDA-based specimens.
Temperature, K
293
323
Time to rupture, min

in air
in distilled water
in sunflower oil
in 3% solution of
lactic acid
6070
30
40
25
1200
1200
50
20
Note: Testing stress, 3.0 MPa.
Estimation of sanitary-chemical properties of test batches of materials and articles

from them, obtained by vacuforming and deep drawing, showed that more than 92% of the
specimens had satisfactory organoleptic parameters: a small (0.5 mg/l) dry residue, a small
amount of brominated compounds (1.55.6 mg Br/l). The amount of TA migrating to water
from ethrol-based material is 0.05 g/l; that of acetic acid, 5 mg/l; which do not exceed the
maximum permissible levels of migration.
Thus, consumer containers based on ethrol should be recommended for prepackaging
of spreads with an increased content of fat; lactic-acid products, as well as hot beverages at
their short-time effect.
3.4
Interaction of cellulose with water
Chemically, cellulose is a polymer whose elementary link is anhydro-D-glucose. The structure of the cellulose macromolecule can be represented by the following formula:
CH2OH
CH
CH2OH
O
HOHC
CH
CH
HC
OH
OH
CH2OH
O
OHC
CH
CH
CH
OH
OHC
HC
OH
O
CHOH
CH
n
OH
HC
OH
Each elementary link contains three hydroxyl groups. Two of them are secondary; one
is primary. This explains the different reactivities of the hydroxyl groups. The interaction
energies of these groups with water molecules are different, too, which would be discussed
in detail in Chapters 2 and 3. Here, we would like to note that the high hydrophilicity cellulose is due namely to the presence of three hydroxyl groups in the elementary link; these
groups interact with water molecules by forming strong hydrogen bonds.
Sorption of water by cellulose can be radically changed only by substitution of the hydroxyl groups. Indeed, a gradual substitution of the hydroxyl groups for other groups of atoms changes the sorption properties of cellulose. Thus, unetherified cellulose at 65%
relative humidity absorbs 1112% of water; cellulose diacetate, 6.5%; and triacetate, 3.2%.
Cellulose esters with a longer aliphatic residue absorb only fractions of a percent of water.
CHAPTER 3
131
The effect of the end groups of cellulose macromolecules of the sorption of water is
small, as the (number-average) extent of polymerization for common specimens of cellulose is comparatively large (greater than 200300).
Cellulose materials used in practice have natural contaminants of other polysaccharides and lignin (the satellite of cellulose in wood), which have some influence on the sorption of cellulose water; besides, there are disturbances in the chemical composition of
macromolecules of cellulose proper. These disturbances mainly consist of a partial oxidation of the hydroxyl groups in the links of chains up to carboxyl groups (without or with the
rupture of the anhydro-D-glucose ring). These partial disturbances have a small influence
on the sorption of water, but the sorption of cations from the aqueous solutions of metal
salts, e.g., the sorption of iron ions, may increase substantially.
Partial destruction of cellulose in its purification leads to a decrease of the extent of
polymerization and to the emergence of low-molecular-mass products, which can be partially soluble in water, especially at increased temperatures. Without having a noticeable
direct effect on the equilibrium values of water sorption by cellulose materials, under certain conditions this can affect the water sorption kinetics. One of the hypotheses explaining
the differences in the reactivity (kinetics of the process) during the etherification of various-origin cellulose materials is related to the account for the physical transformations of
low-molecular-mass admixtures during the drying of cellulose at high temperatures.
Though the presence of the hydroxyl groups in cellulose is a factor, which mainly determines its sorptivity with respect to water, a significant role is also played by the physical
structure of cellulose material, which has an effect on both the equilibrium values of water
absorption and on the kinetics of the sorptiondesorption processes.
First of all, it should be noted that cellulose is a crystallizable polymer. The energy of
hydrogen bonds emerging between water molecules and hydroxyl groups of cellulose
proves to be insufficient to break the crystalline lattice. Therefore, the sorption of water occurs only in amorphous regions and does not affect the crystalline regions (except the hydroxyl groups, which are on the surface and in the defect regions of the crystallites). The
extent of crystallinity of cellulose depends on the origin (prehistory) of the specimen. Natural cellulose (cotton, ramie) has the greatest degree of crystallinity. Cellulose regenerated
from solutions of cellulose and its ethers (following the saponification of the latter) has a
much lower crystallinity. Usually, the extent of crystallinity estimated from X-ray diffraction measurements is 6070% for natural cellulose and about 2540% for regenerated cellulose.
The values of water sorption differ accordingly. As a rule, the sorption of water by regenerated cellulose (viscose fibres) is approximately two times as high as that of natural
cellulose (e.g., cotton or ramie).
Alkaline and temperature treatments of cellulose can cause transitions between particular types of crystal lattices. Thus, a cellulose modification I, which occurs in natural specimens, during the transfer of cellulose into the solution followed by regeneration from
solution or during the treatment in moderate-concentration alkali and then the washout of
alkali passes into a crystalline modification of cellulose II, which differs from cellulose I
by interplane distances and angular ratios in the lattice. At increased temperatures, cellulose
II passes to a modification of cellulose IV. All these transformations, apparently, would not
have a strong effect on the sorption of water by cellulose, if they would not have been accompanied by the simultaneous changes in crystallinity. During the mercerization (alkaline
treatment) and at the regeneration of cellulose from solutions the extent of crystallinity decreases significantly, as we mentioned above. Some increase of the extent of crystallinity
132
occurs during the temperature treatments of regenerated cellulose in moist state, which is
accompanied by a partial transition of cellulose II to cellulose IV. This treatment leads to a
cellulose sorptivity decrease with respect to water, though the isomorphic conversion
proves to be not the determining event but a process occurring in parallel.
Cellulose can be totally amorphized by dry mechanical grinding. This can be seen from
the results of the X-ray diffraction study and from the fact that the heat of the interaction of
this cellulose with water is three to four times as high as the heat of wetting the nonground
cellulose. But the interaction with water is followed by the crystallization process, and cellulose again becomes insoluble. Incidentally, during the formation of viscose fibres in the
initial stage after the saponification of cellulose xanthogenate these fibres very strongly
swell in water (after the washout of precipitation-bath salts), but after some time the swelling strongly decreases as the result of the completion of the crystallization processes.
Besides the important role of the phase state in determining the sorption properties of
cellulose, we should also note the effect of such a factor as the physical structure of cellulose
material. The matter is that besides the true sorption of water (absorption) determined by
the amount of the amorphous component of polymer, there occurs a capillary uptake of water by cellulose materials due to porosity, which can be obvious (capillaries in natural fibres,
interfibrillar spaces in wood, pores in cells of plant cellulose and in artificial cellulose fibres, capillaries and pores in paper and textile materials) and hidden, revealed during the
wetting in water and representing the pores and capillaries, which are collapsed in the drying of moist cellulose materials and are capable of being restored due to the relaxation of
internal stresses remaining in the dry specimen.
Experiments confirming the thermodynamic nonequilibrium of real cellulose materials, which determines the dependence of the sorption properties on their prehistory, were
described.
It should be noted that this nonequilibrium renders an especially serious effect on the
kinetics of absorption processes.
4
4.1
Compositions for Decorative

Finish and Protection of
Packaging Products
Bases of the formation of protective and decorative finish coatings
Aqueous dispersions of polymers are the most promising class of film formers in paper and
printing industries, applicable for fabrication of protective and decorative coatings on packaging products.
The use of polymers aqueous dispersions has a number of advantages as compared
with solutions of polymers in organic solvents, making it possible:
to eliminate the danger of fire and to decrease occupational hazards of work
to decrease considerably the power intensity of production and to eliminate the use
of heavy equipment
in a number of cases to achieve a higher quality of articles produced.
Fabrication of polymer coatings for packaging products with a required set of properties is the final aim of using latexes or aqueous dispersions of polymers for finishing printing products. In this connection, of great importance is the quality of polymer coatings and
the mechanism of their formation.
Formation of films from polymer solutions has been studied by many researchers,
primarily by Russian scientists V.A. Kargin, P.V. Kozlov, A.Ya. Drinberg, P.I. Zubov,
S.S. Voyutsky and others.
In contrast, the formation mechanism and structure of films from polymer dispersions
have been studied insufficiently. The effect of the chemical composition, structure of latex
particles and coatings on the decorative and protective properties has not been studied; the
impact of the nature of the support, especially of fibrous materials, on the formation and
properties of latex coatings has not been studied sufficiently enough.
In works of the recent years the physicomechanical properties of the coatings have
been shown to depend not only on the chemical structure of the film former, but also on the
colloidalchemical nature of latex, size and structure of latex particles, nature and concentration of polar groups.
It follows from these data that the complex structure of latex particles, which are supramolecular formations consisting of simpler structural elements, determines the incompleteness of the relaxation processes and has an effect on the values of internal stresses, the
kinetics of their buildup and relaxation.
The specific features of polymer coatings used for finishing printing products are that,
134
along with good physicomechanical properties, they should have a high light resistance,
gloss and have no tackiness.
The dependence of these parameters on the structure and chemical composition of a
polymer has not been studied sufficiently. This impedes the correct scientifically grounded
choice of film formers for finishing the printing products and does not make it possible to
formulate the requirements for finishing compositions.
The effect of the chemical composition of polymer, the structure of latex particles, the
nature and concentration of polar groups, the colloidalchemical nature of latex on the formation of the coatings, decorative and physicomechanical properties (strength, adhesion,
relative strain, internal stresses) was studied. This was done by comparing the kinetics of
forming the structure and properties of the coatings on a model non-porous glass support
with the mechanisms of forming the coatings on fibrous bases of the type of offset paper
and offprints.
One of the ways to increase the quality of printed matter is application of transparent
polymer coatings on printed material, which improves its decorative appearance and increases mechanical strength.
The following requirements are imposed on polymer films on printed matter (offprints): high gloss, elasticity, transparency, absence of tack, water resistance, light permanence, stability and mechanical strength.
Application of protective and decorative coatings to the surface of printed matter is
done in two different techniques: lamination of the end polymer film to offprints and direct
application of a film former to offprints.
In application of coatings to printed matter by the latter technique, film formers of
three different types can be used, which differ significantly by their film-formation mechanism:
solutions of polymers
compositions of oligomers
dispersions of polymers.
The method of producing coatings from polymer solutions is used the most for finishing printed matter in Russia and abroad. This is due to the simplicity of producing coatings
and the absence of additional components in their composition (emulsifiers, hardeners,
etc.), which in some cases worsen the properties of the coatings.
The chemical composition of these lacquers is approximately as follows (in %):
Polymer
Plasticizer
Solvent
4050
25
5845
Amorphous polymers of the type of polyvinyl acetate, polyvinyl butyral, polyvinyl alcohol, cellulose esters etc. are mainly used as film formers.
Coatings from polymers with a large extent of crystallinity are distinguished by a high
strength, but they have not found use in finishing printed matter due to poor adhesion to the
coated surface.
The decorative and protective properties of the coatings are affected by the nature of
solvents used. The most widespread classes of solvents are alcohols, ethers and esters,
hydrocarbons, etc.
CHAPTER 4
135
The hydroxyl group confers a greater polarity and strong hydrophilicity to alcohols.
Methyl, ethyl and propyl alcohols are totally mixed with water. A decrease of hydrophilicity
with the molecular mass increasing affects the dissolving capacity. The higher members of
the homologous series, e.g., butyl alcohol, improve the flow behaviour and prevent the
blooming of films produced by application of nitrocellulose lacquers. Alcohols are rather
stable compounds and find application for many types of lacquer-and-paint materials.
Ethers, such as ethyl ether and propyl ether, in a mixture with other solvents, for instance, dissolve cellulose. These ethers are too volatile, readily form peroxides, and are used
in compositions of lacquer-and-paint materials on a limited scale.
Esters are similar to ketones by polarity, but are less hydrophilic. Formates, which are
esters of lower molecular masses than acetates, are unsuitable due to their instability, are
easily hydrolyzed by water and are too volatile. Acetates (ethyl acetate, butyl acetate, isopropyl acetate) are very widely used, especially in nitrocellulose materials.
To impart elasticity to the film, plasticizers are introduced into the solution of a film
former. Fluids with a relatively small molecular mass are usually used as plasticizers.
Earlier printed-matter finishes made use of lacquers based on natural resins of the type
of copal, wood rosin and sandarac in ethyl alcohol.
Copal is a hard resin of plant origin, of transparent yellow or reddish colour. The heat
treatment of copal at 280320C improves its solubility in ethyl alcohol as the result of
stripping volatile substances. Manila copal, completely dissolvable in ethyl alcohol, is used
for fabrication of lacquers.
Wood rosin is conifer resin; it can be of two types depending on the method of production: gum rosin and wet-process rosin. Gum rosin is produced from raw gum of conifers,
wet-process rosin is extracted from resinous wood with alkali. Wood rosin is a mixture of
isomeric monobasic rosin acids of the general formula C20H30O2. Rosin acids present in
wood rosin are a mixture of dextropimaric acid with conversion products of levopimaric
and -sapinic acids, the major of which is abietinic acid. The structure of abietinic acid is
expressed by the formula:
H3C
COOH
CH3
CH3
CH
CH3
Sandarac is an thick aromatic resin of the North-African Sandarac tree.

The approximate composition of these lacquers, in %:
Copal
Wood rosin
Sandarac
Ethyl alcohol
25.525.0
17.510.0
5.0
5760.0
Lacquers were also used for lacquering dust wrappers and other kinds of printed matter. Lacquers from imported natural resins are expensive, are produced in minor amounts
and have not found wide use in printed-matter finishing.
Finishing of printed matter in the West is done using nitrocellulose lacquers. Their formulation includes nitrocellulose, a plasticizer and organic solvents methyl alcohol,
136
methyl acetate, ethyl acetate, butyl alcohol, toluene, xylene.

These lacquers give high-quality coatings on chalk-coated paper. Nitrocellulose lacquers are toxic and explosive. In spite of this, they are manufactured as modified compositions on a large scale by a number of companies: Grafisk Farg (Sweden), Sadolin (Finland),
lacquer L-186; Sicpa (Switzerland), rapid-setting lacquer intended for application to offprints printed on chalk-coated paper; Herbol (Germany), gloss lacquer with high gloss of
the coating; Herberts (Germany), brilliant lacquer GL; Lorilleux-Lefrans (France), delta
lacquer and lacquer for finishing offprints printed by high-print and offset methods.
Iditol lacquer is an ethyl-alcohol solution of the product of polycondensation of phenol
with formaldehyde in the presence of a catalyst (oxalic or hydrochloric acids).
OH
OH
O
+ n HC
O
OH
CH2
OH
CH2
CH2 ...
n H2O
Coatings based on this resin are light non-permanent.

Carbinol lacquer is a solution of MBK-10 resin in ethyl alcohol. Products of polymerization and copolymerization of vinyl ethyl carbinol are called carbinol resins. Resin
MBK-10 is produced by copolymerization of dimethyl vinyl ethynyl carbinol containing
no inhibitor, with technical-grade methyl methacrylate and butyl methacrylate in the presence of benzoyl in ethyl cellosolve. Carbinol lacquer forms a glossy film with a yellowish
tint on the offprint. The lacquer has a sharp unpleasant smell, preserved in the coating even
after a prolonged drying at 80C.
Lacquer KS-235 is a solution of low-molecular-mass carbinol resin and cyclohexanone-formaldehyde resin in hydrazite. The film of this lacquer is light-permanent, elastic, but has an increased tackiness, which leads to the agglutination of offprints in a paper
sheet stack.
For finishing printed materials, home industries manufacture polyvinyl acetate
lacquer, which is a 40% solution of polyvinyl acetate in ethyl alcohol. Polyvinyl acetate is
a thermoplastic colourless transparent solid product obtained by polymerization of vinyl
acetate.
n CH2
CH
O
CH2
CO
CH3
CH
O
CO
CH3
To impart polyvinyl acetate with rubberlike properties, it is plasticized with dibutyl

phthalate. The alcoholic solution of polyvinyl acetate is used as a lacquer for lacquering offprints; it forms a light-permanent, transparent, elastic, colourless film without smell but
with a low gloss, even on chalk-coated paper.
Formation of the film from polymer solutions on the surface of printed matter is accompanied by the emergence of local physical links between the most active groups of
structural elements as the result of the evaporation of the solvent and the slowdown of the
relaxation processes.
It has been shown that the incompleteness of the relaxation processes during the formation of coatings from polymer solutions (polyvinyl alcohol and its derivatives, nitrocellulose and others) leads to the emergence of significant internal stresses reducing the service
life of the coatings.
CHAPTER 4
137
Coatings from lacquers based on polymer solutions, along with good decorative and
high physicomechanical properties, have a number of drawbacks. They contain toxic and
fire-hazardous solvents, are distinguished by the low content of dry matter at a working viscosity, poor light permanence; evoke the dissolution of alcohol-nonresistant pigments.
Organic solvents in lacquers are, as a rule, lost irreversibly, they pollute the air in production facilities and necessitate special measures to be taken on safety regulations and occupational sanitation (among solvents, aromatic hydrocarbons are poisonous).
According to the data of Western statistics, the level of occupational diseases in workers of paint shops and bays is five times and more higher than the average level in industries.
In this country, where human health is given great attention, abandonment of organic
solvents in protective coatings technology is not only a technical but also a social problem.
The use of organic solvents is a critical drawback of lacquer-and-paint materials also
because it creates problems of technological character lacquers should be diluted with organic solvents before application; this makes their compositions, dissolving capability, volatility, viscosity etc. variable.
One of the directions in solving the problem of excluding organic solvents from the
formulations of lacquer-and-paint materials is to develop aqueous lacquer-and-paint compositions, i.e., such systems, where the role of a medium determining the required conditions of applying and forming a coating is played by water.
When using aqueous lacquer-and-paint systems, it becomes possible not only to save
on the cost of irrevocably lost organic solvents, on ventilation and safety measures, to make
the painting process safe and flame-proof, but also to receive a number of technical advantages:
possibility of applying the coating at increased humidity
use of electrophoretic sedimentation, a method special for aqueous systems; in the
West, this method found use in paper-making plants in fabrication of high-gloss paper rolls
harmlessness and smaller labour intensity of cleaning the equipment
water as a solvent or dispersant is extremely convenient.
In this country, some printing plants attempted to use alcoholwater solutions of polymers, whose composition is approximately as follows (in %):
Polymer (alcohol/water-soluble)
Additives
Solvent (a mixture of water and alcohol, 1:2)
1015
510
8575
Special additives are meant to be materials, which are introduced into the composition
for hardening, crosslinking of the polymer (e.g., boric acid for polyvinyl alcohol, etc.). They
form films of high strength and good decorative properties, but the use of these polymer
solutions for finishing printed matter is made difficult due to the sharply increased viscosity
of film formers at a comparatively low percentage of polymer in the lacquer. In some cases,
this considerably affects the gloss of the film. Special additives should be introduced into
the lacquer immediately before its application to offprints, as the life time of such a lacquer
is several hours. A large amount of water in the formulation leads to the notwettability of
the most ink-saturated regions of the offprint, to a decreased adhesion to the substrate and
to a deformation of the products as the result of strong wetting. A considerable energy is
required to remove such a large amount of water, and the rate of the drying process of lacquered offprints does not correspond to the general rate of the lacquering process.
138
For instance, a nonexplosive and nontoxic lacquer PVSK based on polyvinyl alcohol
...
CH2
CH
CH2
CH
...
OH
OH
has been developed, with an addition of boric acid and emulsifier OP-7. The lacquer is not
in use due to the duration of drying of lacquered offprints at high temperature and their curling, although it has good decorative and physicomechanical properties (high gloss, resistance to abrasion, transparency, light permanence of the film).
Lacquers based on vinyl resins have been developed for lacquering specific kinds of
production labels and others. The lacquer PVM-1 is a solution of polyvinyl butyral with
an addition of water-soluble phenol formaldehyde film VMCh-4, whose formula is as follows:
HOH2C N CH2 N CH2 N H
HOH2C
HN
O
CH2O(CH)2OC2H5
This resin is added as a crosslinking agent to increase the water resistance of the film.
A special class of compounds for production of coatings are oligomers. Their specific
features are that the monomer present in them performs the role of a polymerizing solvent.
In film formation, it is involved in the polymerization proceeding on the support and leading
to the formation of a three-dimensional network structure. This provides for the production
of materials with a low initial viscosity at an increased concentration of the film former.
The use of oligomer systems enables a sharp decrease of the content of volatile solvents and
yields coatings with high mechanical and adhesion properties.
Oligomer compositions include oligomers and polymerizing solvents and, in some
cases, evaporating solvents. Synthetic resins (condensation polymers alkides, phenol
formaldehyde polyesters, amino formaldehyde esters, and others) are used as oligomers.
Oligomer systems are not used in pure form in printing industry for finishing printed
matter. They are used in a mixture with natural resins of the type of wood rosin, copal, sandarac and vegetable oils. Hard resins, used since long time ago in production of oil lacquers,
interact with oils by way of reetherification to form products similar to alkyds in their structure.
Thus, for instance, the lacquer for overprinting is a solution of hard resin in a mixture
with vegetable and mineral oils. Fixation of the lacquer on offprints occurs due to a partial
soaking-in of oils followed by the formation of a strong film as the result of oxidative polymerization. In spite of a number of advantages such lacquers present (lacquering can be
done typographically and by the offset method, sometimes selectively from the printed elements of the mold), they do not make it possible to produce films with high mechanical
and decorative properties in one run on papers with high absorptivity and low smoothness.
Formation of the film under normal conditions of drying is very slow, so anti-setoff preparations have to be used, offprints have to be kept in stacks not higher than 3040 cm and
shook every hour to avoid tackiness. To produce a continuous film, high drying temperature
and long drying time are required, as the mechanism of coating formation from these compositions is complex and is accompanied by the removal of solvent, by the oxidation and
polymerization processes to form the three-dimensional network. It is reported that electromagnetic waves of a frequency fro 0.3 up to 3000 Hz are used to accelerate stacking of printed materials with the aim to rapidly obtain a dry protective lacquer film on offprints.
CHAPTER 4
139
The most widespread in home industry is a lacquer (CF-1) based on an oligomer film
former the cyclohexanoneformaldehyde resin. The CF-1 lacquer is a solution of the following composition (in %):
Cyclohexanoneformaldehyde resin
Plasticizer
Colophony (pine wood rosin)
Ethyl alcohol
52
2
5
41
When used to lacquer papers with high absorptivity (e.g., offset papers), this lacquer
does not form a film with good physicomechanical and decorative properties. To impart the
coating with gloss and to increase the abrasion resistance of the offprint, two layers of lacquer should be applied, which is extremely unproductive and uneconomical.
4.2
Application of aqueous dispersions of polymers for finishing products
Aqueous dispersions of polymers have advantages in comparison with aqueous solutions

of polymers, as they enable production of film formers with a greater concentration of polymer (4050%) at a comparatively low viscosity and rapidly dry to form the film. The viscosity of dispersions does not depend on the extent of polymerization of resins.
Film formers for finishing packaging materials were chosen in two directions:
first, Russian-make aqueous dispersions of polymers were used for finishing; the decorative properties of coatings on their basis were studied
based on the analysis and studies of Western patents and literature, the most promising aqueous dispersions of polymers were chosen and recommended to Russian chemical
enterprises for the development of special compositions of latexes with account for the requirements of the qualitative finishing of printed materials and for availability of Russian
raw materials for production of latexes.
Aqueous dispersions consists of an aqueous dispersion medium and polymer dispersed
in it. Polymer dispersions used for coatings on paper are obtained predominantly in the reaction yielding high-molecular-mass substances in an aqueous medium in the process of
emulsion polymerization: in the presence of an emulsifier and an initiator.
Dispersions used the most for application of surface coatings to paper are vinyl acetate
dispersions, copolymers of this type, as well as acrylate dispersions. The company Hoechst
(Germany) manufactures an aqueous dispersion of polyvinyl acetate under the name of
Movilit for fabricating decorative coatings on paper.
Many researchers deal with synthesizing novel compositions of aqueous dispersions.
Western patents recommend an aqueous dispersion containing a linear polymer and the ammonium salt of the copolymer of diisobutylene with maleic acid monoamide. The quality
of this coating is good: butadienepolystyrene copolymers and polyacrylates can be used
for coatings on paper; DuPont (USA) manufactures a dispersion of blended polymers of
polyvinyl acetate and polyethylene under the trademarks of Elvax 150 and Elvax 250,
which form a glossy coating on printed material.
Methods of producing aqueous dispersions of polymers are different. Bayer et al. propose the following method: vinyl esters (e.g., vinyl acetate, vinyl propionate) as well as
mixtures with other polymerizing esters (e.g., esters of acrylic, maleic and fumaric acids)
140
are polymerized in a neutral or weakly acidic medium in the presence of water-soluble activators and protective colloids.
A method for producing polyvinyl acetate dispersions stable at low temperatures was
developed. The release of an aqueous dispersion of a copolymer of vinyl acetate with other
monomers under the trademark of Wallpol 9120 is reported; the formulation is used for lacquer coatings. This dispersion is produced using esters of unsaturated (maleic, fumaric) acids and acrylic-acid esters as a copolymerization monomer.
Films of polymer aqueous dispersions on paper, as well as lacquer films for finishing
printed materials, should possess certain properties: gloss, elasticity, transparency, water
resistance, light permanence, mechanical strength, stability and low-temperature resistance.
Low-viscous dispersions forming thin films (1015 m) on paper can be used for coating printed and packaging materials. The gloss of films of vinyl-polymer and polyvinyl acetate dispersions depends on the size of their particles. Coarse dispersions with particle size
of 0.52.0 m form mat coatings. Fine dispersions with particle size of 0.050.2 m form
glossy elastic coatings. Films of polymer coatings on paper are transparent.
Water resistance of polymer coatings is of great significance. Water-resistant coatings
can be produced using polymers obtained by polymerization of vinyl acetate with additions
of acrylic- or nitrile acrylic-acid esters.
Coatings from aqueous dispersions of polyvinyl acetate have a high light permanence.
A polymer coating for single- and multicolour offprints, which possesses a mechanical
strength, has been developed.
There are stable and low-temperature-resistance aqueous dispersions of polymers. The
stability of the dispersions at a temperature of 15C for six months is achieved by using
a mixture of water and (ethyl, methyl) alcohol at weight ratios of 190:10100:100 as an
emulsion medium.
It is proposed to introduce synthetic (acryl, butadiene styrene, polyvinyl acetate) resins
into dispersions of epoxy esters to produce stable dispersions. A dispersion possessing both
a stability and low-temperature resistance was produced. The patent literature also recommends stable and low-temperature-resistant dispersions consisting of a homogeneous polymer or copolymer (e.g., ethylene and alkylacrylate, in the hydrocarbon chain of which
2.525% of carbon atoms are substituted by carboxyl, carboxylate or carbamyl.
Viscosity is of great significance in application of dispersions to paper. It has been
found that at the same dry residue a coarse dispersion of polyvinyl acetate has a viscosity
of 100 ps; a fine dispersion, several poise. It is proposed to regulate the viscosity of the dispersion of vinyl resins with crotonic acid. For this purpose, crotonic acid is added to the
dispersion of vinyl acetate, and copolymerization is carried out. By changing pH of the copolymer obtained, the viscosity of the dispersion is regulated within the required limits.
The dependence of viscosity and temperature has been studied; the viscosity of a polyvinyl acetate dispersion with particle size of 0.22.0 m was found to decrease with its temperature increasing.
Divinyl styrene latexes are used as coatings for paper to increase its printing properties
and the quality of typographic and offset printing; herewith, the resistance of the offprint to
abrasion in dry and moist state increases.
Divinyl styrene latex SKE-30, modified by an aqueous solution of polyvinyl alcohol,
is used to produce special lacquer-and-paint materials for the printing industry. Special
primers for producing paper-based binder materials were developed on the basis of this
latex.
However, coatings from these latexes are characterized by low decorative properties.
CHAPTER 4
141
A latex based on the copolymer of acrylate with vinylidene chloride Rhoplex A-9
is widely used for coatings on paper for packaging materials. This latex is colourless, preserves the flexibility of paper, causes no sticking, yields well to dyeing, but its film is not
light-permanent. Copolymers of vinyl chloride and vinylidene chloride are used for finishing packaging materials, paper and paperboard.
A possibility of using latexes manufactured by Russian industries for finishing printed
materials has been studied.
With this in mind, a large set of fine dispersions of polyvinyl acetate,
...
CH2
CH
...
OCOCH3
obtained under diverse conditions of synthesis (Table 4.1) and differing by their molecular
masses (Table 4.2), was synthesized in the presence of various emulsifiers (Table 4.3), with
introduction of phenol-formaldehyde resins. Analysis of the data presented in the tables
shows that PVA dispersions synthesized under various conditions yield no coatings with
the required set of mechanical and decorative properties. Regulation of the molecular mass
of polymer and the nature of emulsifier (Tables 4.2 and 4.3) failed to improve the decorative
properties of coatings. Modification of the PVA dispersion by phenol-formaldehyde resin
improves the decorative properties, but leads to a sharp increase of brittleness of the film
and to light nonpermanence.
Table 4.1
Type of latex
Dry residue, %
Fine-particle
polyvinyl acetate
(PVA) dispersion
48
49
47.8
48.7
49.0
48.5
47.9
49.2
Characteristics of dispersion and quality

of coating on offset imprint
Slightly sticky, light nonpermanent; grains in the
coating
nonsticky; good gloss but light nonpermanent
mat nonsticky film
low gloss; dispersion does not wet saturated areas
of offprints
dispersion soaks into the offprint without forming
a glossy coating even after two layers of coat
high gloss, coating non-sticky; dispersion unstable
(coagulates on day 3)
Table 4.2
Type of
latex
Dry residue,
%
Emulsifier
Fine-particle
PVA
48.7
OP-7
49.1
OP-10 with 0.2%

sulfanol addition
Characteristics of coating on offset imprint

no gloss; dispersion does not moisten black
ink
no glossy film is formed; dispersion does not
moisten saturated areas of offprint
142
Table 4.2 (continued)

Type of
latex
Dry residue,
%
Emulsifier
49.5
OP-10
48.3
technical-grade
proxanol 228
16% proxanol
alphanol 12
48.5
47.9
Characteristics of coating on offset imprint

cast film is lusterless; dispersion does not
moisten black ink
cast film is lusterless; dispersion does not
moisten black ink
no film is formed
film is lusterless but non-sticky
Note: PVA, polyvinyl acetate dispersion; alphanol and sulfanol, anionogenic preparations; OP-8,
OP-10 and proxanol, nonionogenic preparations.
According to the data of patents, PVA dispersions have found wide use owing to their
relatively low cost.
Their major drawback is that at a normal temperature they are incapable of forming a
continuous film and, thus, need plasticizers to be added. Due to the volatility and migration
of plasticizers, the film is rapidly aged and becomes brittle. Besides, vinyl acetate ester is
apt to saponify. By introducing various additives, we succeeded in obtaining a composition
for finishing printed products; however, its use on the existing equipment is associated with
a number of technological difficulties.
To avoid introducing a plasticizer into the ready polyvinyl-acetate dispersion, a method of internal plasticization was used, namely, fabrication of copolymers of vinyl acetate
with other monomers (esters of unsaturated acids maleic, fumaric; esters of acrylic acid).
Table 4.3
Type of latex
Fine-particle PVA
Dry residue,
%
Molecular mass
43.7
96.600
45.6
47.3
45.2
48.3
79.700
67.900
53.300
90.600
43.7
44.3
Specimen of aqueous
dispersion from
Germany
non-sticky, with good gloss; dispersion

does not moisten black ink
dispersion coagulates on day 3
low gloss
no gloss at all; dispersion unstable
dispersion coagulates on day 2
hydrocarbon: H2O Monomer

ratio
dosage
Fine-particle PVA
with different
proportions of
monomer
Fine-particle PVA
Characteristics of coating
on offset imprint
2:3
1:1
with addition of water-soluble

phenol-formaldehyde resin
1/20
1/10
cast film has high gloss

but is very brittle
cast film is lusterless
rigidity of film increases and

non-light-resistance appears; in time,
introduction of resin causes coagulation of
dispersion
forms nonsticky coating, with high gloss;
cast film grows turbid in the light (on day
3); opacity increases in time
CHAPTER 4
143
Copolymers of vinyl acetate (VA) with ethylene grafted in several cases with acrylamide were tested. Aqueous solutions of solvars with various ratios of the hydroxyl and acetate groups, and dispersions of copolymers of polyvinyl alcohol with acrylonitrile and
acrylic acid (Table 4.4) form coatings with poor decorative properties. The decrease of the
number of acetate groups in solvar increases the gloss, but the adhesion of coatings becomes
worse in this case.
Table 4.4
Type of latex
PA copolymer : AAN
Ratio of
Dry Content of
components residue, acetate
%
groups, %
64:36
Latex rapidly soaks to form a

low-gloss film
PA:PVA (solvar)
PA copolymer : AA
VA copolymer : DAC
Characteristics of coatings
on offset imprint
21
18.2
9
Content of AA
7.6%
38%
25%
10.5
7.4
8.4
96:4
94:6
90:10
88:12
47.5
46.7
35.8
42.3
Gloss increases with decrease of

acetate groups, viscosity of solutions
increases
Coating has no gloss; viscosity of latex
increases with percentage of AA,
causing warpage of imprint
Cast films are yellow and
nontransparent; latexes are unstable
(peel off with time)
emulsion N-542
Film light-nonpermanent; gloss is

high after two coatings; lacquer film
can be calendered
NC with different
degrees of branching
Initial suspensions are very viscous;

when diluted, soak into imprint
without forming a glossy film
Note: PA, polyvinyl alcohol; AAN, acetic acid nitride; PVA, polyvinyl acetate; AA, acrylic acid;
VA, vinyl acetate; DAC, diallyl cyanamide; NC, nitrocellulose.
According to the literature data, at a certain ratio of components the copolymer of vinyl
acetate with ethylene has a higher strength and elasticity as compared with high-pressure
polyethylene; is resistant to cracking, action of ultraviolet rays; has good adhesion properties; is resistant to alcohols, glycols, organic acids and is used in a paper-finishing composition. The copolymer of vinyl acetate, ethylene and triallyl cyanurate is used to form a
smooth glossy coating on paper and paperboard.
Coatings with unsatisfactory decorative properties also form dispersions of vinyl acetate with diallyl cyanamide. Coatings from the emulsion based on nitrocellulose are distinguished with a low light permanence.
Aqueous dispersions based on copolymers of vinyl acetate with ethylene, grafted in
several cases with acrylamide, and introduced polymethyl siloxane (Table 4.5), as well as
copolymers of divinyl with methacrylic acid or methacrylamide fabricated at the S.V. Lebedev All-Russian Institute of Synthetic Rubber were tested as film formers for finishing
144
printed products. As seen, coatings based on these dispersions have poor decorative properties and low strength.
Table 4.5
Type of aqueous
dispersion
Colloidal characteristic Surface Characteristic of

tension,
free film
dyn/cm
dry pH ratio of
elong- tensile
residue,
components
ation, % strength,
%
MPa
VA copolymer:ET
49
49
3.9
3.9
VA copolymer:
ET:AA
47.4
80:15
82:12
Characteristic of
coating on offset
imprint
900
500
0.079
0.10
Very sticky
Very sticky
3.5 80.5:17:2.5
47.1
500
0.42
48.2
47.8
3.4
3.6
43
41.7
570
550
1.5
2.4
Coating is sticky,
dispersion does not wet
saturated areas
of imprint
Ditto
Ditto
VA copolymer:ET
with addition of
PMS-200
57.7
5.3 80:20 and

10%
39.3
550
2.7
Sticky due to residual

monomer (6.5%)
VA:ET with
addition of SiO2
44.3
5.5 90:10 and

20%
39
400
6.9
copolymer
DMMA-65-1GP
DMMA-65(60)-2
43.0
8.5
42.0
8.3
Grains in dispersion
make coating rough,
latex does not wet black
ink
Gloss not high; latex
does not wet black ink
Gloss not high; total
wetting of black ink
82:17:1
79:20:1
Note: VA, vinyl acetate; ET, ethylene; AA, acrylamide; PMS, polymethyl siloxane; DMMA-65-1GP,
divinyl and methacrylic acid; DMMA-65(60)-2, divinyl and methacrylamide.
As shown by the preliminary selection of dispersions and analysis of Western literature, acrylic dispersions of polymers proved to be the most promising for finishing coatings.
Acrylates begin to exhibit a film-forming ability almost at 0C; what is more, the produced
films are distinguished with a sufficient mechanical strength, as well as a high light and atmospheric resistance. A characteristic property of polyalkylacrylate films is their high
gloss, resistance to the action of UV light and molds.
Good results using these dispersions for finishing reel paper suggest that there is a tendency to use aqueous dispersions of polymers for finishing printed packaging material.
The employment of aqueous dispersions of polymers requires special equipment for
their application, development of special process regimes and method of drying polymer
coatings. These important issues are being dealt with for several years now by many advanced companies in developed countries.
Dispersions based on triple copolymers of ethylacrylate, nitrile acrylate, -m-styrene
with various ratios of the components were obtained (Table 4.6), as well as copolymers
based on ethylacrylate, nitrile acrylate, -m-styrene and 2-ethyl hexyl acrylate. It is seen
CHAPTER 4
145
that coatings based on these copolymers have poor gloss and do not wet the saturated regions of offprints.
Table 4.6
Ratio of components
Colloidal characteristic of Condition of

latex
synthesis
dry residue, sp
%
Characteristic of coating
pH
EA:NAC:-m-styrene
75:20:5
37.5
2.6
EA:NAC:-m-styrene
75:20:5
EA: 2-EHA: NAC:
-m-styrene 50:25:20:5
EA:NAC:-m-styrene
65:20:15
EA:NAC:-m-styrene
80:5:15
37. 5
2.0
37.6
3.4
3.45 Emulsifier was Coating has a pungent smell,

fed batchwise bad gloss; latex does not
moisten greasy areas of imprint
3.65 Emulsifier was Ditto
batched
4.7 Ditto
Ditto
38.1
1.9
3.6
Ditto
37.6
1.9
2.7
Emulsifier was
fed batchwise Ditto
Ditto
Note: EA, ethyl acrylate; NAC, nitrile acrylate; 2-EHA, 2-ethyl hexyl acrylate.
Thus, latexes produced by home industries and specially synthesized with the view of
using them for finishing printed products, do not form coatings satisfying the required set
of decorative and physicomechanical properties. Coatings based on these systems, as is
seen from the presented data, are sticky, with low gloss; they crack and have a smell.
4.3
The formation mechanism, structure and properties of finishing

packaging materials from aqueous dispersions
The mechanism of forming coatings from aqueous dispersions of polymers has not been
sufficiently studied until now. Most works in this field deal with the synthesis of latexes
and the development of the technological bases of their use. The reason for this is that the
processes of film formation from latexes have been studied using the methods, which do
not make it possible to investigate the kinetics of the process and the character of structural
transformations at particular stages of film formation. Methods of studying the kinetics of
moisture removing and electrical-conductivity changes were the most widespread. These
methods are not sensitive to the changes of the properties of films after moisture is removed.
It is known that the process of coatings and films formation does not end at this stage and
is accompanied by further structural transformations after the removal of moisture.
Most works analysing the film-formation mechanism consider latexes as typical
colloidal systems without taking into account the polymer specifics of the disperse-phase
material. It is assumed that certain conditions different from those in production of films
from polymer solutions should be met to produce a continuous film from latex.
This is due to the fact that a polymer in latex is distributed not in the form of more or
less associated molecules, but in the form of particles containing sometimes tens of
thousands of macromolecules.
146
1-3
r
F2
F
1-3
Figure 4.1 An action pattern of forces contributing to the coalescence of latex particles.
Film formation from latexes is associated with the consideration of factors, which
affect the rate of deformation and coalescence of latex particles, such as surface tension,
capillary forces, diffusion, nature of polar groups, film formation temperature, etc.
In a number of works, the driving force of film formation is taken to be the surface
tension at the polymerair interface, which tends to reduce the surface of the polymer
phase.
It is assumed that after the evaporation of water latex particles flow in under the
action of the surface tension force, which depends on angle (Fig. 4.1), the value of which
is determined from the Frenkel equation
3 13 t
= ---------------,
2 r
where 13 is the surface tension at the polymerair interface, t is the contact time of particles, is the viscosity of polymer and r is the radius of a polymer particle.
It is assumed that the force of interaction between latex particles depends on their size;
herewith, it is not taken into account that particles themselves can have diverse shapes.
In works by Brown, of crucial importance in the film formation process are capillary
forces, which act against forces of electrostatic repulsion and forces of strain (deformation)
resistance identified with polymers elasticity modulus. At a certain value of the modulus,
particles are not able to get deformed, so no film is produced.
The capillary forces depend on the surface tension at the polymerair interface and
the capillary radius rc
2
F = --------1- .
rc
Assuming that aqueous streaks between latex particles have the form of a cylinder
(Fig. 4.2a), we can determine the radius of a capillary
r ( 1 cos 30 )
r c = ---------------------------------- ,
cos 30
where r is the radius of a latex particle.
CHAPTER 4
rc
147
FH
Fn
30
r
rc
Figure 4.2 An initiation pattern of capillary forces during the drying of latex: a, initiation pattern of
capillary forces; b, resolution pattern of capillary forces.
According to Brown, the film-formation process occurs when

F1 + F2 + F3 + F4 > F5 + F6 ,
where F1 are the capillary pressure forces, F2 is the force depending on the surface tension
at the polymerwater interface, F3 are the forces of molecular interaction, F4 the force of
gravity, F5 is the resistance to strain, F6 the force of electrostatic repulsion.
At the same time, it has been found that the size of particles, on which the capillary
pressure depends, has no effect on the film formation process, and the last stage of film formation from latex can be determined by its polarity or autoadhesion.
Film formation can have the diffusion-osmotic mechanism. In this case, it is assumed
that water is fed to the surface not only through capillaries, but also via latex particles themselves, proceeding from the assumption that for real latexes the surface tension at the water
phaseair interface is greater than 30 dyn/cm and the wetting angle is greater than 0.
Therefore, a force applied to the wall of a capillary can be resolved into two components
(Fig. 4.2b): normal, Fn = 2 rc 23cos and tangential, FH = 2 rc 23sin , where Fn is
the compressing force directed inside the specimen and FH is the force directed along the
surface and tending to close the openings of the capillary. For synthetic latexes, FH > Fn.
The polymer film formed on the surface of drying latex is permeable for water vapours,
not impermeable for water itself; because of this, an osmotic pressure emerges, which is
directed inside the film and is compacting its structure. It is concluded that the main source
of energy in film formation is ambient heat transformed into effective work in the evaporation of water via latex particles. The action of capillary forces has to do with faster drying
of latex films if the polymer is in a rubberlike state as compared with the polymer in a viscoelastic state.
The main criterion of film formation in a number of cases is taken to be the minimum
film formation temperature (MFFT), i.e., the temperature above which globules of thermoplastic polymer are capable of deformation to form a continuous film. MFFT is an essential
characteristic of the film-forming latex. It is assumed to correspond to the temperature of
the transition from the glassy to the rubberlike state. However, it has been shown that formation of films can occur at temperatures lower than the glass transition temperature of a
polymer; as the result of the contact of latex particles one with another, there will be the
148
interpenetration of macromolecular segments on their surface, possessing a significant freedom of rotation. Therefore, it is suggested that the temperature of film formation should be
the function of the ratio of the surface to the volume of the polymer phase. On the other
hand, one of the works showed not only the feasibility of film formation but also its kinetics
to depend on the physical state of the polymer.
Film formation depends not only on the colloidal and rheological properties of latex
but also on the chemical composition of the polymer.
Studies of the effect of polymer polarity on the rate of film formation by the example
of latexes of various copolymers of ethylacrylate have shown that the rate increases with
the polarity of the polymer going up.
An essential drawback of those works is that they fail to take into account the crucial
role of structural transformations during the formation of the properties of latex films. This
was first noted in the works by S.S. Voyutsky and coworkers, who considered formation of
films from latexes as a multistage process. Of crucial significance is the last stage of film
formation associated with the redistribution of emulsifier, the deformation and coalescence
of latex particles. The redistribution of emulsifier and its dissolution in the polymer can be
contributed to by the diffusion of macromolecules similar to how it takes place in the formation of films from other systems. Even at a very low content of emulsifier in the latex
film, its water absorption was shown to depend on the structure of the latter. Water absorption of acrylate latexes synthesized at the same consumption of the initiator and emulsifier
decreases with the increase of the elasticity modulus of the polymer and an increase of its
molecular mass. This can be explained by the increase of the intermolecular interaction, at
which the number of holes, formed in the thermal motion of polymer macromolecules
and responsible for water absorption, decreases. A similar dependence of water absorption
of latex films from polyvinyl acetate and its copolymers with butyl acrylate on polymers
deformation resistance was obtained.
In all these works, latex particles were considered as a ball of irregularly intertwined
macromolecules kept together by the forces of intermolecular interaction.
Studies of the fine structure of latex coatings and its effect on the properties of the latter
have not been given due attention. Studies of latex particles were mainly reduced to the revelation of their size; and studies of structures of films, to observations of replicas from their
surfaces in an electronic microscope.
We investigated the structure of latex particles and its effect on the structure and properties of coatings by the example of commercial latexes. For electron-microscopy studies
of the fine structure of latex particles, we used the method of oxygen etching.
As a result of these studies, we found latex particles to be complex supramolecular formations consisting of simpler structural elements. The size and morphology of the structures occurring in latex particles depends on the chemical composition of the polymer, the
nature of the functional groups, the colloidalchemical nature of latex.
To study the mechanism of formation of latex coatings, in these works we used new
methods enabling us to investigate the properties of latex coatings at various stages of film
formation and to assess the emerging internal stresses in the coatings, which cause spontaneous curling and warping of the materials. A relationship between the structure and properties of latex coatings was established.
Internal stresses emerging in the formation of coatings are determined by the rate of
inhibition of the relaxation processes, which depends on the architecture of molecules and
the character of supramolecular structures they form.
The significance of the relaxation processes in drying was first noted in the works by
CHAPTER 4
149
Academician A.V. Lykov, who proposed methods for the calculation of internal stresses,
with account for the fields of temperature and moisture content, and deduced a dimensionless criterion of crack formation depending on the operational parameters of drying.
V.A. Kargin et al., G.L. Slonimsky, P.I. Zubov and T.I. Sogolova investigated the nature of the relaxation processes in polymers and their role in the formation of coatings; this
process was shown to be accompanied by the emergence of local links between the most
active groups of polymer molecules. The number and nature of these links, as well as the
conformation of macromolecules, render an effect on the rate of the relaxation processes
and the value of internal stresses.
A peculiar feature of the formation of latex coatings is the nonmonotonic change of
internal stresses in the film-forming process. First they increase and reach a maximum after
the removal of moisture, and then relax to a constant value.
Studies of the structure of the initial dispersions and coatings on their basis revealed
that after moisture removal the coatings preserved latex particles whose diameter, depending on the nature of polymer, changed little within the limits of 0.15 up to 0.17 m. With
this in mind, special attention was paid to studies of the structure of latex particles; it was
shown that they were complex supramolecular formations consisting of simpler and finer
supramolecular structures.
A direct relationship was established between the structure of latex particles and the
rate of the relaxation processes; the relaxation processes are completed the fastest in coatings with the least number of globules (equal to 50, of about 30 nm in diameter) in a latex
particle. As the number of globules in a latex particle increased by two orders of magnitude
and their diameter decreased to 910 nm, the relaxation processes were sharply slowed
down and were completed in 30 days of formation.
Studies of the supramolecular structure at particular stages of formation of latex coatings have established that the removal of moisture was accompanied by the preservation of
latex particles with the emergence of local links between them and structural elements that
form them.
The subsequent relaxation processes are associated with the breakdown of latex particles and the rearrangement of their constitutive structural elements.
Thus, formation of latex coatings is not completed after moisture removal and consists
of two stages. The first stage is associated with the increment of internal stresses as the result of establishing local links between latex particles and their constituent structural elements during the removal of moisture from the system.
The second, longer stage is to break down latex particles and to rearrange their constitutive structural elements, which leads to the relaxation of internal stresses.
The methods of measuring the kinetics of increment and relaxation of internal stresses
and measuring the thermal and physical properties of coatings, proposed in these works, are
of significant interest for coating formation studies and of great practical importance.
In contrast with the methods of studies of other mechanical and electrical parameters,
they make it possible to follow the complete process of forming films on the support on one
specimen and to assess the change of the properties of latex coatings after moisture removal.
The earlier used methods of studying the film-formation kinetics by the change of
moisture and electrical resistance failed to detect structural transformations in latex coatings after removal of moisture from them.
Using this method for studies of internal stresses, it has been shown that the character
of the kinetic curves of the increment and relaxation of internal stresses does not depend on
the nature of the support, which has a significant effect on the value of internal stresses.
150
Ways to decrease internal stresses during the formation of latex coatings were proposed by regulating the character of structural transformations and by forming an ordered
supramolecular fibrillar-type structure in latexes and coatings on their basis, using modified
additives and changing the colloidalchemical nature.
This made it possible not only to reduce internal stresses in the system, but also to considerably decrease their formation period, to sharply increase adhesion and strength of latex
films.
Studies of the effect of structural transformations in latex films on the decorative properties of coatings have not been given due attention. This complicates the choice of latex
systems for finishing packaging and printed products and does not make it possible to define
the main requirements to the structure and chemical composition of a latex formulation,
which provide for the required set of mechanical and decorative properties of coatings.
The process of forming coatings from aqueous dispersions of polymers on fibrous
bases of the type of paper and printed products has been little studied. The effect of the
chemical composition of the dispersion, the nature and concentration of polar groups, the
colloidalchemical nature of latex has not been investigated.
The most promising class of film formers for finishing printed products are aqueous
dispersions of polymers.
To develop aqueous dispersions of polymers used for finishing printed products, the
effect of various physicochemical factors on the decorative properties of the coatings, such
as the structure of latex particles and coatings, the nature of the functional groups and their
distribution on the surface of latex particles, the colloidalchemical nature of latex has been
studied.
These studies made it possible to develop the physicochemical bases of the synthesis
of latexes forming the coatings with high decorative and protective properties.
4.4
Characteristics of finishing packaging materials
The mechanism of film formation from aqueous dispersions of polymers has not been studied sufficiently. The earlier used methods of studying the kinetics of moisture removal, the
changes of electrical conductivity; of plotting the thermomechanical curves, do not make it
possible to investigate completely the kinetics of the process and the character of structural
transformations occurring as the result of incompletion of the relaxation processes.
To study the process of coating formation from latexes, we investigated the kinetics
of the increment and relaxation of internal stresses. The internal stresses were determined
by the polarization-optical method broadly used in various industries.
The peculiar feature of the method we used is that stresses are assessed by the value
of the birefringence in the support at the interface with the film. This excludes the need for
measuring additional physicomechanical characteristics for calculating internal stresses,
which change during the formation and ageing of the coatings.
Glass isotropic prisms in the form of parallelepipeds, 102030 mm in size, which are
an optically sensitive material with a linear dependence between voltages and birefringences within a broad range of voltages and temperatures were used as a support. The error of
the method does not exceed 510%. The value of the method is also that, along with internal
stresses, it determines adhesion of coatings, which is assessed by the maximum critical
stresses causing the spontaneous delamination of the film from the support at a certain
thickness of the coatings. The critical stresses were developed by forming an epoxy coating
on the latex coating obtained on a glass support. The optical schematic of the recording
CHAPTER 4
10
11
Figure 4.3
151
+
Rcr
The electro-optical schematic of the instrument.
instrument is given in Fig. 4.3.

A beam of light from incandescent lamp 1 (170 W, 17 V) passes through condenser 2
and is fed via polarizer 3 to measured specimen 4. Through slit 5 (0.50.5 mm in size) and
object lens 6 the light comes to analyzer 7 crossed with polarizer 3 and goes to measuring
photocell 8. Compensation photocell 9 is connected in parallel to the measuring photocell.
A light beam from source 11, which has a system of diaphragms and neutral wedge 10, is
incident on the compensation photocell. The compensation part of the circuit, connected toward the measuring photocell, serves for the exact zero point adjustment in the electric circuit. Internal stresses in various planes are measured by automatic displacement of the table
with the specimen at a rate of 4 mm/min.
Studies of stresses by the optical method during the formation of coatings on various
supports can be done by preliminary pasting or depositing a support in the form of a layer
10 to 100 m thick on the surface of the glass prism, followed by the application of a polymer coating to this support. Various supports were pasted by a glue based on epoxy resin
ED-5 applied as a thin layer 36 m. Using this method of pasting, there were practically
no internal stresses in the glass prism before the application of coatings.
Using the optical method, we studied the effect of various factors on the value and
increment/relaxation kinetics of internal stresses, such as the chemical composition of film
formers, the colloidalchemical nature of latex, the nature and polarity of the functional
groups, the effect of the nature and structure of the support, the formation conditions and
methods of drying the coatings.
The kinetics of drying latex coatings was studied by the weight method. The same
amounts of latex of a known concentration (in our experiments, it was 0.010.015 g at a
latex concentration of about 50%) were applied to glass plates of 1020 mm. The glass
plates were periodically weighed at room conditions (at a temperature of 20C and relative
humidity) at certain time intervals on an analytical balance until a constant weight was
reached.
Penetration of polymer into the fibrous support in the process of drying of the coatings
was determined by the fluorescence of transverse sections of papers (offprints) with a coating in an ML-2 ultraviolet microscope. The source of light is a DPSh-250 mercury lamp,
which gives an intensive radiation in the blue-violet region of the spectrum up to the wavelength of 340 nm. The operation of the instrument is based on the use of the fluorescence
of belofors, which occurs under the action of beams of a certain spectral composition. The
152
6
5
2
to pressure gauge
4
cooling
to pump
Figure 4.4
light of the fluorescence has a longer wavelength than the light exciting the fluorescence.
Belofors having an affinity to the polymer (Belofor SNPA) were used as optically bleaching
substances. A minor amount of belofor (0.0054 g per 50 g latex) was introduced into the
initial dispersion, and then the dispersion was evenly applied to the supports by means of a
spreading knife; the weight of the applied dispersion was controlled.
The supramolecular structure of latex coatings was studied using an electron microscope by means of the method of carbon replicas. In some cases, the specimens were subjected to oxygen etching to reveal the structure more clearly.
Activation of oxygen was performed in an electromagnetic high-frequency field. The
advantage of this method of etching is that the substance is treated not for a long time and
evenly without increasing the temperature or increasing it comparatively little within the
limits of 24C.
The specimen was etched in a tube presented schematically in Fig. 4.4.
After specimen 2 is introduced through the side tap, a vacuum of up to 10 3 mm Hg
is created and an oxygen flow at a pressure of 34 10 2 mm Hg is set by means of a needle
valve. Then a discharge is carried out. The etching time was adjusted experimentally to
810 min.
Oxygen etching contributes to a more pronounced revelation of the structure, without
changing its character, as the result of the elimination of a low-molecular-mass less ordered
structure.
Preparations were observed at an UEMB-100 electron microscope.
The molecular structure of the coatings, with account for the distribution of the polar
groups on the surface of latex particles and the formation of hydrogen bonds between them,
was studied by the method of IR spectroscopy. Formation of films from latexes was
performed on fluorite plates. IR spectra of the latex coatings were recorded by an UR-20
instrument.
CHAPTER 4
153
The size of latex particles was determined by the method of electron microscopy by
preparing preparations from very dilute dispersions at a concentration of 0.001%; these data
were simultaneously compared with those of the diameter of particles obtained by means
of an FEKN-57 nephelometer.
The macrostructure of the initial papers was examined in reflected light on an MIM-7
microscope. Specimens of papers studied were preliminarily contrasted.
The microstucture of the initial papers was examined in an UEMB-100 electron
microscope. Specimens were obtained by dispersing papers by means of an UZDN-1 ultrasonic disperser at a frequency of 15 kHz for 30 sec.
The rheological properties of latexes, depending on their composition and colloidal
chemical nature were studied on a viscosimeter with Shvedov-type coaxial cylinders and
were assessed by the character of the viscosityshearing stress curves.
Stressstrain characteristics were recorded at room temperature by a Polyani instrument to characterize the mechanical properties of films. Specimens for tests were cut as
rectangles 455 mm in size from the most even-thickness part of a film. The area of the
working part was 105 mm2; the loading rate, 610 mm/min. The mean values of the
stress-strain characteristics were obtained from 910 parallel determinations.
The thermomechanical properties of polymers were assessed by the change of strain
on temperature. The thermomechanical curves were registered on a Kargin balance at a constant load and heating rate.
Factors affecting the quality of lacquering printed offprints at various types of papers
were studied. The method of determining the extent of lacquering is based on the assessment of the rate of lacquer penetration into the support and depends on the absorption properties of the support.
To assess the extent of lacquering of saturated regions of an offprint with dispersions
studied, we measured the contact angle of wetting at the offprint surface /drop of
dispersion/air interface and determined the wetting as a function of time (rate of absorption)
by the drop contour projection method.
The character of the kinetic curves of wetting is similar, so the data of measurements
are summed in the table.
The gloss of the coating is one of the major decorative parameters of the coating quality. Objective methods of measuring the gloss have been developed. The Fairchild glossmeter is the most advanced, as it enables measuring the gloss of paper continuously by
means of a comparative method, can be used at a high temperature, humidity in the presence
of corroding chemicals and vapour, has a number of design advantages. The gloss of coatings under study was measured by a glossmeter, was assessed with respect to black glass
and was expressed in percent.
Cohesion of lacquered offprints was determined by the method proposed for binding
fabrics. The method consists in determining the force of cohesion emerging as the result of
the contact of the face surfaces of lacquered offprints at a certain temperature, pressure and
time. Specimens were prepared as follows. Straps of lacquered products of 3050 mm in
size were preliminarily held at a 100% relative humidity on an exciccator mesh (with the
face part up) for 30 min, them placed into a press mold heated up to 302C, were subjected
to compression at a pressure of 2005 kgf for 1 min, removed from the press mold and put
between glass plates under a load of 1 kg for 24 h. Then the specimens were subjected to a
load, required for a shift of the surfaces, in a tensile tester.
The force of cohesion (B) in kg/cm2 was determined by the formula:
154
P
B = --- ,
S
where P is the load at the shift of the surfaces in kg and S is the contact area of the specimens
in cm2 (of 57 parallel tests to an accuracy of up to 0.1).
The lacquer film on an offprint should have an abrasion resistance and elasticity. The
resistance of a coating to abrasion can be defined by the length of a path, in passing which
the coating is being broken, and be characterized by the number of turns of a prism before
the appearance of the paper base. Specimens studied are fixed on to the prisms; the specimens are in contact with a closed band made from the fabric used as a counterbody in abrasion. The fabric band is cut of the same size as the base, is pulled tight by a load of 3 kg,
and then the cross with the prisms is rotated at a speed of 60 revolutions per minute. The
mean arithmetic of six parallel determinations was taken as the abrasion result.
Elasticity of the coating was assessed by the number of double bends in tests on an
MIDP-1 instrument used in printing industry. The method consists in determining the number of double bends to an angle of 150 to each side from the vertical position of the material
being under tension, up to the emergence of cracks on the film coating or the break of the
specimen.
Durability of coatings on paper is assessed not only by the values of internal stresses,
but also by its resistance to ultraviolet radiation. The light permanence of coatings was estimated by a faster method from the change of the colour of the specimens as compared with
the reference methods under the action of ultraviolet radiation of a PRK-4 lamp. A correlation between the data obtained by the faster method and under natural testing conditions
was established.
4.5
Aqueous dispersions of polymers for finishing coatings, offset papers

and inks
To enable the use of aqueous dispersions of polymers for finishing printing products, the
mechanism of forming coatings from latexes was studied with the aim to establish relations
between the chemical composition of the dispersion, structure of latex particles and decorative properties of coatings.
Latexes manufactured by home industry were tested. However, the coating produced
from these compositions on offprints does not conform to the requirements imposed on the
quality of lacquered products. These were systems based on copolymers of vinyl acetate
and other monomers (coatings possess a high tackiness, low gloss; and dispersions themselves, unstable properties). The major characteristics of tested latexes are given in the table. Taking account of this, acrylic dispersions both commercially manufactured and
specially synthesized were chosen as promising film formers.
Of commercial dispersions, the latexes tested were polyalkyl acrylates based on acrylCH3
ic acid CH2
R ,
namely:
CH
COOR
and methacrylic acid CH2
and their esters, where R H1CH3
COOR
copolymer of butyl acrylate with meth- or ethacrylate and MAA
CHAPTER 4
CH3
MBM-5s
...
CH2
...
CH
CH2
COOC4H9
CH3
...
155
CH2
COOCH3
...
COOH
copolymer of butyl acrylate with methyl acrylate and MAA

CH3
MBM-3
...
CH2
CH
...
CH2
COOC4H9
...
CH
CH2
...
COOH
COOCH3
copolymer of methyl acrylate with vinyl acetate and MAA

CH3
MVM-1.5s
...
CH2
CH
...
CH2
COOCH3
CH
...
CH2
OCOCH3
...
COOH
the composition and colloidal characteristic of which are given in the table.
Coatings from these latexes on offprints possess a tackiness and low gloss.
A dispersion based on polyalkyl acrylates, which forms coatings with high decorative
and physicomechanical properties, was developed. As the result of the studies, it was found
that latex BM-12, of the structure
CH3
CH3
...
CH2
CH
...
COOC4H9
CH2
...
COOC4H9
CH2
...
COOH
forms a glossy, nonsticky coating with high adhesion and physicomechanical properties.
This latex is produced in the presence of an emulsifier (sulfanol) and an initiator (ammonium persulfate, 0.15 parts by weight).
Dispersions of the BM-12 formulation with pH from 2.5 up to 8.4 were synthesized to
study the effect of the colloidalchemical nature of latex, namely, pH of the medium. These
latexes were produced by the method of hot neutralization by introducing various amounts
of ammonia (Table 4.12) into the latex.
Latexes with various polar groups carboxylic (COOH), amide (CONH2) and
nitrile (CN) are obtained by the method of emulsion polarization with equal amounts of
the same emulsifier (sulfanol), with the other similar conditions observed, by introducing
12 wt.% monomers with various functional groups: methacrylic acid, methacrylic-acid
amide and a mixture of methacrylic acid and acrylic-acid nitrile (Table 4.13).
A peculiar feature of investigated latexes with various amounts of methacrylic acid
from 2 up to 15 wt.% is that it was introduced as a monomer in emulsion polarization performed by a semicontinuous method with the triple dosage of monomer and emulsifier. The
colloidal characteristic of synthesized latexes is given in the table.
To study the formation process of polymer coatings on offset papers and offprints, the
following were chosen: plain offset paper and an offprint obtained under production
156
conditions by the offset method during the application of inks of the 2513 series. Papers for
different methods of printing differ mainly by their moisture resistance (degree of sizing),
smoothness, elasto-plastic properties, absorptivity (porosity and capillarity) and strength of
the surface. These are the essential printing properties of a paper, on which its behaviour in
the printing process depends.
A number of requirements are imposed on offset paper; these are stipulated by the specific features of offset printing, when an ink image is transferred from the offset plate to
paper by means of the offset rubber cylinder, and the offset plate is systematically moistened with water in the process of printing.
Therefore, offset paper should be sufficiently moisture-resistant, i.e., well sized with
rosin size, and sometimes additionally with starch. Highest quality offset paper, e.g., map
paper, is obtained by using melamine-aldehyde resin in combination with wood rosin as
size. A high degree of sizing of offset paper (1.25 mm) is required, first, to avoid excessive
deformation of paper in its contact with the moistened offset cylinder and, second, so that
there is no decrease of strength of the surface of paper in moistening and an associated fluffing of paper by ink.
The elastic and plastic properties of offset paper are undesirable, as in printing they
cause ink squeezing on the offprint. For this reason, the content of filler in the offset paper
is always lower than in printing paper or in intaglio paper.
The absorptivity of offset paper can be limited, if the inks used are fixed by oxidative
polymerization or evaporation of a high-boiling solvent, especially in gas-flame drying of
offprints. However, when using inks fixed by selective absorption of the bonding adhesive,
the absorptivity of offset paper should be high, which is achieved by increasing the capillarity of the paper owing to the increased content of filler (more than 15%) and preservation
of porosity and capillarity of the paper in its fabrication on a paper-making machine. Besides, in offset printing some roughness of paper prevents ink scuffing.
The major types of plain papers, depending on their purpose, composition with respect
to fibre content and technical parameters, are produced as numbers 1, 2 and 3, which denote
certain compositions (Table 4.7).
Papers of each number are divided into several grades denoted by letters A, B, C and
D for the same composition, having slightly different degrees of smoothness, ash content
and bulk density.
Table 4.7 Composition of printing paper (in %).
Fibrous semi-finished products
Bleached sulfite cellulose, no less than

Unbleached sulfite cellulose, no less than
White woodpulp, no more than
Paper
No 1
No 2
No 3
100
50
50
35
65
Map paper is a high-grade offset paper intended for printing topographic, hydrographic and geographic maps. The requirements to map paper include those for offset paper
and some additional requirements due to the specific features of map production and conditions of map use. Map paper should have a high degree of whiteness (without any additional tint), the homogeneous smooth, closed-up surface, additional abrasion resistance,
resistance to moisture and atmospheric effects (rain, snow), minimal and even deformation
157
CHAPTER 4
in moisturing, minimal speckiness (specks of more than 15 mm are inadmissible), high light
permanence.
Map paper is fabricated from bleached sulfite cellulose and linen rag pulp (Table 4.8),
has a wood resinmelamine sizing of no less than 1.75 mm, i.e., much greater than common
offset papers.
Table 4.8 Composition of atlas paper.
Fibrous semi-finished products Grade A (hydrographic
and topographic)
Bleached linen rag pulp, no less
than
Bleached sulfite cellulose, no more
than
Grade B
(geographic)
Grade C
(geographic)
30
50
70
50
100
With this in mind, to study the formation mechanism of coatings from polyalkyl acrylate latexes, we chose different papers, whose properties are given in the table.
As ink sublayers, printing inks intended for offset printing were used.
When fabricating offset colour inks, account should be made of the offset printing process and, mainly, the character of the printing plate and regime of its moistening in printing.
Therefore, offset colour inks are usually fabricated on viscous and sticky bonding adhesives
from absolutely water-proof pigments (or lacquers).
Earlier, offset inks were produced predominantly on alkid and natural drying oils;
nowadays, on composition drying oils.
Composition drying oil is a mixture (composition) of specially selected resins, synthetic polymers, highly viscous drying oils, mineral or vegetable oils, and high-boiling organic solvents. To accelerate ink fixation, the formulation of inks is supplemented with a
siccative a catalyst of oxidative polymerization of the bonding adhesive.
The inks of the series used are the most advanced. The composition of the ink is
approximately as follows:
pigment
composition drying oil
thinner
siccative.
Depending on the colour of the ink, respective pigments are used:
Ink number
011
231
331
531
Ink colour
Pigment name
black
magenta
cyan
yellow
channel carbon black

ruby lacquer SK
heliogen blau LBGN
yellow clear 0
Offset inks of this series are fixed on paper due to the partial selective ink penetration
and oxidative polymerization of the bonding adhesive.
Polyalkyl acrylate dispersions were applied to dry offprints.
Conducted research in the field of printed-matter finishing enabled the major
158
conclusion that the finishing material should be chosen to match paper and inks. It is not by
chance that in the West acrylic dispersions are used in the paper-making process with the
aim to improve their printing properties; printing aqueous acrylic inks are being developed.
4.6
Properties of finishing coatings from aqueous dispersions of acrylic

polymers
Studies of the formation of coatings from industrial latexes have established that the structure of latex particles has a significant effect on the rate of relaxation processes, kinetics of
increment of internal stresses, adhesion and other physicomechanical properties of the
coatings.
It could be expected that the structure of latex particles, which depends on the chemical
composition of a polymer, the nature and concentration of polar groups, the colloidal
chemical nature of a latex, should also have a significant effect on the decorative properties
of the coatings, determining the quality of finish of printing products.
With account for this, we studied the effect of the chemical composition of polyalkyl
acrylates on the structure of latex particles and coatings, established the relationship
between the character of structural transformations in the formation of latex coatings, decorative and physicomechanical properties of the coatings.
For solving this problem, we studied the effect of the chemical composition of polyalkyl acrylates on the structure and properties of coatings, chose the composition forming
a coating with the required set of properties.
The latex coating formation process was studied by investigating the kinetics of increment and relaxation of internal stresses.
It follows from the analysis of the data on the kinetics of increment and relaxation of
internal stresses in the formation of coatings from latexes of acrylic copolymers of various
chemical composition (Table 4.9) that for coatings from latexes MBM-3, MBM-5s,
MVM-1.5s the internal stresses change nonmonotonically: first they increase and then relax. A specific feature of the hardening of coatings from latex BM-12 is associated with a
rapid increment of internal stresses in the initial stage of formation and their stability in the
subsequent formation of the coatings (Fig. 4.5).
Table 4.9 Characteristics of various latexes.
Synthesis
No
Latex
name
50 shopfloor
MBS-5s
278 shopfloor MBM-3
133-1
MVM-1.5s
112
BM-12
experimental
Ratio of components, wt. %
Colloidal characteristic
of latex
BA
MA
VA
dry
residue,
%
sp
pH
55
62
30
35
70
28.5
49.0
40
48.0
49.0
2.5
7.4
2.5
3.6
4.5
6.0
3.0
3.0
BMA MMA MAA
70
40
5
3
1.5
12
Note: BA, butyl acrylate; MA, methyl acrylate; VA, vinyl acetate; BMA, butyl methacrylate; MMA,
methyl methacrylate; MAA, methacrylic acid.
CHAPTER 4
159
b10, MPa
16
12
4
3
1
2
8
4
12
400
600
800
1000
, h
Figure 4.5 Kinetics of increment and relaxation of internal stresses in the formation of coatings
from latexes of various chemical compositions: 1, BM-12; 2, MBM-3; 3, MBM-5s; 4, MVM-1.5s.
u, %
100
80
60
40
20
1
2
10
, min
Figure 4.6 Kinetics of drying of coatings from latexes of various chemical compositions: 1,
BM-12; 2, MVM-1.5s; 3, MBM-3; 4, MBM-5s.
Analysis of the curves of drying of various-composition latexes indicates that the most
rapidly drying coatings are those from BM-12 and MVM-1.5s (Fig. 4.6). Comparison of
the kinetics of drying of the coatings with the kinetics of increment of internal stresses indicates that the most sharp inhibition of the relaxation processes is observed in the period
of the dropping rate of drying and is due to the formation of local physical links between
structural elements. Significant differences in the mechanism of formation of the coatings
from latexes of acrylic copolymers, differing by their chemical composition, are determined
by the specific features of the structure of latex particles and the distribution of polar groups
on their surface. These factors determine not only the mechanism of formation of the coatings from latexes, but also the properties of polymer dispersions.
Figure 4.7 presents a dependence of viscosity on shearing stress for dispersions of various chemical compositions. It is seen that dispersions from copolymers MBM-3 and
MBM-5s are weakly structured systems passing to a state of viscous flow at a comparatively
small shearing stress. The system of copolymer BM-12 is more structured and breaks down
160
, 10 Pa . s
24
20
12
8
4
3
2
2 4
40
80
120
160
P, 10 Pa
Figure 4.7 Dependence of viscosity on shearing stresses for latexes of various chemical compositions: 1, MBM-3; 2, MBM-5s; 3, BM-12.
at a shearing stress by an order of magnitude higher than BM-type latexes.

This is, evidently, due to the smaller size of latex particles in the BM-12 dispersion,
determined by the results of electron-microscopy studies (Table 4.10), and also by the concentration of a significant amount of polar groups on their surface. For this reason, coatings
from the dispersion of BM-12 are characterized by a considerably smaller formation time.
Table 4.10
Adhesion A,
Relative
Copolymer Particle size, Adhesiveness Gloss relative Strength p,
MPa
MPa
elongation ,
m
of coating, to black glass,
%
MPa
%
MBM-5s
MBM-3
MVM-1.5s
BM-12
0.175
0.225
0.22
0.14
sticky
very sticky
0.34
0.100.12
12
14
11
49
7
4.6
8.0
8.0
400
1500
500
90
1.8
1.6
4.0
IR spectra recorded for films from latexes of various chemical compositions have a
broad band in the region of 3300 cm 1, characteristic of a hydrogen bond, apparently forming as the result of intermolecular interaction of polar groups. The largest intensity of this
band is indicative of a larger concentration of hydrogen bonds in the system for a coating
from test latex BM-12 (Fig. 4.9).
Studies of the adhesion of latex coatings to glass by the value of ultimate critical stresses causing the spontaneous delamination of the film from the support have found that coatings from latex BM-12 are characterized by a greater adhesion of about 4 MPa. In coatings
from MBM-type latexes the relaxation processes determined by the disturbance of adhesion
interaction are observed at stresses of about 1.62 MPa (Table 4.10).
Figure 4.8 presents the stressstrain characteristics of coatings formed from latexes of
various copolymers. It is seen that films from latex MBM-3 are characterized by a very high
CHAPTER 4
80
p 10, MPa
161
60
2
40
20
40
80
120
400
800
1200 1600
, %
Figure 4.8 Stress strain characteristics of films formed from latexes of various chemical compositions: 1, BM-12; 2, MVM-1.5s; 3, MBM-5s; 4, MBM-3.
1 23 4
Transmission, %
3460
3300
2990
3600
3400 3200
3000 2800 2600 2400

cm1
Figure 4.9 Spectrogram for films from latexes of various chemical compositions: 1, MVM-1.5s; 2,
MBM-3; 3, MBM-5s; 4, BM-12.
relative breaking elongation and the smallest strength as compared with films from the other
systems studied. Introduction of methyl methacrylate considerably increases the strength
of the system and contributes to the decrease of relative elongation.
Films from latex MVM-1.5s become hazy in the process of deformation and change
their structure, which stipulates the complex character of the stressstrain dependence. The
physicomechanical properties of coatings from latexes of various chemical compositions
were compared with the process parameters characterizing the decorative properties of
coatings (Table 4.10). It is seen that coatings from latexes MBM-5s, MBM-3, MVM-1.5s
are distinguished by a high tackiness and low gloss.
Coatings from test latex BM-12 were found to have the best decorative properties.
The thermomechanical curves taken on a Korgin balance (Fig. 4.10) show that the
162
70
60
50
40
30
20
10
-10 0 +10
+30
+50
+70
+90
+110
T, C
Figure 4.10 Thermomechanical curves plotted for films from latexes: 1, MVM-1.5s; 2, BM-12.
copolymer MVM-1.5s has a low glass-transition temperature and passes into the rubberlike
state at a lower temperature as compared with copolymer BM-12.
Films from MBM latexes start to exhibit a plastic flow at a temperature of +10C.
Comparison of the kinetics of the formation of coatings with their process parameters
and physicomechanical properties indicates that the high tackiness of coatings from MBMand MVM-type latexes and low gloss are related to the instability of their properties in the
formation process, to the incompleteness of the structural transformations and the prolonged formation time.
The supramolecular structure of latex coatings was studied using the method of oxygen etching to elucidate the causes of such significant differences in the formation mechanism, in the physicomechanical and decorative properties (Fig. 4.11).
The structure of coatings produced from MBM-, MVM- and BM-12-type latexes was
studied. Coatings from MBM latexes were found to be characterized by a globular structure
with globules of about 30 nm in diameter. For coatings from MVM latex, the structure was
observed to be inhomogeneous, more dense by the borders of latex particles and with a
loose packing of anisodiametric structural elements inside each particle. A specific feature
of coatings formed from a dispersion of BM-12 is that they are characterized by a very fine
structure, which is not revealed using an electron microscope even when oxygen etching is
applied. The presence of this structure facilitates the coalescence of latex particles, considerably shortens the formation time of coatings, increases their strength and significantly improves their decorative properties by providing for a high gloss in the finishing of printed
matter.
These data suggest that coatings, which meet the requirements of the printing industry
small formation time, high gloss, absence of tack can be produced from polymer dispersions of the type of BM-12, which are characterized by a very fine structure of latex particles consisting of separate molecules and the occurrence of a large amount of polar groups
in their surface.
As the result of studies of the effect of the chemical composition of polyalkyl acrylates
on the structure and properties of coatings, the chemical composition of a latex was chosen,
which forms coatings with an optimal set of decorative and physicomechanical properties
satisfying the requirements of the printing products.
The effect of various physicochemical factors (pH of the medium, nature and concentration of polar groups) enabling the regulation of the decorative and protective properties
CHAPTER 4
163
b 10, MPa
Figure 4.11
Structure of latex coatings from MBM (a), BM-12 (b) and MVM (c).
5
1
50
100
, h
Figure 4.12 Kinetics of increment and relaxation of internal stresses for coatings from latexes with
different pH at 20C: 1, pH 2.5; 2, pH 5.3; 3, pH 7.7; 4, pH 7.9; 5, pH 8.2; 6, pH 8.4.
of coatings from latex with an optimal chemical composition on the formation and properties of the coatings was studied.
Dispersions with pH from 2.5 up to 8.4 were obtained by the method of hot neutralization by introducing various amounts of ammonia into the latex.
Figure 4.12 presents the data on the kinetics of increment and relaxation of internal
stresses in the formation of coatings at 20C. It is seen that the character of the kinetic curves
and the value of internal stresses depend on pH of the medium.
164
, 10 Pa
2
100
80
60
40
3
20
20
40
60
80
P, 10 Pa
Figure 4.13 Dependence of viscosity on shearing stress for latexes with different pH: 1, pH 3.2; 2,
pH 7.7; 3, pH 7.9; 4, pH 8.2.
The internal stresses first increase up to an ultimate value and then relax. The formation period of coatings up to extreme and equilibrium values of internal stresses increases
with pH of the medium going up. At pH from 2.5 up to 5, the formation of coatings is completed very rapidly in 1530 min, however, the internal stresses in this case are comparatively high to make 0.40.5 MPa. As pH is increased up to 7.7, the coating formation period
increases up to 4 h at considerably smaller equilibrium magnitudes of internal stresses, not
exceeding 0.3 MPa. In the subsequent increase of pH up to 8.28.4, the equilibrium values
of internal stresses are reached in 5070 h at a simultaneous increment of their magnitudes.
Figure 4.13 shows a dependence of viscosity on shearing stress for latexes with various
pH. It is seen that dispersions of acrylic copolymers at various pH values are structured systems. As pH is increased from 2.5 to 7.7, the ultimate shearing stress and viscosity of the
broken structure increase. In the subsequent increase of pH, the ultimate shearing stress decreases and the character of the rheological curves changes. At pH equal to 8.2, a sharp differential is observed between the upper and lower levels of viscosity, which is indicative of
a small number of contacts between the structural elements and a weak intermolecular interaction between them. The most structured dispersion is a latex with pH equal to 7.7. As
seen in Fig. 4.12, coatings produced from this dispersion reveal the least internal stresses.
The data on the rheological properties of dispersions were compared with the size of
latex particles determined by the method of electron microscopy.
The microstructure of latex particles obtained from very diluted dispersions of a concentration of 0.001% was studied. The diameter of latex particles was found to change nonmonotonically. As pH was increased from 3 up to 7.7, the diameter of latex particles
decreased from 0.15 down to 0.06 m and then, at a subsequent increase of pH up to 8.4,
rose up to 0.2 m.
CHAPTER 4
165
0.5 m
0.5 m
0.2 m
Figure 4.14
A peculiar feature of dispersions studied is that, starting from pH 7.7, the polydispersity of latex increases significantly, and, along with large particles of 0.06 up to 0.2 m,
globules of 1520 nm in diameter, corresponding to the size of separate coiled molecules,
were found.
These data suggest that the most structured dispersions are latexes with particle size
of 15 up to 60 nm. As the diameter of particles increases up to 200 nm, the ultimate shearing
stress decreases and the character of the rheological curves changes, which is indicative of
the fast degradation of this structure at a small increase of the shearing stress.
The occurrence of globules in dispersions commensurable with the size of coiled molecules at pH larger than 7, and a significant effect of pH on the physicomechanical properties of dispersions and coatings on their basis indicates the interaction of ammonia atoms
with carboxylic groups of polymer molecules, a decrease of the intermolecular interaction
and dispersion of latex particles at optimal pH. At a further increase of pH, ammonia acts
as an astabilizing agent promoting the coalescence of latex particles.
To elucidate the peculiar features of structure formation in the dispersion depending
on pH of the medium, the structure of coatings corresponding to the equilibrium values of
internal stresses depending on pH of the medium was studied (Fig. 4.14).
It has been found that for coatings from dispersions with pH from 2.5 up to 7 the fine
structure of latex particles is not revealed, which indicates that they are formed by uncoiled
166
80
b 10, MPa
1
4
60
40
20
40
80
100
200
300
400
, %
Figure 4.15 Stress strain characteristics of films from latexes with different pH: 1, pH 3; 2, pH 7.7;
3, pH 7.9; 4, pH 8.2.
densely packed molecules. At a small pH value, the capability of coalescence of latex particles becomes worse. At pH equal to 7.7, a network structure of anisodiametric structural
elements is observed. At the further increase of pH, an inhomogeneous globular structure
is formed, with the diameter of globules commensurable with the size of coiled macromolecules and their clusters. two lines
Thus, introduction of alkali contributes to the decrease of the intermolecular interaction, dispersion of latex particles and rearrangement of their constituent macromolecules.
The presence of a set of supramolecular different-size structures in dispersions with
an alkaline medium extends the formation time of coatings owing to the incompleteness of
the relaxation processes in these systems, and contributes to the nonmonotonic change of
internal stresses in the formation of coatings.
Formation of an ordered structure in dispersions with pH equal to 7.7 and coatings on
their basis promotes a sharp decrease of internal stresses and an improvement of the physicomechanical properties of latex films.
Figure 4.15 presents stress-strain characteristics of films from acrylic latexes with different pH. It is seen that films from the latex with pH equal to 7.7 have the greatest strength
at a relative elongation. The dependence of strength and relative elongation on pH of the
medium is nonmonotonic and reveals a maximum at pH 7.7. A similar nonmonotonic dependence on pH of the medium is revealed for the adhesion of coatings (Table 4.11). The
greatest adhesion is seen to be observed for coatings from a dispersion with pH 7.7.
To elucidate the cause of a sharp increase of adhesion of coatings at pH 7.7, the effect
of pH of latex on IR spectra of the coatings was studied. As the result of those studied, it
was found that a new band in the region of 1560 cm1 characteristic of free carboxyl groups
emerged on the spectrograms with the increase of pH up to 7. It is seen in Fig. 4.16, which
presents the data on the effect of pH on the concentration of carboxyl groups, that the
amount of these groups increases significantly at pH equal to 7.78.2. It follows from the
comparison of these data with the structure of coatings that at pH 7.7 the coatings feature
ooooo
CHAPTER 4
167
Table 4.11 Effect of pH of latex on the physicomechanical and decorative properties of coatings.
pH of latex
Strength p,
MPa
3.0
5.3
7.7
7.9
8.2
6.8
8.3
6.5
6.8
Adhesion A,
Relative
MPa
elongation , %
210
310
320
305
4.0
7.8
14.0
12.0
11.0
Gloss,
%
Agglutination,
MPa
3540
3540
4045
2530
2328
0.100.12
0.150.18
0.070.09
0.150.18
0.100.13
the most ordered structure from anisodiametric structural elements. A sharp increase of
adhesion at pH 7.7 is, apparently, due to the concentration of free carboxyl groups on the
surface of these structures.
100
Transmission, %
75
50
25
0
0
8 pH
Figure 4.16 Effect of pH of latex on the concentration of carboxyl groups.
The effect of pH on the kinetics of film formation is also revealed in the formation of
coatings at a higher temperature (6070C). Figure 4.17 presents the data on the kinetics
of increment of internal stresses in the formation of latex coatings at 70C from dispersions
with different pH. It is seen that the rate of the formation of coatings under these conditions
increases considerably irrespective of the pH value of the medium. However, in coatings
from dispersions with pH from 3 up to 7.7, internal stresses were observed to have some
rise as compared with coatings formed at 20C.
The effect of the nature of the polar groups on the formation process, supramolecular
structure, physicomechanical and decorative properties of coatings from latexes based on
polyalkyl acrylate was studied.
Latexes with various (carboxyl, amide, nitrile) polar groups were produced by the
method of emulsion polymerization with an equal amount of the same emulsifier (sulfanol)
and the other conditions equal by introducing 12 wt.% monomers with various functional
groups: methacrylic acid, methacrylic acid amide, acrylic acid nitrile and a mixture of
168
b 10, MPa
3
2
4
1
, h
Figure 4.17 Kinetics of increment of internal stresses for latexes with various pH at 70C: 1, pH
2.5; 2, pH 3.0; 3, pH 7.7; 4, pH 7.9; 5, pH 8.2; 6, pH 8.4.
methacrylic acid and acrylic-acid nitride (Table 4.13).
Table 4.12 Characteristics of latexes of different colloidal and chemical nature.

Latex
Composition and ratio of

components, wt. %
BA
30
BM-12
BMA
70
Dry
residue, %
MAA
12
46
49.0
40
40
40
40
40
sp
pH
viscosity by
VZ-4, sec
2.9
3.6
6.1
6.1
6.1
6.1
6.1
2.55
3.0
5.0
7.7
7.9
8.2
8.4
13
15
20
16
41
210
24
Table 4.13 Characteristics of latexes of different nature of polar groups.

Chemical composition and ratio of
components, wt. %
BA
BMA
MAA
AAN
AAA
30
30
30
30
70
70
70
70
12
12
12
12
12
Dry residue,
%
pH
49.7
38.5
46.2
50.4
2.65
6.3
3.1
3.4
Particle size, Surface

m
tension, ,
103 N/m
0.131
0.808
0.925
0.102
53.5
50.9
57.0
49.1
Note: BA, butyl acrylate; BMA, butyl methacrylate; MAA, methacrylic acid; AAN, acrylic acid
nitrile; AAA, acrylic acid amide.
methacrylic acid and acrylic-acid nitride (Table 4.13).

Figures 4.18 and 4.19 present the data on the kinetics of increment and relaxation of
internal stresses in the formation of coatings from latexes of acrylic copolymers with
CHAPTER 4
169
b 10, MPa
6
2
10 , h
from latexes with various functional groups: 1, COOH; 2, CONH2; 3, COOH, CN; 4, CN.
6
2
b 10, MPa
1
4
8 , h
from latexes with various functional groups at 70C: 1, COOH; 2, CONH2; 3, COOH, CN; 4, CN.
various functional groups. It is seen that the formation at 20 and 70C is completed the most
quickly for coatings from latexes containing the carboxyl groups. The greatest internal
stresses at the initial stage of coating formation emerge in the system from a latex containing
the amide groups. However, as the result of the relaxation processes during the storage of
coatings under room conditions, the internal stresses decrease significantly. By the equilibrium values of internal stresses, the coatings can be arranged in the following sequence. The
internal stresses are the greatest in the formation of coatings from a latex with the carboxyl
groups; the smallest, in coatings from a latex with the nitrile groups. Latexes with the amide
groups and a mixture of carboxyl and nitrile groups form coatings with intermediate values
of internal stresses.
These data are well consistent with the results of studies of the stresses for coatings
from a latex based on the copolymer of butyl acrylate and methyl acrylate with various polar
groups. However, the effect of the nature of the functional groups manifests itself differently on the character of the kinetic curves depending on the chemical composition of the copolymer.
The data on the kinetics of the change of internal stresses in the formation of coatings
170
u, % 50
40
30
CN
20
CONH2
10
COOH
0.1
Figure 4.20
0.2
3 , h
Curves of the drying of coatings of various chemical compositions.
from latexes with various functional groups were compared with their drying kinetics. Figure 4.20 presents the drying curves for coatings of various chemical compositions. It is seen
that the drying process is completed the most quickly for coatings from latexes with the carboxyl groups; the slowest drying coatings were those from a latex with the nitrile groups.
Internal stresses reach a maximum after the removal of moisture from the latex and the
emergence of the largest number of bonds between latex particles.
To elucidate the cause of the nonmonotonic change of internal stresses in the formation
of coatings from latexes with various functional groups, the structure of the film was studied
at particular stages of the film formation process by the method of replicas without their
additional treatment and using oxygen etching to reveal the fine structure of latex particles.
From the data on the structure of coatings from latexes with the carboxyl groups at the
stage corresponding to the maximum internal stresses and their equilibrium value, it follows
that in coatings from latexes with the carboxyl groups latex particles are found on unetched
specimens at the initial stage of coating formation.
In coatings from a latex with the nitrile groups under the same formation conditions,
a more dense structure is observed by the interfaces of the latex particles.
The structure of latex particles was revealed using the method of oxygen etching.
Coatings from latex with the carboxyl groups reveal a fine structure, which is indicative of the presence of a homogeneous molecular structure of latex particles. In coatings
from a latex with the nitrile groups, an inhomogeneous globular structure is observed
(Fig. 4.21).
As the result of their coalescence, no latex particles were observed in coatings from
latexes with the carboxyl groups at the final stage of formation, corresponding to the equilibrium value of internal stresses.
For coatings from latexes with the nitrile groups, owing to the rearrangement of the
structural elements, a homogeneous globular structure (revealed by the method of oxygen
etching) is observed at the final stage of formation.
The structure of latex particles, nature of polar groups and their distribution on the
surface of particles renders a significant effect on the adhesion of coatings (Table 4.14).
171
CHAPTER 4
Mixture of CN
with COOH
0.4 m
Mixture of CONH2
with CN
Figure 4.21
Table 4.14 Effect of the nature and concentration of functional groups on the properties of films.
Characteristic
of latex
Breaking Abrasion, Strength Relative Adhesion Agglutination, Gloss, %

MPa***
number turns of p, MPa elongation, A, MPa
, %
of bends* prisms**
Functional group
Carboxyl
COOH
Amide CONH2
50
300
0.80
90
0.55
0.0850.10
4055
65
400
0.58
400
0.70
2030
Nitrile CN
75
0.52
630
0.15
Mixed (COOH,
CN)
offprint without
coating
Amount of
methacrylic acid
(MAA), %:
55
350
0.80
130
0.40
0.170.20
(rupture of
paper)
very sticky
coating
0.0120.014
1520
1015
1517
3045
172
Table 4.14 Effect

of the nature and concentration of functional groups on the properties of films.
(continued)
Characteristic
of latex
Breaking Abrasion, Strength Relative Adhesion Agglutination, Gloss, %

MPa***
number turns of p, MPa elongation, A, MPa
, %
of bends* prisms**
80
3.0
700
1.0
6
8
10
12
15
75
62
58
50
35
230
300
280
4.5
7.5
9.0
8.2
520
400
350
110
1.6
2.0
3.0
4.5
8.0
very sticky
coating
ditto
sticky
0.120.14
0.0950.10
0.0850.10
low
ditto
ditto
1520
4555
4045
*By preliminary requirements, no less than 30.

**By preliminary requirements, no less than 20.
***By preliminary requirements, no more than 0.12.
As seen in the table, coatings with the amide and carboxyl groups are characterized by
the highest adhesion equal to 0.507 MPa. The lowest adhesion is observed for coatings
from a latex with the nitrile groups. A sharp decrease of adhesion was also observed in the
introduction of nitrile groups to the copolymer of butyl acrylate and methyl acrylate. However, unlike the system we studied, this copolymer formed coatings with the highest adhesion in the presence of carboxyl not amide groups, To elucidate the cause of the high
adhesion of coatings with amide groups, we studied IR spectra of coatings from latexes with
various functional groups.
Figure 4.23 presents spectrograms of coatings. It is seen that a sharp increase of intensity of the absorption bands in the region of 3340 cm 1 and their shift towards lower frequencies for coatings from latexes with the amide groups indicates a high concentration of
the polar groups, forming the hydrogen bonds, on the surface of latex particles as compared
with latexes containing the nitrile and carboxyl groups. However, the high concentration of
1
10, MPa
80
2
3
60
4
40
20
50
100
150
300 400 500 600 , %
Figure 4.22 Stress strain characteristics of acryl coatings with different groups: 1, COOH; 2,
COOH, CN; 3, CONH2; 4, CN.
CHAPTER 4
173
Transmission, %
100
2
0
3600
Figure 4.23
3, CONH2.
3400
3200
cm1
A spectrogram for films from latexes with various functional groups: 1, CN; 2, COOH;
amide groups on the surface of latex particles not only increases adhesion of coatings on
their basis, but also leads to an instability of the system and to the formation of an inhomogeneous defect structure, which stipulates their comparatively low strength as compared
with coatings from latexes with the carboxyl groups.
Figure 4.22 presents the stressstrain curves for films from latexes with various polar
groups. As seen, the lowest strength and high relative breaking elongation is observed for
coatings from latexes containing nitrile and amide groups. The highest strength is characteristic of films from latex with carboxyl groups. The nature of the functional groups proves
to have a significant effect on the decorative properties of coatings and their tackiness.
As seen in Table 4.14, coatings from latexes with the carboxyl groups and a mixture
of the carboxyl and nitrile groups are characterized by the highest decorative properties. The
greatest tackiness and low gloss are observed for coatings from latexes with the nitrile and
amide groups. One of the most important characteristics of a decorative coating on a printing product is the transparency and light permanence of the lacquer film. Acrylic copolymers are known to form films with a high transparency and light permanence. The latexes
studied are characterized not only by a high light permanence but also form coatings capable of protecting paper from yellowing under the action of ultraviolet radiation. The latter
is very important, as photodegradation of cellulose is a surface phenomenon. Films with the
carboxyl and amide groups remained the same after 8 h of irradiation by a PRK-4 lamp
those with the nitrile groups, yellowed.
Absorption of water by a film from a latex with the carboxyl groups was significantly
lower than that from latexes with the amide and nitrile groups, and made 2% in 24 h.
Coatings on offprints from latexes with the nitrile groups have a smell inadmissible
for printing products.
Thus, coatings with the COOH group are distinguished by the lowest internal stresses
and formation time, high adhesion and good decorative properties; so it was of interest to
study the effect of the concentration of methacrylic acid on the formation process and properties of coatings.
In studies of the effect of the concentration of methacrylic acid on the formation mechanism of coatings from industrial specimens of divinyl latexes, we found that introduction
of an additional amount of methacrylic acid into the ready latex is accompanied by a nonmonotonic change of adhesion of the coatings. Adhesion is observed to be maximal at a
174
b 10, MPa
5
1
10
20
, h
from latexes with various percentage contents of MAA: 1, 15%; 2, 12%; 3, 10%; 4, 86%; 5, 4%.
small concentration of methacrylic acid of about 3%.

The further increase of the concentration of methacrylic acid was found to slow down
the rate of the relaxation processes and a sharp increment of internal stresses in the system.
The cause of this phenomenon is, apparently, due to the fact that methacrylic acid introduced in the latex adsorbs mainly on the surface of latex particles. At a large concentration
of methacrylic acid, the coalescence of latex particles becomes worse and the rigidity of the
system increases. Similar regularities in the change of adhesion depending on the concentration of methacrylic acid are observed for films based on natural rubber and divinyl styrene latexes.
A specific feature of latexes studied is that different amounts of methacrylic acid (from
2 up to 15%) were introduced as a monomer in the course of emulsion polymerization performed by the semicontinuous method with the triple dosage of monomer and emulsifier.
In this section, we studied structural transformations, physicomechanical and technological properties of coatings based on latexes from alkyl acrylates containing various
amounts of carboxyl groups in the polymer chain.
Figure 4.24 presents the data on the kinetics of increment and relaxation of internal
stresses in the formation of coatings at 20C. It is seen that coatings from latexes with a
small concentration of methacrylic acid (46%) are characterized by minor internal stresses. Owing to the incompleteness of the relaxation processes, their formation proceeds comparatively slowly and completes in 34 h. A lower content of methacrylic acid yields
unstable latexes forming very sticky coatings. As the concentration of methacrylic acid is
increased, the coating formation time becomes smaller and the character of the kinetic
curves of increment and relaxation of internal stresses changes. At the introduction of
1012% methacrylic acid into the reaction system the formation of coatings is completed
practically in 3040 min of drying. At a large concentration of methacrylic acid, along with
the increase of the stability of the physicomechanical properties, the internal stresses in the
coatings are observed to increase.
As the concentration of methacrylic acid is increased up to 15%, internal stresses become commensurable with the strength of the coatings and induce their spontaneous cracking in the process of formation.
Formation of the coatings at 70C (Fig. 4.25) is accompanied by similar regularities
in the change of the kinetics of increment of internal stresses depending on the concentration of methacrylic acid in the system; herewith, the relaxation processes in the coatings
from latexes with a greater concentration of methacrylic acid (812%) proceed faster than
175
CHAPTER 4
b 10, MPa
6
1
2
4
7
, h
Figure 4.25 Effect of the concentration of MAA on the kinetics of increment and relaxation of
internal stresses at 70C: 1, 15% MAA; 2, 12%; 3, 10%; 4, 86%; 5, 4%.
under conditions of hardening at 20C.

A significant rate of the increment of internal stresses in the formation of coatings from
latexes with a large concentration of methacrylic acid is stipulated by the slowdown of the
relaxation processes, which is related to a more intensive removal of moisture from these
systems. This is indicated by the data presented in Fig. 4.26 on the drying kinetics of coatings at 20C. From the comparison of the data on the kinetics of increment of internal stresses and drying of coatings, it follows that internal stresses in latex coatings sharply increase
in the second period of drying and reach a maximum after removal of moisture.
Table 4.15 Characteristics of latexes with various amounts of the third component MAA at a
constant ratio of two monomers BA:BMA (30:70).
Colloidal
characteristic of
copolymer
Amount of methacrylic acid, wt. %

15
Dry residue, %
49.9
pH
2.5
Specific viscosity
1.74
Size of particles, m 0.086
Surface tension, , 56
103 N/m
12
10
49.7
2.65
1.98
0.097
55
49.3
2.55
1.9
0.082
57
49.2
2.8
1.82
0.09
57.5
49.4
3.0
1.73
0.087
58.5
49.9
2.65
1.68
0.063
59.7
49.3
48.9
2.5
2.7
1.48
1.36
unstable
ditto
ditto
Note: (1) Dispersions with MAA of 0 to 2% are unstable and coagulate already on day 5. Films from
these latexes are very sticky. (2) In all specimens, the same amount of emulsifier sulfanol was used
during the synthesis.
Under coating formation conditions at 70C, the drying process (Fig. 4.26) is complete
in 20 min; herewith, the concentration of methacrylic acid in the system has no significant
effect on the character of the kinetic curves and the rate of drying.
As the concentration of carboxyl groups in the polymer chain increases, adhesion and
strength are observed to increase monotonically (Table 4.14). The concentration of methacrylic acid in the latex changes the stressstrain properties of the coatings. Figure 4.27
176
urel, % 100
80
60
at 70C
40
20
0
2
urel, % 100
at 20C
10
25 , min
60
2
3
20
10
20
30
40
60 , min
Figure 4.26 Kinetics of drying of coatings from latexes with various percentage contents of MAA:
1, 4%; 2, 8%; 3, 12%; 4, 15%.
100
1
p 10, MPa
80
2
60
40
3
4
20
50
100
200
400
600
800 , %
Figure 4.27 Effect of the concentration of MAA on the stressstrain properties of films: 1, 12%
MAA; 2, 10%; 3, 8%; 4, 6%; 5, 4%.
presents the data on the effect of the concentration of methacrylic acid on the character of
the stressstrain curves of the films.
It is seen that at a small concentration of methacrylic acid the films are distinguished
by a high relative elongation and low elasticity modulus. The change of the character of the
strainstress curves is observed for films from latexes with 12% methacrylic acid, which
are characterized by a high elasticity modulus and strength at a comparatively large relative
CHAPTER 4
177
breaking elongation. Films from latexes with 15% methacrylic acid spontaneously crack in
the formation process at stresses not exceeding 1 MPa. To elucidate the cause of this phenomenon, we studied the structure of coatings from latexes synthesized with different
amounts of methacrylic acid.
The structure of latex coatings from alkyl acrylates with various concentrations of
methacrylic acid was studied by the method of electron microscopy. It is seen that coatings
from latexes with 4% methacrylic acid reveal no supramolecular structure. At a methacrylic
acid concentration of 6%, separate globules of 25-40 nm in diameter and their aggregates
are observed. At the further increase of the concentration of methacrylic acid in the system,
the number of globules per surface unit increases. At a methacrylic-acid concentration of
15% striped structures are found, by the boundaries of which, owing to the concentration
of internal stresses, a spontaneous cracking of the coatings is observed.
It follows from these data that during the formation of coatings from latexes synthesized in the presence of a minor amount of methacrylic acid, no supramolecular structures
are formed in latex particles and coatings as the result of a strong branching of molecules
of other constituent monomers. As the concentration of methacrylic acid in the system is
increased, the intermolecular interaction goes up and, along with the fine molecular structure not revealed by electron microscopy, separate globules of 25 up to 50 nm in diameter
are observed, probably formed as the consequence of the aggregation of macromolecules.
In studies of the effect of the concentration of methacrylic acid on the coatings decorative properties determining the possibility of their use for finishing printing products, the
best gloss and absence of tack were found to occur in coatings with a high concentration of
methacrylic acid (1215%) (Table 4.14).
The entire set of data obtained indicates that coatings from latexes with 12% methacrylic acid are characterized by the best physicomechanical and decorative properties.
4.7
Specifics of forming coatings on paper and offprints
The physicomechanical and decorative properties of coatings used for finishing printed
products have been shown to depend on the structure of latex particles and coatings. High
gloss, strength, adhesion, the absence of tack, the small formation period of latex coatings
and minor internal stresses are characteristic of coatings from latexes with the homogeneous molecular structure of latex particles and a large concentration of the carboxyl groups
on their surface, which contributes to the fast coalescence of latex particles in the formation
of coatings.
When working out the formulation of compositions for coatings with optimal physicomechanical and decorative properties, suitable for finishing packaging products, developers studied the effect of the chemical composition of copolymers based on alkyl acrylates,
the colloidalchemical nature of latex, the nature and concentration of polar groups on the
structure and properties of coatings.
However, all those studies were performed in the formation of coatings on a glass support. The glass support was chosen as a model containing a considerable amount of hydroxyl groups on the surface and differing from the supports used in the printing and packaging
industry (paper, offprints) by the absence of a fibrous porous structure. This model made it
possible to exclude the effect of a specific structure of the support and its inhomogeneity
on the formation of latex coatings.
This section investigated the effect of the nature of the supports surface and the
character of its structure on the formation of latex coatings by comparing the kinetics of
178
increment and relaxation of internal stresses with the drying rate, depth of impregnation,
rate of absorption and the contact angle of wetting, and the decorative properties of
coatings.
The physicochemical ways for decreasing the internal stresses in the formation of latex
coatings on paper and offprints were developed by studying the effect of structuring additives and the drying method on the formation of latex coatings.
The object of the study was the latex based on polyalkyl acrylate BM-12.
As supports, we used offset papers of various densities and types (see Table) and offprints. Halftone prints were obtained under production conditions by the offset method by
applying four inks (series 2513) on paper (of the Goznak Paper Plant). The most saturated
sections of the prints were used for the study.
It is seen in Table 4.16 that the most porous papers with low sizing and large unevenness of the surface are those of the Kamenogorsk Paper Plant and the Goznak Paper Plant.
A more dense paper with the closed-up structure of pores, small porosity and high smoothness is map paper.
Table 4.16 Characteristics of papers studied.
Parameter
Bulk weight in g/cm3, no

less than
Mass of 1 cm2 in g
Breaking length (on
average in two
directions) in meters, no
less than
Fracture (number of
breaking bends) in
transversal direction, no
less than
Sizing in mm, no less
than
Ash content in %, no less
than
Smoothness on average
on the face side and grid
side in sec, no less than
Strain after soaking in %,
no more (in transversal
direction)
Moisture in % (VEB-36)
Porosity in sec
State standard Offset paper

Offset paper
GOST for Cartographic
(GOST) for No 1 (Goznak No 1 grade G cartographic
paper,
offset paper Paper Plant) (Kamenogorsky
paper
grade C
Offset Paper
Plant)
0.75
0.8
0.78
0.87
100,120
2400
120
2905
120
2500
120
120
2300
44
30
62
1.25
1.25
1.25
on average in
two directions
no less than
50
1.75
1.75
10
12
16
no less than 4
4.8
30
3762
3853
no less than
35
90110
+2.5
+1.6
+1.8
+2.2
+1.5
5.57.0
5.8
27.3
5.7
21
6.51
4.7
17
Note: In all papers, the fibre is directed longitudinally. Acclimatized conditions: equilibrium air
moisture 5560%, temperature 21C.
CHAPTER 4
b 10, MPa
24
179
20
16
12
4
8
4
2
10
12
14 , h
Figure 4.28 Formation of latex coatings on various papers and offprints at 20C: 1, Kamenogorsk
Paper-Plant paper; 2, Goznak paper; 3, map paper; 4, offprint.
Films from blue and black inks (included in the series 2513) applied to the surface of
glass prisms as a sublayer of 5-7 m thick were also used as supports to elucidate the effect
on the values of internal stresses and adhesion of the lacquer film to the surface of offprints.
Internal stresses in the formation of coatings on fibrous supports (paper, offprints)
were studied by the polarizationoptical method using the earlier developed technique for
preparing specimens, which consists in pasting paper onto the surface of glass prisms followed by the application of a film former onto it.
Adhesion was assessed by the values of ultimate critical stresses causing the spontaneous delamination of the film from the support. The effect of the nature of nonporous supports of the type of glass, black and blue inks on the kinetics of increment and relaxation of
internal stresses in the formation of coatings. It is seen that coatings are formed the most
rapidly on a blue ink sublayer, with the stable properties settled. Formation of coatings on
a blue and black ink sublayer is accompanied with a decrease of the internal stresses in the
system. However, the adhesion of coatings decreases simultaneously from 5 MPa on glass
down to 1.82.2 MPa on an ink sublayer, respectively, black and blue.
Worse adhesion of coatings to the ink sublayer is due to the fact that offset inks include
polymerizing composition drying oils based on wood rosinmaleic or phenol-aldehyde
resins, which contain in a hardened state a much smaller amount of active polar groups capable of specific interaction with the latex coating.
Figures 4.284.29 present the data on the kinetics of increment and relaxation of internal stresses in the formation of latex coatings on the surface of various kinds of papers
and offprints at 70 and 20C. It is seen that internal stresses in the formation of coatings
both at 20C and 70C on offprints and paper change nonmonotonically, the way they do
on glass. Figure 4.30 presents the drying curves of latex coatings on various papers and on
an offprint. It is seen that drying to a constant weight is completed the most quickly in an
offprint and in map paper. It is seen from the comparison of Figs. 4.25 and 4.27 that considerable internal stresses emerge at the initial coating-formation stage associated with the
elimination of moisture and the emergence of local links between latex particles. A sharp
increase of internal stresses in the formation of coatings on fibrous supports is, apparently,
due to a partial impregnation of the fibrous base and the reinforcement of the boundary layers of the coatings. However, during the storage of coatings under room conditions, owing
to the relaxation processes, the internal stresses are sharply decreased and do not exceed
0.40.5 MPa. From the comparison of Figs. 4.24 and 4.26, it follows that the relaxation processes in coatings formed on glass are completed much faster than in coatings on paper and
on an offprint.
180
32
b 10, MPa
1
24
4
16
9 , h
Figure 4.29 Formation of latex coatings on various papers and offprints at 70C: 1, Kamenogorsk
Paper-Plant paper; 2, Goznak paper; 3, map paper; 4, offprint.
u, % 100
80
60
40
20
5
10
15
20
25
30
45 60 , min
Figure 4.30 Kinetics of drying of latex coatings on various papers and offprints: 1, map paper; 2,
Goznak paper; 3, Kamenogorsk Paper-Plant paper; 4, offprint.
The cause of this phenomenon is, probably, due to a partial reinforcement of the coating by the fibrous support and to the effect of its structure on the rate of the relaxation processes. When specimens are dried under room conditions, the relaxation processes are
completed the fastest in coatings applied on to offprints.
Thus, it follows from these data that the character of the kinetic curves of the change
of internal stresses during the formation of latex coatings does not significantly depend on
the nature of the support. The nature of the surface of the support, its structure and porosity
render a considerable effect on the increment and relaxation rates, the values of internal
stresses, the formation period, the decorative properties of coatings.
The structure of various types of papers and its effect on the impregnation of paper and
offprint with latex was studied using optical and electron microscopies with the view to elucidate the specific features of latex coating formation on fibrous supports.
5
5.1
Technology
of the Development
of Canning Containers
Purpose of canning containers
Despite the development of new methods, equipment and technologies for processing food
products, canning still remains one of the methods of preserving perishable products during
the mass slaughter of livestock and delivery of milk. A broad use of canning makes possible
a gradual supply of meat and dairy products over the year and their delivery to regions distant from processing plants.
Metal containers from aluminium, chrome-plated steel or tinplate are the traditional
type of packaging for canned products in meat and dairy industry, in production of canned
fruits, juices, drinks, stewed fruits. Application of metal containers reduces labour intensity
and sterilization time, increases labour efficiency, decreases the requirement in storage
facilities.
The progress of canning industry is closely related to the development and manufacture of advanced, mainly metal, canning containers. Though they give way to polymer containers in the assortment and production rates of new types, metal containers are
nevertheless successfully used and their output is predicted to double by the turn of the
century.
In Russia, annual output of tinplate cans is 34.6 bln; of them, 26.3 bln for packaging
various food products; for alcohol-free beverages, 4.4 bln; and for non-food purposes, 3.9
bln.
In the UK, one of the leading European countries manufacturing metal food containers, production of canning containers was 3.6 bln cans for foodstuffs; 2.2 bln cans, for animal food; and 7.38 bln cans, for drinks.
According to the data by the American Iron and Steel Institute, eight leading US companies members of this institute manufacture annually 3715 thousand tons of
light-gauge tinplate, used mainly in fabrication of metal cans; including tinplate, 2611 thousand; tin-free plate, 889 thousand, and black plate, 215 thousand. On the whole, the world
demand is over 50 bln cans. The development of a new metal can takes three years on
average. This time is required to solve numerous issues: fabrication of a container and a set
of equipment; filling of the container; processing of the packaged product; reliability; air
tightness.
182
In Russia and Kazakhstan, electrolytical tinplate is manufactured on five lines; in particular, in Magnitogorsk Integrated Works of Metal Containers and Ispat-Karmet Steel
Works.
Owing to the change in the level of requirements to tinplate by processing plants,
which is due to the implementation of advanced can-producing lines and the development
of new canning container-producing technologies, these enterprises can not meet the demand on some items of assortment and quality. First and foremost, this is high-plasticity
tinplate for production of beverage cans by the deep-drawing method. There is also a deficit
of wide-format (more than 850 mm), thin-gauge and fine (0.20 and less) tinplate. Manufacturing of these types of tinplate in Russia is impossible due to the absence of respective
equipment.
The ecological and technological problems of tinplate production have been solved in
the recent decade. The quality of tinplate has been significantly improved due to the increase of the uniformity of distribution of the tin coating over the width of the band by
2535% or 0.30.4 g/m2 depending on the mean thickness of the coating; elimination of
some characteristic defects of the coatings, affecting the consumer properties of tinplate,
such as non-reflown edge and matte appearance; increase of the corrosion resistance
of tinplate by 3040% depending on the mean thickness of the coating.
An important problem is also a limited assortment. The system of assessing the quality
of tinplate does not include the set of issues related to corrosion resistance and other performance characteristics of material. Of all parameters affecting the corrosion and operational behaviour of material (lacquering, soldering, integrity), in practice only the
roughness is rated and checked. Totally excluded from the rating system are such parameters as corrosion resistance, composition of the chromate film, thickness variation of the
coating. These parameters are especially important for tinplate.
Traditional types of containers used for production of canned products are glass jars
with lids from tinplate or chrome-plated steel or aluminium. Production of canned products
in metal canning containers ensures the rise of the productivity of the process equipment,
the decrease of labour intensity and sterilization time, the reduction of the demand for
storage facilities.
In the recent years, aluminium, chrome-plated steel, aluminized steel are widely used
along with tinplate, which is in short supply. New materials are characterized by a lower
corrosion resistance as compared with hot-dip tinning and electrolytic tinning tinplate. In
this connection, other oligomers and polymers are used for protection of canning containers
along with traditional film formers, such as oil systems and epoxyphenol lacquers. The requirement in new lacquer-and-paint materials is also due to the production of metal canning
containers of changed design (deep-drawn cans, composite cans with soldered seam, twopiece stamped and composite cans, readily opened lids, special lids for glass containers,
tubes).
All this specifies the high requirements to lacquer-and-paint coatings intended for protection of containers, with respect to adhesion, physicomechanical properties and resistance
to the action by canned products in their long-time storage. At present, coatings of canning
containers are produced using phenolic-oil, epoxy, acrylic, polyester etc. bonding adhesives as film formers.
A broad assortment of lacquer-and-paint materials for protection of metal canning containers is due to the fact that at present there is no universal paintwork material suitable for
any metal support and canned product. The diversity of materials used to produce canning
containers and the difference of the properties of products packaged into them make it
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necessary to develop diverse lacquer coatings ensuring the protection of containers and
products under various technological conditions of production, canning and storage.
5.2
Field of application and efficiency of use
When producing containers for packaging meat, dairy, fish, juices and fruit-and-vegetable
canned products, tinplate due to the deficit and appreciation of tin is increasingly more
often replaced with aluminium and its alloys, although they are more expensive than tinplate (1015% or, by some other information, 25%).
Aluminium possesses a number of properties, which make it indispensable container
material: light weight (density of aluminium is almost 3 times larger than that of tinplate),
good formability, plasticity, high protective properties, heat resistance; resistance to water,
gases, smells, fats, action of bacteria and pests; high reflectivity; good protection of the
product from the action of heat and cold; possibility of combining it with other materials.
Increased use of aluminium materials is also stipulated by the development of aceptic
canning, increased production of frozen foods, increased demand of extended storage time.
Prospects of the further application of aluminium are determined not only by its merits,
but also by the reduction of costs for reprocessing of discarded containers. On average, 1
ton of aluminium is required to fabricate 32 thousand cans; 1 ton of tinplate, only 15 thousand. Expenses for the fabrication of an aluminium container are on average 1% of the cost
of canned product it contains.
According to the data by US companies, production of 1 kg aluminium from bauxites
requires 18.6 kW h of electric energy and 57.1 kJ of thermal energy. These data also include
total energy costs for extraction of ore, its processing and melting, as well as transportation,
heating, illumination, collection and utilization of wastes.
In production of an aluminium sheet, a considerable part of material charged into the
melting furnace is scrap of all sorts, including used aluminium containers. This type of secondary raw materials should be subjected to pretreatment, which includes its cleaning and
removal of the lacquer coating. With the required energy expenses in mind, as well as additional consumption of energy for transportation, illumination and heating, the total consumption of energy for melting of 1 kg of aluminium from scrap is 0.11 kW h of electric
energy and 8.0 kJ of thermal energy. Therefore, production of aluminium from secondary
raw materials requires only 0.6% of electric energy and 13.8% of thermal energy necessary
for production of this material from ore.
The ratio between the total reduced energy intensity of the treatment of primary and
secondary aluminium raw materials is 28.5:1. Calculations performed by US companies
have shown that collection and reprocessing of 60% of used aluminium containers reduces
the total energy intensity of container production almost two times. Two major US companies Reynolds Metals and Alcoa annually collect and reprocess over 200 thousand tons of
used aluminium containers, which enables the output of about 9.6 bln cans. These companies utilize about 75% of containers produced. On the whole in the USA, about 60% of aluminium cans and packs are utilized annually, which makes possible the re-use of 650
thousand tons of aluminium.
In France, 27% of aluminium is produced from secondary raw materials. In Sweden,
about 80% of manufactured aluminium packs are reprocessed. However, there are organizational problems of collecting, sorting out and transporting the used aluminium packs. On
the whole, the return of this metal to the production cycle can reach 50150 bln tons per
year.
184
5.3
Requirements to the properties of coatings for canning containers
The purpose of a lacquer-and-paint coating is to protect the surface of canning containers

from the action of food products. The larger is the continuity of a lacquer-and-paint coating,
the lower its permeability is, and, therefore, the more reliable its protection properties are.
The major requirement to lacquer-and-paint coatings is their continuity, as well as chemical
endurance, mechanical strength and high adhesion.
The performance properties of coatings for protection of metal canning containers depend on the composition of their ingredients, the physicochemical and technological properties of lacquers and enamels.
Of great importance is the ability of film-forming solutions to spread well and be well
distributable on metal upon application. Viscosity of the lacquer-and-paint materials and
the dry residue content are also of great significance.
Protection of the inner and outer surface of canning containers is provided for by the
use of mainly lacquer-and-paint materials, which harden at high temperatures from 180 up
to 360C.
The physicomechanical properties of coatings are determined by the structure of polymer macromolecules. Linear and network polymers under the action of an external force
change their properties differently. Network polymers extend in tension insignificantly and
then break down. Linear polymers are deformed in tension, then a thickening appears on
specimens at the further increase of stresses, and polymer extends four and more times with
the orientation along the extension axis of macromolecules and their aggregates.
Linear polymers are characterized by three major types of strain: elastic, rubberlike
and plastic. Elastic strain is caused by large stresses and is due to the change of interatomic
distances in polymer crystals or molecules. They are totally reversible and do not exceed
1%. Rubberlike strains can reach 1000% and are totally reversible; however, the initial
shape is recovered not immediately but in time.
Plastic strain of polymers is irreversible. It is associated with the regrouping of macromolecules or their aggregates relative to one another. The process of changing the state
of stress in transition from an inequilibrium arrangement of its structural elements to the
equilibrium state is stipulated by the relaxation of stresses. Relaxation phenomena are especially dangerous for those technological processes, where the strongly deformed coating
is under the action of high temperatures.
The disturbance of a polymer coating, due to the formation of cracks, a partial delamination and other defects can be observed in thermal sterilization in the container fabricated
by deep drawing from lacquered tinplate or aluminium, as well as in drying of the sealing
paste on lids pressed from lacquered tinplate.
Internal stresses can occur in coatings not only as the result of their deformation upon
film formation, in particular in drying of coatings, but also as the consequence of inhomogeneity and imperfection of the structure. Inadmissible shrinkage of a polymer coating in
the process of drying is determined by the decrease of its volume at an invariable surface
area of the material. The cause of shrinkage is the removal of solvent and the polycondensation reaction in coatings with evolution of side products of the reaction. An increase of
the molecular mass of the film former leads to a larger shrinkage of the film; solvents with
a smaller vapour pressure, as less volatile ones, contribute to the decrease of shrinkage of
the coatings.
To reduce the shrinkage of coatings in fabrication of metal container materials, their
thickness should be decreased down to 36 m. If thicker coatings up to 1218 m
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185
are to be applied, for instance, for protection of black plate, they are applied, as a rule, in
two or three layers.
A large role in defining the protective properties of coatings is played by the adhesion
properties. Adhesion is determined by the force of interaction of two contacting surfaces of
materials different by their nature. The extent of adhesion of a film to a solid surface is assessed by the force spent for its delamination from the support. At strong deformations of
material in fabrication of containers and partial destruction of the coating, three types of
adhesion disturbances are observed:
adhesion forces are stronger than cohesion forces, peeling-off occurs by the material
of the coating; this is the cohesion detachment of the film;
adhesion forces are smaller than cohesion forces, peeling-off occurs by the area of
the contact of the film with the support; this is the adhesion detachment of the film;
adhesion forces are approximately equal to cohesion forces, the mixed peeling-off
occurs; this is the adhesioncohesion detachment of the film.
When applying a lacquer-and-paint coating to the metal surface at the first stage of the
process in the liquidsolid system, adhesion forces exceed cohesion forces significantly.
However, as the film-formation process proceeds further, cohesion forces increase and in
most cases start to exceed those of adhesion.
Formation of a polymer film includes a complex of processes chemical, physicochemical, electrostatic, as well as mechanical interaction of the polymer coating with metal.
The value of adhesion is greatly affected by the state of the surface and its microgeometry,
as well as the nature of the film former. The more the amount of active polar groups in the
composition, such as hydroxyl, carboxyl, epoxy etc. groups, the stronger the interaction of
the polymer coating with metal is.
Lacquers based on comparatively low-molecular-mass substances (phenol formaldehyde and epoxy oligomers) form films with good adhesion owing to the high mobility of
molecules and their orientation at the interface.
The nature of forces responsible for adhesion is defined differently in works by different authors. According to the electrostatic theory, adhesion of polymer coatings to metal is
explained by the electrostatic attraction of the charges of the double electrical layer by analogy with microcapacitors, whose interfaces are films of polymer and metal. Considering
that adhesion of various kinds of lacquer-and-paint materials is different and depends on
the nature of metal, the method used in practice consists in using special systems of coatings, such as primercoating systems. In this case, the coating consisting of two layers of
polymer provides for adhesion to any of these materials. Of crucial significance in this case
is the diffusion phenomenon, which provides for a strong cohesion of two polymer film
formers. When considering the phenomena at the metalpolymer interface, the crucial factor in its determination is the formation of special bonds providing for the chemical interaction.
Permeability of polymer coatings is one of the main characteristics determining its
protective properties. It depends on the following major factors:
molecular permeability, which is determined by the nature of polymer, molecular
structure, packing density of molecules;
nature of a lacquer-and-paint material and its preparation;
process procedures in application and formation of coatings.
Chemical endurance of polymer coatings depends on the nature of a film former, as
well as on the conditions of chemical reactions leading to the formation of a crosslinked
molecular structure.
186
Oleo-resinous lacquers are characterized by an insufficient chemical resistance, which

is affected by the drying oils in their compositions, owing to the large content of ester
groups subjected to oxidation and determining the swelling of coatings in aggressive media.
Resistance of coatings to ageing in the process of operation is determined by the extent
of deterioration of the mechanical properties, such as elasticity and shock resistance. This
process is determined by the following factors: destruction of the film former, occurrence
of chemical reactions, loss of the plasticizer or residual solvent by the film, rate of the relaxation processes.
The film former can be destroyed under the action of light, oxygen, high temperatures
or aggressive media. As the result of the destruction, the molecular mass decreases, the
strength and elasticity of the coating go down. Ageing of the films due to the erosion or
blooming of plasticizers and residues of solvents is of no great significance for can varnishes, as they are not used in formulations of varnishes, and the coatings are dried at high
temperatures.
The effect of factors that accelerate ageing is attenuated by using antioxidants as additives. Introduction of pigments, such as aluminium powder, titanium and zinc dioxide
slows down the ageing process, as the formation of various aggressive substances in liquid
and gaseous state is made difficult.
5.4
Coatings for protection of canning containers
The corrosion resistance of aluminium is insufficient for most food media; an additional
protection is required, which is done by anodization followed by lacquering the metal. The
type and stability of can varnishes mainly determine the possibilities of using metal container materials. Owing to the protective property of a varnish, the canned product is separated from the metal of the can. If metal is not lacquered, then sweet, sour, salt- or
protein-containing food products cause its corrosion. The action of metal compounds
formed as the result causes changes of the appearance, colour and taste of ready-prepared
products, reduce the integrity of sterilized preserves. Application of a lacquer coating on
the surface of chrome-plated plate decreases the rate of penetration of iron and chromium
into the product tenfold.
The protective lacquer coating should have the following properties: a good adhesiveness to metal and a corrosion resistance; inertness with respect to a food product; a good
capability of deep drawing; a maximal resistance to strain, action of hot water and acids, as
well as to sterilization and pasteurization; a large range of applications for various food
products; processibility, stability of the properties of compositions in storage (no less than
1 year); the possibility of coating thickness variation within wide limits; formation of an
almost pore-free lacquer film with a high scratch resistance at its weight of 58 g/m2 of the
film; a small duration of hot drying, no more than 3060 sec to achieve an optimal
crosslinking of the polymer using a high-capacity equipment; a possibility of endowing the
antiadhesion properties, preventing the adhesion of the contents to the can.
These requirements are met using epoxyphenol and oleo-resinous lacquers; enamels
with zinc oxide, titanium dioxide and based on polyvinyl chloride and copolymer of vinyl
chloride; lacquer-and-paint materials from water-diluted, -soluble, -dispersion bonding adhesives, as well as systems with a high content of film former; powder inks.
Various raw materials and semi-finished products mainly synthetic oligomers and
polymers are used to produce lacquer-and-paint materials intended for protection of metal
canning containers. To modify some of them, natural products are used plant oils,
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187
products of wood rosin reprocessing. Enamels are prepared with application of mineral pigments, such as zinc oxide, titanium dioxide and aluminium powder. To dissolve
lacquer-and-paint materials, organic solvents are used.
Plant oils are produced from seeds or fruits of oil-bearing crops. The major component
of plant oils (over 95%) are glycerol esters of fatty acids (triglycerides) containing from 14
up to 18 carbon atoms.
The properties of oils depend on the composition and structure of fatty acid radicals,
which are components of the esters. In particular, the ability to dry is determined by the
number of double bonds in the triglyceride molecule, as well as by their mutual position.
By the drying ability, oils are divided into the following groups: oils with the greatest drying
ability, drying oils and semidrying oils.
Castor oil is used in production of lacquers in dehydrated form. It is distinguished by
a number of valuable properties and is close to Chinese wood oil. It is widely used abroad
in production of can varnishes, in particular, to produce protein-resistant coatings. It is also
used to produce dimerized acids, which are used in the synthesis of epoxy esters.
Maleinized oil is obtained by the interaction of oil with maleic anhydride; it is attached
to the fatty acid radical by the side of the coupled bond. As the result of maleinization, the
oxidation of oils slows down, and they dry slower in the air than the initial products.
For protective coatings, wood rosin modification products are used. By its chemical
composition, wood rosin of plant origin is a mixture of resin acids. The most stable isomers
are abietinic, dextropimaric and levopimaric acids. In lacquer-and-paint industry, mainly
wood rosin ethers are used, which are a product of etherification of resin acids of wood rosin
by pentaerythritol.
As film formers, epoxy oligomers are used, which are compounds whose molecule
contains no less than two epoxy or glycide groups, at the expense of which there occurs the
formation of a three-dimensional network structure in the hardening of coatings.
The main advantage of epoxides is high adhesion to most materials, the physicomechanical properties and chemical endurance, determined by the absence of readily
hydrolyzed functional groups in their composition.
As hardeners of the compositions, the most frequently used substances contain amino
groups, anhydrides of organic acids, phenol- and aminoformaldehyde oligomers, isocyanates. A disadvantage of the epoxy coatings is their low stability to stamping.
Epoxy ester oligomers are used to fabricate lacquer-and-paint materials, including can
varnishes. Widespread materials are epoxy esters of fatty acids of plant oils, as well as synthetic fatty acids with the radical length C10 C13 and C10 C16 in a mixture with fatty acids
of flax oil. Modified oligomers in production of can varnishes include alkyd epoxy resin of
grade E-30. It contains glycerophosphate GF-019 and epoxy resin E-40. Resin E-30 is used
as a bonding adhesive in epoxyphenol lacquers.
Lacquer EF-0188 belongs to epoxy esters. It is the product of etherification of epoxy
resin E-44 by fatty acids of flax oil.
The same group of film formers includes epoxy ester of grade EM-34. It is a ester obtained in the interaction of epoxy resin E-40 with monomer methyl esters of acids. This
composition is used to produce white enamel.
Production of can varnishes, along with melamine-formaldehyde oligomers, makes
use of the derivatives melamine-acetoguanamine and benzguanamine. A complex of high
physicochemical and technological characteristics of these oligomers, as well as the admissibility of their contact with food media specify the possibility of their use for production
of can varnishes.
188
Epoxy esters based on dimerized acids of dehydrated castor oil are used in epoxyphenol can varnishes to increase their flowability. The coatings on their basis are characterized
by high adhesion, elasticity and chemical endurance.
Phenol-formaldehyde oligomers used to form coatings of canning containers are a
product of polycondensation of mono- and polybasic phenols with aldehydes, mainly with
formaldehyde.
Phenol-formaldehyde oligomers based on a mixture of phenol with o-cresol, n-tertbutyl phenol and technical-grade xynenols are produced under industrial conditions.
Carbamide-, melamine- and benzguanamine-formaldehyde oligomers for canning
containers are obtained by polycondensation of carbamide, melamine or benzguanamine
with formaldehyde in a neutral or weakly alkaline medium. These oligomers are widely
used in lacquer-and-paint industry as a constituent part of many canning materials.
Oligoesters are used to produce can varnishes. They are obtained by the polycondensation reaction of polyatomic alcohols with polycarboxylic acids or their derivatives. Can
varnishes based on oligoesters are synthesized using benzguanamine or melamine-formaldehyde resins, which contribute to the increase of chemical resistance of films. Coatings
hardened at 180200C for 10 min withstand boiling and sterilization.
Polyvinyl chloride and its copolymers have lately found wide use, especially abroad,
in production of can varnishes. Copolymers of vinyl chloride with vinyl acetate or with mixtures of vinyl acetate with maleic anhydride or acrylic acid, as well as copolymers of vinyl
chloride with partially saponified vinyl acetate, are used the most frequently. Coatings
based on these copolymers should satisfy stringent requirements to the content of residual
monomers and emulsifiers in products, absence of off-flavour and smell, which determines
their sanitary-hygienic properties.
For coating the outer surface of canning containers of food purpose, lacquers based on
polyacrylates are used. They represent copolymers based on acrylic CH2 =CHCOOH and
methacrylic CH2 =C(CH3)COOH acids and their derivatives, such as methyl methacrylate, butyl methacrylate, acrylamide with the general formula CH2 =rC(CH3)COR. Acrylic
copolymers are well soluble in esters of aromatic hydrocarbons, ketones.
Coatings on their basis are characterized by a high thermal stability, hardness, resistance to mechanical loads.
Polyvinyl acetals are also used for production of canning containers. They are produced by the interaction of polyvinyl alcohol with aldehydes. They are a valuable raw material for lacquer-and-paint industry. For this purpose, polyvinyl butyral a product of the
interaction of polyvinyl alcohol and butyl aldehyde - is produced in this country on an industrial scale. Polyvinyl butyral combines with alkyds; phenol-, carbamide- and
melamine-formaldehyde; epoxy oligomers, cellulose nitrate, natural resins, various plasticizers. In this connection, polyvinyl butyral is widely used in production of lacquers, enamels, primers and powder inks for protection of canning containers, items from steel and
aluminium.
Along with film formers, the composition for coating canning containers includes solvents, pigments, hardeners, modifiers. Most polymer coatings are applied from solutions.
By their chemical composition, solvents are divided into several classes: aliphatic and naphthenic hydrocarbons, for instance, white spirit; aromatic hydrocarbons (toluene, xyol, solvent naphtha); terpenic hydrocarbons (turpentine); alcohols (ethanol, butanol, etc.); ketones
(acetone, methyl ethyl ketone, cyclosanone); ethers and esters (ethyl acetate, butyl acetate,
cellosolve).
The most important requirements to solvents are their dissolving power, incombusti-
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bility and toxicity. Upon evaporation of the solvent, the film should have no smell.
Pigments are introduced into lacquer-and-paint materials to obtain filled coatings. In
most cases, they endow the coatings with a corrosion resistance and can be corrosion inhibitors. Pigments also contributed to fabrication of coatings resistant to processes of atmospheric ageing and possessing decorative properties.
Aluminium powder produced from aluminium-containing raw materials looks like
scales 0.20.5 m thick and 250 m wide. The content of aluminium in the raw material
should be no less than 99%. For lacquer-and-paint industry, aluminium powder is manufactured as paste. It is fabricated from aluminium powder of grades A-5E, A-5, A-6, A-7.
White spirit is used as a solvent.
Zinc white paint by its chemical composition is zinc oxide a white crystalline powder with the size of particles of 0.11 m. The content of zinc oxide in the pigment is
98.099.7%. Being a weakly basic pigment, zinc white dissolves in acids and alkali. It reacts to free fatty acids of oil-containing film formers.
Colloidal zinc oxide is used in production of protein-resistant enamels for protection
of canning containers.
Titanium dioxide is a white pigment. It is produced in two rutile and anatase modifications. The content of the base substance in titanium dioxide manufactured by the industry should be no less than 9598%.
Titanium dioxide is used in production of lacquer-and-paint materials for external and
internal protection of metal canning containers. Coatings based on these compositions are
resistant to aggressive canning media and external effects.
An important component of the compositions are hardeners. In production of canning
containers, the hardeners used are reactive compounds introduced into lacquers and enamels based on various film formers (epoxy, acrylic, polyester ones and copolymers of various
chemical compositions). Phenol-formaldehyde and aminoformaldehyde oligomers, polyesters, anhydrides of carboxylic acids, isocyanates are used as hardeners.
Catalysts are introduced into the compositions in minor amounts to accelerate the
hardening process. In some cases, they make it possible to reduce the temperature of hot
drying. In some cases, catalysts are used together with hardeners; for instance, orthophosphoric acid, mono- and dibutyl esters of phosphoric acid are used for epoxyphenol lacquers,
as well as tetrabutoxytitanium, para- and orthotoluene sulphoacid, aluminium alcoholate.
One of the components of a film former are gliding additives. They are introduced to
endow the coating with a resistance to scratching in the mechanical treatment of lacquered
tinplate in fabrication of metal container from it; for instance, additive PVO-30. It is oxidized polyethylene wax and is used as a 5% solution in xylol.
To improve the flow behaviour of lacquers and to eliminate crates on the surface of
coatings in the application of lacquers and enamels, special additives are introduced into
them, for instance, lacquer KO-815. Abroad, the formulations of lacquers include additives
on an acrylic or silicone basis to improve the flow behaviour, for instance, products of
grades BIK-304 or BIK-344 manufactured by German firms.
5.5
Compositions based on oligomer systems
A number of requirements are imposed on the lacquer-and-paint materials intended for internal coating of canning containers: they should not contain toxic components, be sufficiently stable in storage and provide for an even and smooth film on the surface of metal at
the application and drying of lacquer-and-paint materials. Coatings on the basis of these
190
systems should possess a good adhesion to metal, elasticity, hardness and strength to be able
to withstand die stamping, seaming, sealing and other mechanical operations in production
of cans and lids.
Home industries manufacture epoxyphenol lacquers used for protection of canning
containers from tinplate, aluminium alloys and chrome-plated steel. The composition of
these lacquers includes various epoxy oligomers, differing by their molecular mass; phenol-formaldehyde oligomers based on various phenols and their mixtures. The high content
of phenol-formaldehyde oligomers contributes to high chemical endurance of the coatings.
Phenol-epoxy lacquer FP-559 is a solution of a mixture of resins xylene phenol
formaldehyde KFE, epoxy E-05K and alkyd epoxy E-30 in a mixture of organic solvents.
The lacquer is applied on tinplate sheets on roller-type lacquering machines; and on the inner surface of one-piece cans, on spray-type lacquering machines.
The predominant component of lacquer FP-559 is phenol formaldehyde, so at a high
chemical stability of coatings on its basis they are distinguished by a low elasticity. For this
reason, it can not be used in production of one-piece cans.
Epoxyphenol lacquer EP-547 is a solution of a mixture of epoxy E-05K and phenol-formaldehyde FP-1 resins in a mixture of organic solvents. It is used mainly for coating
tinplate in production of canning containers. The lacquer is applied on tinplate sheets on
roller-type lacquering machines and is hardened in convection-type furnaces at 200210C
in 1215 min.
As compared with FP-559, lacquer EP-547 forms films of better elasticity, which enables its use in production of one-piece containers. However, the chemical endurance of
coatings based on this lacquer, especially in an acidic medium, is lower than that of coatings
from lacquer FP-559, which restricts the areas of its application.
Lacquer EP-547 is widely used also for lacquering tubes for food and perfumery products. In fabrication of canning containers for strongly aggressive food media, tomato paste
and tinted stewed fruits, lacquer EP-547 is used in combination with other lacquers and
enamels, such as FP-559, EP-5147al, EP-5195p. Coatings on the basis of these compositions play the role of a sublayer. Chemical endurance of coatings based on lacquer EP-54
is increased by introduction of hardening catalysts of the type of tetrabutoxytitanium or chelate compounds of aluminium.
Epoxy phenol lacquer EP-527x is a solution of epoxy E-05K, phenol-formaldehyde
FPF-1 and alkyd epoxy E-30 resins in a mixture of organic solvents. This lacquer is used
mainly for coating chrome-plated steel.
Drying of the lacquer film is performed by high-frequency currents in inductors at a
temperature of up to 350C for 35 s. To increase the chemical endurance of the coating
and extend the applications of containers from lacquered chrome-plated steel, two-layer
coating is recommended to be done.
Epoxy phenol lacquer EP-5118 is a solution of epoxy E-04kr and phenol-formaldehyde FKoF-4 resins in a mixture of organic solvents. The lacquer is characterized by a high
content of epoxy resin. The lacquer is used for inner and outer coating of the band from
aluminium alloys. On the surface of metal, the lacquer is applied by the roller method. The
regime of its drying is 30 s at 340C. The advance rate of the band during the application
of the lacquer is 60 m/s.
Aluminium enamel EP-5147al is a solution of a mixture of epoxy E-05K, phenol-formaldehyde FPF-1, alkyd epoxy E-30 resins; aluminium paste, polyvinyl butyral and
special additives.
Coatings based on this enamel are resistant to the action of protein-containing
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191
products. It is used for coating cans for meat, fish and vegetable canned products.
To improve the physicomechanical parameters of coatings, primarily, scratch resistance, the enamel is applied over a thin layer of lacquer EP-547. This coating is used for
protection of containers for most types of fish preserves.
Seam lacquer EP-5186 is a mixture of solutions of epoxy E-05K and E-30 and phenol-formaldehyde FPF-1 and FKoF-4 resins in organic solvents. This seam lacquer is used
for protection of the soldered side seam of composite electrolytic-tinplate cans. The lacquer
is applied after soldering the seam, by means of pneumatic spraying and a working viscosity
of 1315 s by VZ-4. This viscosity provides for a lacquer film of 34 g/m2 thick; the width
of the lacquer coating lane is 1520 mm. The lacquer dries up due to the residual heat after
soldering and additional drying together with lacquer of grade EP-5194 at 175C for 15
min.
Lacquer EP-5194 is a mixture of solutions of epoxy resins EO-4kr and E-30 with phenol-formaldehyde resin FPF-1 in organic solvents. This lacquer is used for additional protection from corrosion of the entire inner surface of two-piece canning containers, as well
as for covering the lead-containing solder. This lacquer is applied by pneumatic spraying
and is dried for 15 min at 175C.
5.6
Oleo-resinous lacquers
An advantage of coatings based on these lacquers are their high physicomechanical properties, water and salt resistance. A disadvantage of the coatings is the low stability as compared with epoxyphenol materials. These lacquers are used for protection of containers for
certain type of preserves, for instance, crabs.
Lacquer FL-560 is a solution of the product of condensation of phenol-formaldehyde
resin 101 with Chinese wood oil. A mixture of turpentine with white spirit is used as a solvent. The drying is accelerated by using a manganese resinate siccative.
The lacquer is used for coating tinplate cans for crab preserves. This lacquer is characterized by the following technical parameters: a homogeneous and clear solution, viscosity by VZ-4 at 20C, 95120 s; drying time at 185190C, no more than 30 min.
Lacquer FL-561 is a solution of the product of condensation of phenol-formaldehyde
resin with a mixture of oxidized flax oil and dehydrated castor oil in turpentine. A cobalt-manganese siccative is used to accelerate the drying of the lacquer.
This lacquer is used for coating tinplate, which is applied in fabrication of canning containers for preserves with a neutral medium. The drying time of the lacquer at 185190C
is 30 min.
Lacquer FL-5157 is used in production of protein-resistant enamel for protection of
canning containers from tinplate, intended for crab and neural-medium fish preserves. The
cobalt-manganese siccative is used to accelerate the drying of the lacquer. The viscosity of
this lacquer is 7080 s, the content of volatiles is about 55%, the duration of hardening at
180C is 2630 min.
Lacquer KF-281 is used as a protective coating of an enamel composition based on
lacquer FL-5157. It is the product of condensation of fatty acids of flax oil and Chinese
wood oil with pentaerythritol ester of wood rosin. The lacquer contains the cobalt-manganese siccative. The viscosity of the ready-to-use lacquer is 1830 s, the content of volatiles
is about 64%, the drying time at 180C is 2630 min.
Enamels with zinc oxide are manufactured as protein-resistant ones. They are distinguished by an increased resistance to canned protein media, as zinc oxide is dispersed into
192
lacquers and binds sulfurous compounds evolving in sterilization and storage of protein-containing preserves.
To increase the decorative, hygienic and anticorrosion properties of coatings, use is
made of lacquer-and-paint materials with the anticorrosion neutral pigment titanium dioxide. The major parameters of lacquer-and-paint materials for internal protection of canning
containers are given in Table 5.6.1.
Table 5.6.1 Comparative characteristics of canning containers.
Lacquer
Viscosity Content of Hardening Duration of

(by VZ-4), nonvolatiles, temperature, hardening,
sec
%
C
min
FL-559
80115
4550
180185
1215
EP-547
90120
3842
205210
1215
EP-527h 100150
3845
375385
40 (45)
EP-5118 110180
3640
335345
3540
FP-560
95120
FP-561 140170
EP-5186 5080
EP-5147 100150
5054
4952
4248
3845
185190
185190
175180
210215
30
30
15
15
EP-5194
4550
190200
15
90130
Field of application
Glass-container lids, tinplate

containers
Composite containers from tinplate
(elongation ratio, up to 0.4)
Lids and cans from chrome-plated
steel
Aluminium lids and cans
(elongation ratio, up to 0.6)
Composite tinplate containers
Ditto
For lacquered seam
Composite and pressed/punched
containers
Cans and tubes
Note: Thickness of film in these coatings changes from 4 up to 8 m depending on the chemical
composition of a lacquer.
5.7
Polyvinyl chloride-based lacquers
These lacquers also include other bonding adhesives, in particular, alkyd, phenol and epoxy
resins. The major advantages of coatings based on these copolymers is their high elasticity,
good adhesion, especially to aluminium and alloys, as well as an almost complete absence
of the transfer of off-flavours from the coating to the canned products.
Hardening of films based on vinyl copolymers occurs as the result of evaporation of
the solvents and during the lacquering of tinplate in convection-type conveyor furnaces.
The duration of drying is 10-12 min at 120185C. In application of vinyl lacquers on the
aluminium band the drying is usually accelerated 3040 s at 250275C. When using
lacquers based on vinyl copolymers, it is necessary to take into consideration the possibility
of destruction of the bonding adhesive at a drying temperature above 185C. Primarily they
are used for lacquering cans for beverages.
Coatings practically do not transfer foreign smells and off-flavour to the contents of
the can. Another important application are lids for glass containers.
A disadvantage of lacquer-and-paint materials on vinyl basis is the inconstancy of their
properties in storage of no more than 46 months. The difficulty of preparing stable dispersions is the complexity of purification and scarcity of components, a higher consumption
of lacquers on vinyl basis as compared with epoxyphenol compositions, as well as in most
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193
cases a low chemical stability due to the difficulty of achieving a high and stable adhesion
of vinyl lacquers to the protected surface.
5.8
Oligoesters and water-base, water-soluble and water-dispersion

binders
A promising trend in the development of lacquer-and-paint materials for protection of the

outer and inner surface of canning containers is the creation of lacquer and pigment systems
based on saturated oligoesters. Such materials combined advantages characteristic of epoxyphenol and generic systems. Coatings based on oligoesters, along with high adhesion,
thermal and corrosion resistance, possess a high elasticity, hardness and resistance to mechanical loads.
Oligoesters are used as film formers for can varnishes independently or in combination
with thermosetting oligomers, for instance, epoxy, phenol, melamine- and benzguanoformaldehyde and thermoplastic polymers (vinylic, acrylic).
Water-based lacquer-and-paint materials occupy one of the leading places in the assortment of ecologically adequate kinds of lacquer-and-paint products in most developed
countries. A significant part of the total volume of lacquer-and-paint materials on water basis are supplied to the US canning industry and are used for anticorrosion protection of containers intended for packaging beer and alcohol-free beverages. Western companies
manufacture a wide assortment of water-based lacquer-and-paint materials based on epoxy,
vinyl, acrylic polyester and other resins used in formulations of lacquers for protection of
canning containers.
In the recent years, great attention is given to the development of water-dispersion systems for protection of canning containers based on carboxyl-containing epoxyacrylic film
formers, obtained by way of physical or chemical modification of epoxy oligomers by acrylates. These lacquers were first introduced in the US canning industry, and at present more
than half of all beer cans are manufactured using water epoxyacrylic systems. Phenol- or
melamine-formaldehyde resins are used as hardeners; herewith, tertiary amines serve as a
neutralizing agent. Coatings are hardened in several seconds at a temperature of about
200C. Their advantages are high elasticity and correspondence to the sanitary-hygienic requirements to food-purpose coatings.
Changes in the recent years in the assortment of lacquer-and-paint production under
the influence of causes of economic and ecological character affected the canning industry
to a significant extent. Ecologically adequate lacquer-and-paint materials powder materials, with high content of nonvolatile components, aqueous, of radiation hardening started to be widely used for protection of the inner and outer surface of metal canning
containers. Thus, demand for such materials in the USA is over 20%; herewith, water-diluted materials are used to cover over half of beer and drink cans. In the nearest years, this
index would reach 100%.
A significant growth of demand for such compositions is due to the decreased content
of solvent, whose amount does not exceed 1520% as compared with traditional lacquers.
Their advantages are also low toxicity, fire safety, simplicity of application methods. However, for protection of canning containers only those systems are suitable, which satisfy specific requirements to materials in contact with food products. The major of them are
inertness of the coating as compared with the canned product, stability of materials in storage for no less than 12 months, processibility, high adhesion to metal supports, stability to
the action of hot water and acids, stability to sterilization and pasteurization. Coatings from
194
water-diluted materials should be of high quality, should not be inferior than traditional lacquer coatings by their performance characteristics and economical efficiency.
The most widespread water-diluted canning materials are carboxyl-containing epoxy
oligomers and epoxyacrylates. These oligomers are synthesized by various methods. The
simplest of them envisages the interaction of an epoxy oligomer with dibasic acids or their
anhydrides. Disadvantages of these methods are process problems associated with the
two-stage character of the synthesis, large duration of the process, and high cost of the product. Aqueous materials, which are distinguished by a high stability and processibility, are
obtained in the reaction of epoxy oligomers with various aromatic amino acids. These compositions are hardened in 10 min at 204C to form coatings stable to the action of acidic
and protein food products.
As a phenolic component, use is made of epoxy oligomers modified by polyfunctional
phenols. In the West, such oligomers are hardened using amino-, urea- or phenol-formaldehyde resins. Compositions are hardened in 212 min at 200215C to form coatings stable to pasteurization, sterilization; action of acids, alkali and solvents. However, the most
widely used materials for protection of canning containers are water-diluted materials based
on epoxy oligomers modified by acrylates. According to estimates by experts, these materials are used to cover over 60 bln cans.
A number of works note that aqueous materials based on mixtures of epoxy oligomers
with acrylates do not always satisfy manufacturers of canning containers with respect to
their water resistance, chemical stability and other characteristics. Considerably higher performance characteristics are found to have systems containing grafted epoxyacrylates with
carboxyl groups in the side chain as film formers. Dispersions are hardened in the presence
of hexamethoxymethyl melamine at 188C in 60 s. Coatings are distinguished with a high
adhesion to aluminium and stability in hot water.
Carboxyl-containing epoxy oligomers and epoxyacrylates are of interest as potential
film formers for electrophoretic materials for coating the inner and outer surfaces of cans.
Phenol-formaldehyde or nitrogen-containing resins are used as hardeners. Such modified
compositions are used also for coating drawn cans or rolled metal to be used for fabrication
of three-piece composite cans.
Epoxy oligomers modified by polyesters and polyurethanes are used as film formers
of water-diluted materials for coating canning containers. For instance, aluminium and steel
beer cans are recommended to be coated with an aqueous dispersion, which includes
7095% of carboxyl-containing polyester based on trimellitic anhydride and adipic acid
with 530% epoxy dianic oligomer. Upon neutralization with ammonia, the dispersion is
applied to the surface of cans and is hardened for 10 min at 200C. The coating does not
affect the taste of the packaged product.
When producing such compositions, the polyurethane forpolymer is used, which is obtained by the interaction of a mixture of polyester polyol and carboxyl-containing polyol
with polyisocyanate. The latter plays the role of a crosslinking agent. Coatings from these
materials are distinguished by a high chemical endurance, elasticity and adhesion to metal.
Water-diluted materials based on acrylic resins make it possible to obtain coatings
with high durability, light permanence and heat resistance. However, due to the negative
effect on the taste qualities, they are used only for coating the external surface of the container and as coating lacquers for protection of lithographic printing. Such compositions are
produced using alkyl acrylates, methacrylic acid, methacrylates and vinyl acetate.
Coatings based on vinyl materials are distinguished by a high corrosion resistance and
elasticity. However, due to an insufficient heat resistance, they are unsuitable in the cases
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195
when products are subjected to long-time heat treatment. Copolymers of vinyl chloride or
vinylidene chloride with acrylate or other monomers are used the most frequently to produce these compositions.
For protection of the inner surface, use is made of copolymers of methacrylic acid, ethyl acrylate and styrene in a mixture of cyclohexanol and butyl cellosolve containing vinyl
copolymer and epoxy oligomer. Coatings on the basis of water-diluted compositions of this
kind have a high adhesion and render no effect on the properties of canned product.
Aqueous emulsions for coating cans based on polymer of vinyl chloride, ethylene and
acrylic acid have been developed. Copolymerization is carried out in the presence of polyvinyl alcohol, which plays the role of a dispersant. Compositions are used in combination
with melamine-formaldehyde resin for thermosetting coatings.
Aqueous pigmented materials are used for external coating and lithography of cans.
Alkyd, polyester, acrylic or epoxyphenol oligomers are used as film formers in such materials.
Water-diluted materials for coating canning containers are applied on the surface by
rolls, spraying or pouring. The choice of the application method is determined by the type
of container and the process of its fabrication. When producing composite or two-piece cans
by the multiple drawing method, use is made of rolled or sheet material preliminarily painted by any method on a standard equipment. Before formation of cans, the surface of metal
is coated with a layer of lubricant, which facilitates the process of fabrication and protects
the lacquer-and-paint coating from destruction. Two-piece cans produced by the ironing
method are decorated from the outer side and are painted from the inside by spraying. In
this case, the best results are obtained by using double-nozzle sprayers or those with two
mixed nozzles, which enable application of two-layer coatings.
5.9
Compositions with high dry residue and ink powders
An advanced direction of studies in the field of ecologically adequate lacquer-and-paint materials for protection of canning containers is the development of systems with high dry residue. Unlike aqueous compositions, lacquer-and-paint materials with high dry residue wet
the metal support well and do not require special surfactants or other additives. The use of
lacquers with high dry residue has begun from the application of oil-phenolic systems with
dry residue content of 7075%. For instance, lacquers with high dry residue were proposed
for protection of canning containers; as the bonding adhesive, they contain an adduct of an
epoxy oligomer with another oligomer, having amino groups, which perform the function
of a reactive diluter and plasticizer.
Ink powders are a progressive type of ecologically adequate lacquer-and-paint materials; coatings on their basis are characterized by high physicomechanical and protective
properties.
Studies of the use of ink powders for protection of canning containers are carried out
by a number of leading Western companies in the USA, the UK, Germany etc.
However, the use of powder lacquer-and-paint materials for protection of bodies of
canning containers is of limited character due to the high costs of coatings and the complexity of regulating their thickness in the high-speed application process. These drawbacks can
be overcome by using aqueous powder suspensions, which combine the advantages of water-diluted systems and ink powders. Powder suspensions, which make it possible to obtain
coatings of any given thickness, are widely used in the recent years in Japan for protection
of canning containers.
196
5.10 Coatings for protection of the outer surface of canning containers

The following materials are used for protection of the outer surface of containers and application of colour or black-and-white patterns on it:
silver or golden primer lacquers intended for creating the background as well as for
improving the elasticity and formability of the whole coating;
white or colour primer enamels for creating the continuous background for the printed pattern;
white, colour and black printing inks intended for protection of a printed image from
mechanical damage, for offset printing on tinplate from flat plates of figures, background
and text in accordance with the reproduced original;
transparent colourless coating lacquers intended for protection of a printed image
from mechanical damage, for giving the coating a gloss, formability and resistance to sterilization in production of canning containers.
The silver background under the pattern applied by printing is created by using colourless transparent lacquers of various grades: AS-548, EP-5190,EP-547; the golden background is created using lacquers EP-559, FL-561, FL-560.
Enamel AS-576 is a suspension of titanium dioxide in a solution of acrylic copolymer
and epoxy resin in a mixture of solvents xylene, butyl acetate and ethyl cellosolve.
White enamel EP-5239 is a suspension of titanium dioxide in a solution of epoxy resin
E-05K, melamine-formaldehyde resin K-421-04, glycerol polyester of sebacinic acid PE-5
and epoxyester EM-34. A mixture of ethyl cellosolve, butanol and xylol is used as a solvent.
Coating lacquers are intended for application over ink impressions; they can be applied both
over preliminarily dried and raw imprints immediately after printing.
Coating lacquers are produced using various resins and their modifications, such as
alkyd, acrylic, epoxy, epoxyester, phenol-formaldehyde, melamine-formaldehyde, polyester. Aromatic hydrocarbons, esters, ketones, alcohols are used as solvents.
To endow the lacquer coating with a gliding ability and strength to scratches, waxes
and silicon additives are introduced into the composition of the lacquer. The table gives the
process parameters of coating lacquers and enamels.
Coating lacquer AS-548 is a solution of acrylic copolymer 5BV in a mixture with epoxy lacquer E-33R in ethyl cellosolve and propylene carbonate. The lacquer is applied on
a roller-type lacquering machine; the thickness of the dried layer is 6 g/m2. The lacquer
coating has a good gloss, hardness, stability to sterilization in combination with protective
primer enamels, for instance, with acrylic enamel AS-576. The coating has the required
elasticity and stability to the stamping of lids and cans with the drawing depth of up to 36
mm.
Lacquer EP-5190 is a solution of epoxy resin E-05K, melamine-formaldehyde resin
K-421-04 and glycerol ester of sebacinic acid PE-5 in a mixture of solvents ethyl cellosolve,
butanol and xylol.
Upon application over dried inks, the lacquer forms a glossy solid coating and is stable
to stamping. Is recommended in combination with enamel EP-5239 for the outer coating of
containers for nonsterilized products.
Printing of labels directly on metal containers as compared with pasting paper labels
significantly increases the quality of the design of the container and reduces its cost 1.82.6
times.
Formulations of new highly efficient lacquer-and-paint materials for printing on metals and the monitored technological process of their application have been worked out. The
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197
development of rapidly setting materials and technological processes of their application

considerably reduces the costs and increases the quality of printing on metals (Table 5.6.2).
Table 5.6.2 Characteristics of lacquers and coatings.
Material
Viscosity by VZ-4
at 20C
Drying regime,
C
Thickness of
coating, m
Field of
application
Lacquer AS-548
80120
1215 min at
70180C
56
Lacquer EP-5190
5070
1518 min at
170175C
Enamel AS-576
100140
1215 min at
150160C
1518
Enamel EP-5239
white
110180
1518 min at
150160C
1518
Lacquering of ink
imprints for
canning containers
Lacquering of ink
imprints for bodies
of nonsterilized
containers
Bodies of
composite cans,
stamped cans
(diameter up to 36
mm), can lids
Bodies of
nonsterilized
containers
clear
Note: Content of volatiles in the film is from 45 up to 58%.
The technological process of producing an offprint on the metal surface includes three
stages: application of the primer film; printing of an image on the primer film; coating lacquering of the offprint. Formation of lacquer-and-paint films at each of these stages is done
at high temperatures up to 180C for a prolonged time of up to 20 min in large-sized drying
furnaces of up to 10 m in length with large energy intensity up to 1000 kW.
The printing sheet metal is used to fabricate containers for various purposes. The largest thermal, mechanical and hydrothermal impacts to which an offprint on metal is subjected occur in the fabrication of one-piece canning containers. Lacquer-and-paint materials
used to produce an offprint on metal should be stable to these impacts and possess a set of
high adhesion, physicomechanical, waterproof, technological, optical and economic parameters. A number of essential performance properties of lacquer-and-paint materials are
determined not only by the quality composition but also depend significantly on conditions
of their formation. In this connection, the correct protocol of the technological process for
metals is of no less importance as compared with the composition of lacquer-and-paint materials. Most of the recommended compositions for printing on metals do not possess the
set of required properties. They are characterized by a long setting time of 1040 min at
temperatures of 120200C. Many of them become yellow or hydrolyzed, others are not
satisfactory by their mechanical and adhesion properties, which can change depending on
the setting conditions. Due to the multicomponent nature of the recommended materials for
printing on various metals the process of their setting on the offprint is very complex and
is insufficiently studied.
In printing production, two drastically different methods of film formation in printing
on metals are used, such as the removal of solvent and other low-molecular-mass components from the ink and film formation to form a three-dimensional network. Printing inks
for metals are set on the offprint as the result of oxidative polymerization of plant drying
198
oils, natural and synthetic drying oils. For setting primer and coating lacquer-and-paint materials, both hardening methods can be used, i.e., polymerization and polycondensation in
combination with the evaporation of solvent.
To accelerate the processes of film formation of lacquer-and-paint materials on an offprint, various types of irradiation are used thermal, infrared, ultraviolet, electronic the
most widespread of which for printing on sheet metal is the method of thermal intensification. Intensification of the setting of materials in printing on metals requires the use of expensive equipment and a large consumption of thermal energy. About 25% of all production
expenses are used for setting the printing.
A major problem in the considerable improvement of printing-on-metal technologies
is the development of a set of rapidly setting lacquer-and-paint materials and a scientifically
grounded regimes of priming, printing and coating lacquering.
Owing to the specific feature of the technological process, the printing is carried out
not on metal, but on the priming layer, the base of which is a polymer film former. This
technological feature is considered as a prerequisite for constructing the printing ink, whose
setting on the offprint should be performed as the result of the interaction of its components
with the priming film. The basic requirement to the priming film is its high permeability
with respect to the solvent of the printing ink.
Priming compositions were developed based on resin PMK-5, which is a linear amorphous copolymer of butyl methacrylate and methacrylic acid. Modifying additives used
were epoxy resins ED-8 and ED-20, n-tert-butyl-phenol-formaldehyde resin 101l, polyalumophenyl syloxane representing a lacquer of grade KO-810. The compositions were distinguished by ratios of these components. The coatings consisting of 7.5% BMK-5 and
2.5% ED-8 had the optimal properties. As a solvent, the lacquer compositions used a mixture of ethyl cellosolve and butyl acetate at a ratio of 1:1.
Priming films of lacquer compositions of about 10 m thick were formed on supports
at three temperatures of 160, 180 and 200C within the time interval of 1120 min. Destruction of splices was performed on a tensile tester at a displacement rate of the lower
clamp of 30 mm/min. The measurement of adhesion strength was carried out by the method
of shear, which makes it possible to use supports used directly in printing and corresponding
to the conditions of force impact on the film in stamping. In adhesion strength studies, hot
dipped tinplate GZhK-25 fabricated from low-carbon steel band coated with tin on both
sides was used as a support.
Printing inks with the diffusion mechanism of setting on the priming film have been
developed; their basis is a lacquer composition of copolymer BMK-5. The regularities of
migration of free plasticizers based on esters of o-phthalic acid and from solutions of phenol-formaldehyde resins to priming films, as well as the kinetics of ink setting on priming
films of various compositions have been studied. o-Phthalic esters of various compositions,
such as dimethyl phthalate, dibutyl phthalate, dioctyl phthalate have been studied. These
plasticizers are characterized by the largest diffusivity.
Phenol-formaldehyde resins, such as F-60 based on para-tert-butyl phenol and formaldehyde; E-12 based on diphenyl propane and formaldehyde; FT-1 based on para-tert-butyl phenol, diphenyl propane and formaldehyde; modified by various compounds, were
chosen as the film-forming basis of the compositions of printing inks. The absorption kinetics of free phthalates by the priming film of lacquer AE-1 has an exponential character,
and the diffusion increases in the series of the plasticizers dioctyl phthalate, dibutyl phthalate, dimethyl phthalate. The character of the regularity of absorption by the priming film
of phthalates from solutions of resins and the ratio of the diffusion activity between
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199
phthalates remain the same as in the case of free phthalates. The studied regularities are the
basis for developing formulations of printing inks with the diffusion mechanism of setting.
The setting rate on epoxyacrylic and epoxyphenol priming films is considerably lower
when using materials and inks based on dioctyl phthalate F-60 as compared with acrylic
priming lacquer AE-1. This is due to the lower permeability of these materials determined
by the significant differences in the structure-formation mechanism in the formation of
films. With these regularities in mind, a mechanism of setting printing inks on priming films
has been proposed.
Owing to the diffusion of plasticizer to the priming film, a solid film of the printing
ink is formed on the surface of the priming film; this solid film is adhesionally bound to the
priming film. The strength of the adhesion bond is determined by the interaction of free
functional groups, available on the surface of the films. The largest adhesion strength is observed in films of the printing ink and the priming lacquer AE-1, as by the moment of printing the film there occurs a partial formation of a three-dimensional structure. Owing to this,
carboxyl groups of BMK-5, which were not consumed totally, interact chemically with the
hydroxyl groups of phenol-formaldehyde resin F-60, and their macromolecules preserve
the capability of intensive mutual diffusion. Studies of the effect of the printing and finishing processes on the adhesion strength of priming films have been carried out. The priming
film, applied to metal and formed in the process of the first technological operation, experiences various effects of the subsequent technological operations. In this connection, the
effect of such factors as the action of printing inks and coating lacquers, deformation rate
and value of deformation of the priming filmmetal system has been studied. Objects of
study were the following: acrylic lacquer AE-1, epoxyacrylic enamel AS-576, epoxyphenol
lacquer EP-547 and alkyd priming enamel, as well as alkyd inks the basis of the bonding
adhesive of which is F-60 with dioctyl phthalate, coating epoxyacrylic lacquers AS-548, as
well as coating systems from Germany and Japan.
The general regularity of the effect of an ink is a decrease of adhesion and strength, an
increase of the ultimate relative elongation of priming films. A depletion of these characteristics is observed in the series of priming materials AE-1, AS-576, EP-547. A decrease
of the adhesion and strength parameters is observed within the range of 1419 down to
710%; herewith, the relative elongation increases by 718%. The change of these parameters correlates with the permeability of priming films with respect to the solvent. The
mechanism of change of the properties of priming films during the impact of solvent or plasticizer on them is the predominant adsorption of the liquid phase on the surface of metal
and the simultaneous plastification of the bulk of the film. The adhesion strength of priming
films in combination with epoxyacrylic lacquer AS-548 increases especially significantly;
herewith, the adhesion strength of the priming film of lacquer AE-1 increases under the action of the coating lacquer, having one film-forming base, which is used for creating a set
of rapidly setting materials.
An increase of the adhesion strength of priming films occurs owing to the diffusion of
the film-forming components of the coating lacquer through them with the solvent, which
at high temperature contributes to the increase of the concentration of reactive groups on
the surface of the support. These groups can be sorbed on the surface of the support to form
intermolecular hydrogen bonds also by way of iondipole interaction of polymer molecules
with the surface groups of the passivation film of metal.
The results of studies of the effect of film-forming and hydrothermal-treatment conditions on the adhesion and physicomechanical properties of compositions made it possible
to develop formulations of priming lacquers based on acrylic copolymers, as well as rapidly
200
setting acrylic priming enamels and a rapidly setting coating lacquer on the same filmforming base.
The regularities of the studies of the diffusion properties of the priming layers and dissolving plasticizers enabled the development of printing inks of a new type with the diffusion setting mechanism. On this basis, special purpose inks have been developed, for
printing on metals and ready-prepared items from metal and glass. A feature of the developed compositions is that at the initial stage of film formation, simultaneously with the
evaporation of the solvent, an adsorption layer is created; further on, the reaction of hardening proceeds in the bulk of the films and on the surface of metal to form a three-dimensional structure. The setting rate of inks is determined by the rate of solvent diffusion from
resin to the priming film; an increase of temperature sharply increases the rate. The chemical nature and supramolecular structure of the priming film has a significant effect on the
ink setting rate. An increase of the extent of crosslinking of molecules and a rise of density
of packing of supramolecular formations decrease the permeability of priming films with
respect to phthalates, which reduces the ink-setting rate.
Inks set on priming films by the oxidative polymerization mechanism cause no change
in the adhesion and physicomechanical properties of priming films. Inks containing dioctyl
phthalate decrease adhesion and tensile strength of priming films and increase their ultimate
relative elongation. These regularities in the change of properties of priming films depend
on their permeability with respect to the solvent. However, they do not lead to a critical
change of the performance properties of priming films. Coating lacquers containing free
functional groups increase the adhesion strength of priming films.
6
6.1

Compositions for Protection
of Canning Containers
Ways of improving the protective properties of coatings
Despite the broad range of materials for protection of canning containers, most lacquers
used at present are produced on the basis of epoxyphenol oligomers. However, the diversity
and complexity of the technological processes of fabricating modern types of canning containers, various sterilization regimes of canned products, high requirements to the terms of
their storage compel researchers to search for ways to improve the properties of epoxyphenol compositions. Work is under way mainly in two directions: chemical modification
of particular components of epoxyphenol compositions, mainly phenol-formaldehyde
oligomers, and modification of epoxyphenol compositions by various additives.
To improve the physicomechanical characteristics of phenol-formaldehyde oligomers
and coatings on their basis, these oligomers are modified and plasticized. The modifier for
resol oligomers is chosen of such a structure, so that to ensure the chemical interaction of
the components of the phenol fragment by the hydroxyl and methylol groups.
Phenol-formaldehyde oligomers (PFO) on the basis of glycerol esters of parasubstituted phenols, which contain no free phenol hydroxyl groups, are known. In this case, coatings have high adhesion properties and elasticity.
Of great commercial importance is etherification of methylol groups by unsaturated
fatty acids or high-molecular-mass polyesters containing hydroxyl and carboxyl groups, as
well as by unsaturated, e.g., acrylic and methacrylic, acids. A significant effect of plastification is achieved by introduction of long-chain polyoxy compounds into the structure of
PFO. However, the chemical endurance of coatings on their basis is reduced in this case.
The most widespread way of increasing the elasticity of PFO is their etherification by
alcohols, mainly n-butyl and isobutyl alcohols. Exactly these oligomers are used in epoxyphenol compositions for protection of canning containers. Epoxy-phenol coatings based
on butanolized PFO possess a set of such valuable properties as high chemical endurance
and elasticity, determined to a great extent by the level of PFO butanolization. Coatings
with a high resistance to stamping can be formed from lacquers with etherified phenol-formaldehyde oligomer with a molecular mass of 250500, containing 6.011.0 wt. %
methylol groups and 18.032.9 wt. % etherified groups.
A no less efficient way to improve the protective properties of coatings is structural
modification of initial epoxyphenol compositions by various additives, in particular, by
other oligomers. It has been shown that introduction of oligourethane triisocyanate or
202
oligodieneurethane isocyanate in the amount of 0.120.32 wt. % as a crosslinking agent to

the composition based on epoxy and butanolized phenol-formaldehyde resin leads to an increase of elasticity, adhesion and resistance of coatings to the action of organic solvents.
To increase the adhesion strength and especially stability of coatings to sterilization, a modifying additive the product of interaction of epoxy dianic oligomer with a molecular mass
of 5001100 and monopropargyl urethane taken at a molar ratio of 1:(0.21.0) is introduced to the epoxyphenol composition.
Positive results were obtained in modification of commercial lacquer EP-5118 by special additives containing various functional groups (amine, hydroxyl, cyan etc.). The composition obtained in this case forms coatings with internal stresses reduced 25 times as
compared with films from the initial lacquer; high chemical endurance in model food media, as well as increased stability to stamping; the amount of rejects in this case is reduced
by 2030%.
Introduction of low-molecular-mass condensate of fluorinated organosilicon compounds with alkoxylyl groups into compositions makes it possible to obtain coatings for the
internal surface of containers, which prevent deposition of dairy products, oils, vinegar etc.
poured into the containers.
Hardening of epoxy resins by phenol-formaldehyde condensates is accompanied with
a number of reactions, in particular, interaction of methylol and butoxyl groups of phenol
condensate with epoxy and hydroxyl groups of epoxy resin, affecting the quality of the final
product. Therefore, the choice of the optimal ratios of the components and hardening regimes of compositions presents significant problems and is mainly performed empirically.
According to the literature data, acid-resistant coatings are produced using highmolecular-mass epoxy resins with molecular masses above 2500 and alcohol-soluble
resols, for instance, phenol and 1-cresol, both butanolized and nonbutanolized. Novolac
resins and 100% reactive resins can be used as phenol resins. Hardening of epoxyphenol
compositions proceeds better upon addition of 12% phosphoric acid; herewith, epoxyphenol lacquers dry at 180200C for 2030 min. To increase the quality of epoxyphenol
coatings, it is recommended to warm up the mixture of resin solutions preliminarily at
100150C.
The possibility of modifying epoxy resins with phenol-formaldehyde condensates has
been studied, and the properties of coatings on their basis have been investigated.
Low-molecular-mass resins E-40 and E-41, medium- and high-molecular-mass
epoxides E-44 and E-49, as well as resins E-15 and E-05, were used.
Modified and nonmodified resol resins cresol-formaldehyde resin K-212-01, 100%
phenol-formaldehyde resin, phenol-formaldehyde butanolized condensate modified by
Chinese wood oil, as well as xylenolphenol-formaldehyde butanolized resin and maximally
butanolized phenol-formaldehyde condensate were used as phenol-formaldehyde resins.
It has been found that all the above epoxyphenol compositions form water-resistant
coatings. Only coatings with a high-molecular-mass epoxy resin in the amount of no more
than 40% proved to be acid-resistant. Coatings on the basis of low- and medium-molecularmass epoxy resins proved to be non-acid-resistant.
6.2
Effect of the nature of the support on the structure and properties of

coatings
When choosing lacquer-and-paint materials for protection of canning containers, it is

necessary to take into account not only the properties of polymer materials themselves, but
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203
also the characteristics of the metal support. This is explained by the fact that the structure
and properties of the polymer coatings formed depend significantly on the nature of the
solid surface and on their thickness. The effect of the support is especially significant at a
small thickness of the coating (46 m) for canning containers.
It has been shown by example of epoxyphenol lacquer EP-547 and supports from electrolytic tinplate (EZhK), chrome-plated steel (KhZhK), aluminium anodized alloy AMG-2
that the microhardness of coatings essentially depends on their thickness and nature of the
support.
The experimental data obtained indicate the predominant influence of the nature of
supports as compared with the microgeometry of their surface (the character of the distribution and size of defects) on the properties of coatings formed on them. Coatings applied
on KhZhK have greater values of hardness, gradient of its change in particular layers by the
thickness of the film and the strength of the adhesion bond as compared with coatings applied on EZhK and AMG-2. This is due to the differences in the size of structural elements,
in the density of their packing, as well as in the morphology of supramolecular structures,
which differ depending on the nature of the support and thickness of coatings. It has been
found that macromolecules of the phenol-formaldehyde components are sorbed from the
lacquer mixture predominantly on the surface of KhZhK and AMG-2 in the process of hardening on the surface of the support, thus forming the structure of the network framework,
whose cells are filled mainly with the epoxy component. On the contrary, in coatings from
EZhK the basis of the structure is made by the epoxy oligomer with the phenol-formaldehyde component evenly distributed in it.
When the thickness of the lacquer layer is increased, coatings on KhZhK and AMG-2
approach those on EZhK by their structure and properties.
The results obtained indicate that a harder and stronger coating with lacquer EP-547
on KhZhK is more stable to the action of aggressive media as compared with coatings on
EZhK, but is less stable to impact loads in stamping as the result of layer-by-layer inhomogeneity determined by the hardness gradient.
With account for these results, protective lacquer compositions should be chosen for
particular types of metal, used to produce canning containers, and the composition of
canned product.
6.3
Structure formation in solutions of epoxyphenol compositions and

the properties of coatings
The results of studies of chemical transformations occurring in fabrication and hardening

of epoxyphenol systems are contradictory and have not been studied sufficiently.
It is pointed out that the reactions of epoxy groups proper, considering their minor content in a real composition, do not contributed significantly to the formation of the molecular
structure and properties of a polymer. Presumably, the greatest role is played by the reactions of the functional groups of phenol-formaldehyde oligomer, of partially butanolized
resol type on the basis of phenol, and substituted with phenol (-resol, n-tert-butyl phenol
etc.). The kinetics of the reactions was studied by the methods of isothermal calorimetry
and chemical analysis, as well as IRS and NMR.
Interaction of PFO and EO during the hardening of compositions occurs by methylol
and butoxyl groups of PFO with secondary hydroxyl groups and o-hydrogen atoms of phenyl cycles of EO.
It is assumed that the instable quality of coatings is due to dissimilar chemical
204
endurances of films when using different batches of epoxy oligomer. The low chemical
endurance of coatings is related in a number of works to an insufficient crosslinking when
using different batches of epoxy oligomer.
These regularities are explained by the association of epoxy oligomer in solution. To
decrease the extent of association of epoxy oligomers, use is made of better-quality solvents, which leads to a greater density of the polymer network.
An indirect characteristic of the quality of solvent and the extent of associations is considered to be the critical concentration of associate formation. It is determined using rheological methods.
It has been found that for phenol oligomer the critical concentration in ethyl cellosolve
is two times higher than that for epoxy oligomer. It is assumed that the main contribution
to the formation of associates is made by molecules of epoxy oligomer.
A decrease of the extent of association of epoxy oligomer in solution contributes to a
more even distribution of the phenol component in it and leads to an increase in the density
of the three-dimensional network. However, this worsens the performance properties of
coatings, internal stresses increase, chemical endurance goes down. This is assumed to be
due to the formation of an inhomogeneous defect structure.
The increase of internal stresses contributes to the destruction of coatings in stamping
of workpieces of canning containers.
To improve the performance properties, it is customary to perform the preliminary
forcondensation by heating the mixture of solutions of oligomers in ethyl cellosolve for several hours. However, the mechanism of the occurring physicochemical processes in solutions of mixture compositions and coatings on their basis has not been studied.
Using the method of electron microscopy, it has been found that a homogeneous globular structure is formed in coatings from forcondensates, and the size of structural elements
decreases from 500 to 50 nm.
To elucidate the case of this phenomenon, the method of light scattering was used to
study the features of structure formation in solutions of epoxyphenol compositions depending on the forcondensation conditions.
As initial components, use was made of epoxy dianic oligomer E-04Kr and butanolized phenol-o-cresol-formaldehyde oligomer FKoF-4.
Comparing the parameters of the chromatographically determined molecular-mass
distribution of oligomers and the molecular-structural parameters of their solutions, one can
assume the existence of particles in the form of associated molecules in solutions. Close
values of these parameters testify to a sufficiently narrow distribution of associates by mass.
Studies of the structure of forcondensate solutions has shown that the mass of particles
present in solution decreases in the course of forcondensation to reach a minimum in 1 to
1.5 h. Further on, as the duration of the heating increases, the mass of particles grows. A
change of the mean radius of inertia of particles also corresponds to this change of mass.
The thermodynamic characteristic of the affinity of the solvent to polymer is determined by the value of the second virial coefficient. Its negative value, obtained for solutions
of the initial epoxy and phenol-formaldehyde oligomer, indicates a weak oligomerethyl
cellosolve interaction. An increase of this coefficient with the duration of forcondensation
increasing is, evidently, a consequence of an improved compatibility of the components in
the process of forcondensation.
It follows from the electron-microscopy data on the change of the average size of the
structural elements in coatings depending on the forcondensation time that this regularity
is nonmonotonic and has an extremum at an optimal forcondensation time, to which the
CHAPTER 6
205
smallest size of the globular structures corresponds.

From comparison of the data on the effect of the forcondensation time on the structure
of solutions and coatings, it follows that the character of the change of size of structural elements is the same both in the liquid phase and in coatings. Higher physicomechanical and
performance parameters correspond to the smallest size of the structural elements.
The method of light scattering was used to study the effect of the moment of introducing orthophosphoric acid as a structure former on the properties of epoxyphenol compositions. The role of the catalyst on the structural parameters of forcondensates was studied in
solutions of ethyl cellosolve with the initial concentration of 0.4 wt. %. Forcondensation
was carried out at 120C for 1.5 h.
It follows from the data obtained that forcondensation in the presence of orthophosphoric acid leads to an increase by almost an order of magnitude of the mass of associates
as compared with solutions without a catalyst.
The data obtained using the light-scattering method made it possible to establish some
features of structure formation in the process of forcondensation in solutions of epoxyphenol compositions. However, the regularities for diluted solutions of compositions established using this method should have been checked in concentrated solutions.
Structural features of compositions determine their optical properties, which depend
on the transparency and refractive indices of mixed components, as well as the extent of
their dispersiveness. However, the close values of the refractive indices of solutions studied
(for epoxy oligomer 1.416 and for phenol-formaldehyde oligomer 1.409) provide for the
transparency of the mixture irrespective of its morphology in the entire range of compositions, exclude the possibility of assessing the structure of the epoxyphenol composition by
controlling its optical properties.
For this reason, the rheological properties of concentrated solutions of initial oligomers and epoxyphenol compositions, depending on conditions of their formation, were
studied, which reflect the occurring structural transformations.
The character of the rheological curves suggests that within concentrations up to 20%
the solutions of initial oligomers and compositions on their basis are Newton-type systems,
i.e., the dependence of viscosity on shearing stress is a straight line parallel to the abscissa
axis.
As the concentration of solutions is increased up to 4050%, their viscosity is observed to rise; there are some changes in the character of the rheological curves, on which
an area of structural viscosity appears. However, the absence of a region of constant viscosity indicates that in this area of concentrations solutions are weakly structured systems,
in which the number of contacts between structural elements is insignificant.
Evidently, in this case the major part of intermolecular bonds is used to form primary
aggregates of macromolecules, and only an insignificant part of them is consumed for the
bulk structuring of the system. Already at small loads there is the rupture of bonds involved
in the formation of the three-dimensional network and the breakdown of the structure to the
primary associates of macromolecules.
Thus, in the range of working concentrations of solutions from 15 upto 40% the rheological parameters of epoxyphenol compositions are characterized mainly by the lowest
Newton viscosity, whose value is determined predominantly by the size of the primary
structural elements.
The rheological characteristics of solutions of epoxyphenol compositions change similar to the way they change in solutions of individual oligomers. Apparently, the character
of structure formation and peculiarities of interaction of oligomers with the solvent in the
206
mixture composition does not change.

The regularities in the character of interaction of the epoxyphenol-composition components depending on the conditions of their compatibility is well traced in studies of the
rheological characteristics of the composition-dependent solutions assessed by the change
of the relative viscosity of the system. The curve of the viscositycomposition dependence
obtained for a mechanical mixture of epoxy and phenol-formaldehyde oligomers goes
above the additive line, which indicates a more intensive interaction in the mixture as compared with solutions of individual oligomers. This deviation is much more pronounced for
solutions of forcondensates.
The viscosity of a composition changes nonmonotonically depending on the forcondensation conditions and reveals a minimum in the point corresponding to the smallest size
of structural formations. Evidently, an improvement of the thermodynamic compatibility
of the components in the process of forcondensation and a decrease of the size of the structural elements in the solution at a certain warmup time lead to a decrease of the system viscosity. The subsequent increase of the extent of association and the worsening of the
interaction of oligomers with the solvent are accompanied with an increase of viscosity.
As the molecular mass of epoxy oligomer is increased, the regularities in the change
of the rheological properties are preserved; however, the optimal time of warming up the
composition slightly increases.
To establish the relationship between the processes of structure formation in solutions
of epoxyphenol compositions and in the formation of coatings on their basis, as well as to
study the effect of the supramolecular structure of the coatings on their properties, the structure of films was studied by the method of electron microscopy. It has been found that coatings from a mechanical mixture of epoxy oligomer and phenol-formaldehyde oligomer
reveal an inhomogeneous defect structure from large structural elements of 500700 nm in
size, which form a sparse three-dimensional network. A preliminary warming-up of the
composition contributes to an increase of the structural homogeneity of films and a decrease
of the size of supramolecular formations; the more homogeneous structure is formed in
coatings from forcondensates obtained at an optimal warmup time. The size of globular formations in such coatings is 5070 nm. An increase of the forcondensation time as compared
with the optimal time leads to the aggregation of structural elements and the formation of
large associates 0.20.3 m in diameter.
The structural features of films determine the value of vapour permeability and the extent of their swelling in butyl acetate. The lowest value of vapour permeability corresponds
to films with the finest globular structure. The extent of hardening of coatings in this case
is at its maximum, so they are less prone to swelling. An increase of the size of structural
elements with the forcondensation time greater than the optimal value leads to a rise of vapour permeability of the films and a decrease of the extent of their hardening.
Comparison of the data of structural transformations in solutions of epoxyphenol compositions and the results of structure studies suggests that the regularities of structure formation in the liquid phase are well consistent with the structural changes in the formation
of coatings. Evidently, the formation of an ordered structure of the coatings is a consequence of an increased structural homogeneity and an improvement of compatibility of
epoxyphenol-composition components in forcondensation in an optimal temperaturetime
regime.
Structural features of coatings are closely related to the value of internal stresses,
which, in turn, has an effect on the main performance properties of the coatings, for instance, adhesion and mechanical stress. The kinetics of change of internal stresses in the
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207
formation of coatings and the effect of various physicochemical factors on their value,
including the regime and compatibility of components in production of epoxyphenol
lacquers, have been studied.
The kinetics of change of internal stresses in the formation of coatings from epoxyphenol compositions depending on the conditions of matching the initial components has
been studied; it has been found that the rate of increment and the value of internal stresses
depend on temperature and time of forcondensation.
The ultimate values of internal stresses in coatings from a mixture of epoxy oligomer
and phenol-formaldehyde oligomer not subjected to forcondensation settle in 0.51.0 h
after the onset of hardening, and subsequently remain invariable. Forcondensation leads to
a significant acceleration of the coating formation process, which is completed in 1520
min.
The value of internal stresses decreases with the increase of the warmup time of the
compositions up to 11.5 h. The further increase of the forcondensation time increases the
internal stresses. Similar regularities in their change are also observed in the formation of
coatings from forcondensates obtained at lower temperatures; however, in this case the minimum shifts towards larger warmup times and the value of the ultimate stresses slightly increase. An increase of the forcondensation temperature above 120C also leads to the
increment of internal stresses in hardened films.
Comparative characteristics of coatings from epoxyphenol compositions with ratios of
the components E-04Kr : FKoF-4 = 80 : 20 wt. % depending on the heating time are given
in Table 6.1.
Table 6.1
Duration of
heating, h
Content of gel
fraction, %
0
0.5
1.5
6.0
76.1
78.0
80.4
67.2
Internal stress,
Tensile
MPa
strength, MPa
4.55.0
3.53.8
2.8
4.24.5
6.8
7.3
8.0
7.1
Chemical endurance in 3%
CH3COOH at 100C, h
3.5
3.5
4.5
3.5
Comparison of the results of structural studies with the data of the change of the properties of coatings shows that the increase of the structural homogeneity of films in forcondensation in an optimal regime contributes to the increment of the strength and protection
characteristics of the coatings, as well as to a decrease of internal stresses.
The correct choice of the temperaturetime conditions of forming the coatings makes
it possible to create an optimal supramolecular structure, which provides for high performance parameters.
The effect of the hardening regime of epoxyphenol coatings on their structural features
and physicomechanical characteristics was studied. Coatings based on epoxyphenol compositions with the ratio of components E-04Kr with the average molecular mass of 5 103
and FKoF-4 equal to 80:20, heated under optimal conditions at 120C for 1.5 h, were
formed within the temperature range of 200400C. The coating formation process was
studied by the kinetics of change of internal stresses in the process of their hardening. It was
found that the hardening rate increased significantly with the formation temperature rising.
At 300C, this process takes several seconds; herewith, the dependence of ultimate values
of internal stresses is of extremal character and reaches its highest value at 250300C.
208
The dependence of internal stresses on hardening time is also nonmonotonic. Upon

reaching a maximum, they decrease the larger, the higher the temperature is. The completeness of coatings hardening was controlled by the content of gel fraction after extraction in
Soxhlet extraction apparatus, because the theoretical calculation of the crosslinking density
is difficult to make for the systems studied due to the high molecular mass and functional
polydispersity of the components. It has been found that the most complete hardening of
the system is achieved at a temperature of 250300C.
The results of the differential thermogravimetric analysis have shown that in the temperature range of 280300C the polymer is subjected to thermodestruction; with the content of epoxy oligomer in the composition increasing the temperature of the onset of thermodestruction decreases.
It follows from the electron-microscopic studies of the structure of coatings hardened
at various temperature regimes that coatings hardened at 200250C have a homogeneous
structure with the size of supramolecular formations of 5070 nm. Herewith, the features
of structure formation correlate with the structure observed in the solution of epoxyphenol
compositions in the process of forcondensation.
An increase of the coating formation temperature leads to the emergence of more complex structural forms of various morphologies; herewith, globules and associates of
globules are distributed unevenly in the general mass of the film.
Intensive destruction processes at temperatures above 300C lead to the rupture of
chemical and physical bonds to form low-molecular-mass products and the formation of an
uneven network from chain-type structures; herewith, the physicomechanical and protective characteristics worsen (Table 6.2).
Table 6.2
Hardening regime
Characteristics of coatings
Temperature,
C
Duration
Content of gel
fraction, %
Internal stress,
MPa
Chemical endurance in 3%
CH3COOH at 100C, h
200
250
300
390
20 min
10 min
2 min
40 sec
75.6
80.4
81.1
49.5
2.83.0
3.53.8
3.84.0
2.52.8
4.0
4.5
4.5
3.5
Analysis of the obtained results suggests that the warming up of a mixture of oligomers
at 120C contributes to the formation of a homogeneous ordered structure at the coatinghardening temperature of 250300C.
6.4
Dependence of the properties of can lacquers on the structure of

phenol-formaldehyde oligomers
The hardening regime of coatings based on epoxyphenol lacquers depends on the type of
metal, the support. For tinplate, it is 210C for 1015 min; for aluminium, 360390C for
3040 sec. In the latter case, owing to the strong thermal shock, the properties of coatings
worsen in the process of hardening. With account for this, a wide range of epoxyphenol lacquers, for instance, EP-527, EP-547, EP-5118, etc. are manufactured by Russian industry;
mainly lacquer EP-5118 is used, which does not always provide for the required properties
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209
of the coatings, which should combine the high chemical endurance to sterilization in solutions of tartaric and acetic acids and sodium chloride and withstand stamping.
The phenol-formaldehyde component imparts chemical endurance to coatings based
on epoxyphenol compositions, as well as determines the stability of coatings at stringent
hardening regimes 360390C for 3040 sec.
It has been found that the properties of coatings are significantly affected by the characteristics of phenol in synthesis of phenol-formaldehyde oligomer, such as molecular
mass, molecular-mass distribution, content of methylol groups, extent of their butanolization. The currently existing technology for production of these oligomers does not make
possible the directed regulation and qualitative assessment of their characteristics. Using
this process, a large amount of waste waters is produced up to 3000 kg/t; herewith, commercial oligomers contain no more than 10% (by weight) of butoxyl groups.
A new technology of producing phenol-formaldehyde oligomers has been developed.
The process makes it possible to separate in time the reactions occurring in their synthesis
(hydroxymethylation of phenol, polycondensation of methylol derivatives of phenol, etherification of methylol groups) and to decrease the amount of waste waters to no more than
120 kg/t.
The process developed was used to synthesize butoxylated oligomers on various phenols: phenol proper, cresols, xylenols and diphenylol propane. The latter were tested in
epoxyphenol lacquers for internal protection of canning containers.
The choice of this phenol was due to a number of reasons:
use of phenol with the hinged link contributes to the increase of the physicomechanical properties;
high functionality of diphenylol propane with respect to formaldehyde makes it possible to produce oligomers with a sufficiently high content of butoxyl and free methylol
groups;
decrease of the relative share of methylol bridges in these oligomers as compared
with oligomers based on other phenols makes it possible to increase the resistance to
thermal shock.
A new type of high temperature-hardened epoxyphenol compositions based on o-alkylated phenol-formaldehyde oligomers for fabrication of rapidly drying lacquers to form
coatings with high physicomechanical and protective properties has been developed. These
oligomers of grade OAPFO are characterized by a low reactivity of methylol groups at room
temperature and a practically unlimited stability in storage. After 1224 months of storage
they do not change their properties, whereas in other phenol oligomers the formation of gel
particles and delamination are observed. The reactivity of OAPFO strongly changes with
the rise of temperature, owing to which at temperatures greater than 350C the coatings on
their basis are distinguished by a high degree of hardening, thus providing for a good hardness and thermal stability (Table 6.3).
The effect of the features of structure formation in solutions of epoxyphenol compositions has been studied.
It has been shown that epoxyphenol compositions with OAPFO on the basis of mechanical mixtures are not inferior than and sometimes even exceed coatings based on traditional forcondensates with the component matching regime optimal for butanolized PFO.
Based on the data on the studies of the hardening process of epoxyphenol coatings, a general
scheme of the process has been proposed for OAPFO-based compositions. It has been
shown that the determining reaction in hardening, as in the case of coatings based on
210
butanolized phenol-formaldehyde resol oligomers, is the interaction of methylol groups one

with another.
Table 6.3 Optimization of hardening regimes.
Hardening regime
Time, min
60
90
120
15
10
2
40 sec
40 sec
Content of gel fraction, wt. %
Temperature, C
PFO-based coatings
OAPFO-based coatings
100
100
100
210
250
300
360
390
75.6
80.4
81.1
49.5
10.4
12.4
19.8
82.5
83.9
52.1
83.9
88.0
Comparative studies of epoxyphenol coatings, hardened at 360C for 3060 sec,

based on etherified and nonetherified phenol formaldehyde oligomers o-alkylated with
dimethyl sulfate, butyl glycidyl ester and glycilyl ester of higher isomeric carboxylic acids,
as well as commercial oligomer FPF-1 show that coatings based on OAPFO are characterized by a higher adhesion strength, elasticity, chemical endurance and lower vapour permeability as compared with coatings from compositions with butanolized phenolformaldehyde oligomer as the result of the decreased contribution of side reactions.
In the series of epoxyphenol coatings based on those o-alkylated with butyl glycidyl
ester the best set of properties is with coatings with butanolized o-alkylated phenolformaldehyde oligomer synthesized at a phenol : formaldehyde : butyl glycidyl ester molar
ratios of 1.0 : 1.78 : 0.33 and 1.0 : 2.5 : 0.33. In the latter case, coatings have a higher extent
of hardening and low vapour permeability (Table 6.4).
Table 6.4 Properties of epoxy phenol coatings based on forcondensates and mechanical mixtures
of epoxy oligomer and OAPFO oligomer (at ratios 80:20, wt. %), hardened at 360C.
Ratio, mol/mol
phenol
Content, mol/mol OAPFO
Formaldehyde
BGE
Phenol
OH group
CH2OH
CH2 OC4H9
1.78
1.78
2.50
2.50
1.78
1.78
2.50
2.50
0.33
0.33
0.33
0.33
0.50
0.50
0.50
0.50
1.779
1.779
1.659
1.659
0.727
0.727
0.709
0.709
0.908
0.908
1.200
1.200
0.894
0.894
1.200
1.200
0.959
0.959
1.007
1.007
0.946
0.946
1.005
1.005
*mm, mechanical mixture; **fc, forcondensate.
Mn
Fabrication
technique
540
540
620
620
580
580
670
670
mm*
fc**
mm
fc
mm
fc
mm
pc
Chemical
endurance,
points
5.0
5.0
5.0
5.0
3.0
3.0
3.0
3.5
211
CHAPTER 6
For coatings mentioned in the table, the adhesion strength in bending is, in millimeters,
1 (according to a ShG-1 curvimeter), besides coatings from composition 4, for which this
parameter is equal to 3.
Epoxy-phenol lacquers based on diphenylol propane-formaldehyde oligomers with a
high content of butoxyl groups form coatings, satisfying all the requirements imposed on
can varnishes. At any hardening regime, including the rapid high-temperature drying, they
form chemically stable coatings withholding stamping and suitable for fabrication of cans
with the drawing coefficient up to 1.7.
For coatings from lacquer EP-5118 and a composition based on OAPFO, the effect of
the stage of forcondensation on the internal stresses in the formation of coatings was
studied. Forcondensations were shown to contribute to a decrease of stresses in coatings
from lacquer EP-5118; herewith, the forcondensation stage has no effect on internal stresses
and is not required.
Coatings from a composition based on OAPFO without forcondensation are characterized by a higher adhesion strength, chemical endurance in water and acetic acid as compared with coatings from compositions obtained via the forcondensation stage, as well as
by a higher adhesion and stability to stamping unlike coatings from composition EP-5118
(Table 6.5).
Table 6.5 Effect of the forcondensation stage on the properties of epoxy phenol coatings (at an EO
and PFO ratio of 80:20).
Composition
EP-5118 with fc
OAPFO-based without fc
OAPFO-based with fc
Adhesion
strength,
points
Chemical endurance, points

H2O
3% solution of CH3COOH
3
1
2
5
5
4
4
4
3
Stampability,
points
4
5
5
The effect of the ratio of epoxy oligomer and OAPFO on the properties of coatings
was studied. It has been shown that at a component ratio of 80:20, 75:25 and 70:30 the coatings are characterized by the same values of internal stresses. The difference is that at a ratio
of 75:25 and 70:30 coatings harden for 10 sec at 350C, and at a ratio of 80:20, for 1.5 min.
Coatings from compositions with the ratio of 80:20, though they have lower stresses, by
their protective properties and strength are inferior to compositions with the ratio of 75:25
(Table 6.6).
Table 6.6 Effect of the ratio of epoxy oligomer and phenol-formaldehyde oligomer on the
properties of coatings.
Ratio of EP
and OAPFO,
Content of gel
wt. %
fraction,
wt. %
80 : 20
75 : 25
70 : 30
84.0
86.1
81.3
Properties of coatings
Bending
strength,
mm
Adhesion
strength,
points

H2O
3% solution of CH3COOH
1
1
3
2
1
2
5
4
4
4
5
3
212
The use of novel chemically modified epoxyphenol lacquers makes it possible to significantly reduce rejects in container fabrication, to expand the range of packaged products,
to increase storage times of canned products due to a better protection of the inner surface
of metal stamped containers form the impact of biochemically active media.
The effect of chemical composition and synthesis conditions on the molecular characteristic of PFO was studied. As initial components in their synthesis, use was made of phenol, cresols, n-tert-butyl phenol, 3,4-xylenol and mixtures of phenol with these compounds.
The best results using linear PFO were obtained on the basis of n- and o-cresol-formaldehyde oligomers (Table 6.7).
Table 6.7 Properties of coatings.
Base of PFO
p-cresol
o-cresol
n-TBP
3,4-xylenol
p-cresol
p-cresol
p-cresol
o-cresol
o-cresol
phenol
6.5
Mn of
PFO
PFO CH2OH,
mol
A,
points
280
355
350
375
290
250
290
460
500
490
0.92
0.98
0.98
0.96
0.75
0.90
0.96
1.35
1.48
1.68
1
1
3
2
2
b,
MPa
P108,
g/(cm2 h)
Chemical endurance,
points
3.8
3.1
2.0
2.8
2.5
2.9
3.1
5.0
5.4
6.8
3.0
3.5
7.0
4.5
3.5
3.2
3.0
2.5
2.7
2.0
4.2
3.8
1.5
2.4
3.5
4.5
4.5
4.0
4.0
4.0
Fields of application of canning containers and methods of their

modification
Diversification of canning products is accompanied by the improvement of packagings. The

relative share of metal containers increases, as well as that of small consumer containers in
the form of tinplate cans, packagings from combined materials on the basis of aluminium
foil for ready-prepared sterilized and frozen meals.
Sterilized ready-prepared meals and semi-finished convenience products are produced
in tinplate cans of various sizes. They contain several gobbets and by their taste are not inferior than the meals prepared by traditional cooking methods. Before use, they are warmed
up and portioned.
A wide assortment of sterilized ready-prepared meals and convenience foods have
been mastered, for instance, stuffed pepper with meat, stuffed cabbage leaves with meat,
veal with garnish, etc. packaged using metal containers.
Tinplate containers are used for packaging convenience foods, which passed a culinary
treatment and can be used after a small additional processing mixing, addition of spices,
warming-up, roasting. Meat semi-finished products are usually combined with canned vegetable semiproducts.
Tinplate cans are used to package dietary foods, whose output continuously increases.
A ranking place in using this group of packagings is occupied by medicated food products
beverages enriched with pectin, fruit desserts from natural fruit puree apricots, apples,
pears, quince or carrots with addition of sugar syrup. These products are recommended
CHAPTER 6
213
in prophylaxis and therapy of diseases related to the increased content of fats and cholesterol in the blood, chronic coronary insufficiency after infarction.
Metal containers are widely used in production of fruit preserves juices, stewed
fruits, drinks based on fruit syrups, apple concentrates and other fruits with natural aromatizers. Aceptic packagings for tomato concentrate are introduced, as well as special tubes
based on metallized materials.
Traditional types of containers for production of canned food in this country are metal
cans from tinplate and aluminium, as well as glass jars with lids from tinplate, chromeplated steel or aluminium. In the case of glass containers, expenses for transportation and
storage of canned products as well as due to breakage of jars, are much greater. Use of metal
containers decreases the labour intensity and duration of sterilization, increases labour productivity, reduces the requirement in storage facilities.
Production of canning containers in the recent years makes use of advanced materials,
such as aluminium, chrome-plated and aluminized steel instead of deficit tinplate, as well
as materials with a reduced thickness of the tin layer on tinplate.
Protective coatings on rolled metal materials are produced using high-speed lines,
which provide for hardening of the lacquer in several seconds at 350390C. The design
and assortment of produced canning containers have changed. Widely used are deep drawn
cans, welded-seam composite cans, stamped and composite cans from two different metals,
tubes, etc.
Resource-saving technologies and equipment for production of metal containers have
been developed. Machines for fabrication of two-piece aluminium cans provide for the
economy of materials without decreasing the parameters of strength in compression. This
is achieved due to the improvement of the shape of the bottom, which, in turn, makes it possible to decrease the thickness of the walls to 0.28 mm. Based on the use of new equipment,
the extent of the change of can volume in the process of pasteurization is significantly decreased.
Introduction of new types of technological and transport containers, as well as
advanced technologies of their fabrication from preliminarily lacquered aluminium band by
the method of deep drawing impose stringent requirements to the quality of
lacquer-and-paint coatings, especially for its internal protection, and an increase of shelf
life. The major of them are biochemical stability, high strength and elasticity, which provide
for a sharp decrease of internal stresses in the formation of coatings and the impact of mechanical fields in stamping.
Compositions widely used in industry for protection of canning containers are
epoxyphenol compositions based on high-molecular-mass oligomer hardened with
phenol-formaldehyde oligomer EP-5118, modified with a mixture of glyptal and polyphenyl silaxane resin Ko-815. A significant drawback of coatings based on this lacquer are
high internal stresses, small elasticity and low chemical endurance, which hinders their use
in production of one-piece canning containers.
Methods of modifying epoxyphenol lacquers have been developed, which make it possible to increase the resistance of protective coatings to the action of biochemically active
media and mechanical fields in stamping. The modification methods are based on introduction of special texturing agents into compositions.
The object of study were epoxyphenol compositions with the epoxy oligomer and
phenol-formaldehyde oligomer ratio of 80:20, as for commercial lacquer EP-5118. To
make the components compatible, forcondensation at 120C for 1 h was carried out. In the
subsequent mixing, orthophosphoric acid was added as a catalyst, as well as modifying
214
agents, containing various functional groups, such as amine, hydroxyl, cyan etc. As the result, a modified composition with higher protective properties and chemical endurance as
compared with the initial composition was developed. The thickness of coatings, stability
to stamping, chemical endurance and internal stresses were studied.
In accordance with technical specifications, the thickness of coatings was determined
by a micrometer gauge and by the weight method; it was 5 mm. The endurance of coatings
to mechanical impacts was assessed in stamping of cylindrical cups 33 mm in diameter with
the elongation coefficient of 0.6 (the ratio of height to diameter) and was expressed as a
percentage of destroyed coating. The chemical endurance of stamped specimens was studied under standard conditions in model media for 60 min at a pressure of 100 kPa (1 atm)
and 120C. It was assessed in points:
5 points lacquer coatings without changes;
4 points the inner surface with barely noticeable changes in the form of separate
strokes or points by the angles of drawing;
3 points insignificant change of colour and gloss, barely noticeable peeling;
2 points change of colour and gloss, peeling, spots of curling of lacquer;
1 points curling of lacquer over the entire surface.
Chemical endurance of lacquer coatings was assessed by the change of electrochemical potential on a potentiostat P-5827 in an electrolytic cell for electrochemical studies
with the determination of the breakdown potential. The specimen was held in solution for
10 min. In the process of polarization, the current density was measured after each 50 mV.
Internal stresses were measured by the photoelastic method (Table 6.8).
Table 6.8 Protective properties of coatings.
Composition
of lacquer,
3% solution 2% solution 3% solution Distilled
%
of acetic
of tartaric
of sodium
water
acid
acid
chloride
,
mV
Extent of
breakdown
of coatings,
%
b,
MPa
No additives
2.1
3.2
4.5
450
+400
+813
+450
2030
Abrasions
No abrasions
Abrasions
1.0
0.5
0.2
0.4
3/2
4
5/4
4/5
3/2
4/5
5
5
3/2
4/5
5
4/5
3/2
5
5
5
Note: The slashed numbers indicate the limits of measured values for a series of 10 specimens.
It is seen from the table that coatings based on basic commercial lacquers are characterized by a low stability to stamping and protective properties in various media within the
range of 3 and 3/2 points. Chemical endurance of coatings from compositions modified by
organosilicon compounds increased significantly up to 5 and 5/4 points. For modified
coatings, the breakdown potential is significantly shifted to the positive side, the stability
of coatings to stamping increases as the result of the decrease of internal stresses. The supramolecular structure of coatings was studied by the method of electron microscopy; it was
shown that the size of structural elements decreased as the result of modification to 0.4 m.
For nonmodified coatings, larger supramolecular formations of up to 0.85 m in size were
observed. It follows from these data that introduction of a modifier leads to the formation
CHAPTER 6
215
of coatings with an ordered structure.

To improve the performance properties of can varnishes and to impart a high elasticity
to coatings on their basis, they are modified by epoxyesters of various molecular masses.
The properties of coatings based on epoxyphenol compositions from the mixture of epoxy
oligomer E-04kr and phenol-formaldehyde resin FPF-1 at a ratio of 1.5:1 were studied.
The epoxyesters used were synthesized from epoxy oligomers ED-20 with an average
molecular mass of 400; E-44, with a molecular mass1600; E-05k, with a molecular mass of
3000; and oleic acid, taken at an equimolar ratio of 1:1, and in the base of E-05k also at a
ratio of 1:2. The former epoxyesters are monoepoxyesters; the latter, a diester.
The most significant barrier effect for the diffusion of corrosion agents through the
protective film was observed for coatings modified by monoepoxyesters based on the most
low molecular-mass oligomer ED-20 in the amount of 20%.
The effect of epoxyesters on the protective properties of coatings is confirmed also by
the results of the assessment of chemical endurance in sterilization in model media. The
protective action of coatings is determined not only by the barrier properties of polymer
films, but also by the adhesion strength. The results of determining the character of coatings adhesion strength change after sterilization have shown that coatings containing a
modifier based on E-05k have a greater stability of adhesion properties.
The effect of film polarity decrease affecting the diffusion of the corrosion medium
increases with the rise of the concentration of monoepoxyester. This is, evidently, due to
the distribution of weakly polar fatty radicals in the bulk of the polar epoxyphenol matrix.
Studies of epoxy polymers have shown that a decrease of their polarity is accompanied with
a decrease of the sorption of water molecules and electrolyte ions.
By the example of epoxyphenol lacquers EP-547 and EP-547M, it has been found that
a decrease of polarity of coatings using higher-molecular-mass epoxy oligomers leads to an
increased stability at the action of aggressive sterilization media.
When passing from monoepoxyester to diester, the dielectric permeability of coatings
increases. We suggest that this is due to an increase of the volume content of strongly polar
ester groupings, whose dipole moment is 2.5D. Presumably, this explains an increase of the
value of cathodic current in substitution of monoepoxyester (MEE) to diester in compositions based on E-05k. The level of dielectric losses of coatings in the introduction of
epoxyesters increases in all cases because of the rise of mobility of small fragments of sterically structured molecules owing to the plasticizing action of modifiers (Table 6.9).
Thus, introduction of plasticizing epoxyester modifiers into the epoxyphenol composition enhances the mechanical and protective properties of coatings. This effects is more
Table 6.9 Effect of modifiers on the adhesion of epoxy coatings in aggressive media.
Medium
Preservation of adhesion (%) of coatings,

with 20 wt. % modifier
No modifier
Distilled water
3% solution of tartaric acid
3% solution of acetic acid
3% solution of sodium chloride
60
50
70
80
MEE
DE
ED-20
E-14
E-05k
E-05k
100
98
100
100
98
95
95
99
98
98
98
98
100
98
98
100
216
pronounced when using low-molecular-mass epoxyesters as modifiers.

The properties of epoxyphenol coatings depend on the structure and optimal ratio of
the functional groups in phenol oligomer. Mixtures of phenol and n-tert-butyl phenol of the
type of FPF-1 within a broad range of values of functional groups, bridging linkages, average molecular masses were synthesized. The range of values in wt. % of oxymethyl groups
was 2.514.6; of butoxymethyl groups, 9.022.0; methylene bridges, from 1.3 up to 5.6;
oxymethyl bonds, from 0.3 up to 4.4; the molecular mass of the oligomers was changed
within the limits of 290650.
It has been found that epoxyphenol compositions based on the given mixture phenols
with the mass fraction of butoxymethyl groups of 913% do not provide for the required
stability of coatings to stamping, at an increase of their content to 1822% the elasticity of
the coatings was significantly improved. An increase of the mass fraction of the oxymethyl
groups from 2.55.6% up to 814% worsens the elasticity and stability of specimens to
stamping.
It has been shown that coatings from lacquer EP-547 on tinplate provide for a relatively high stability to stamping, combined with the acceptable chemical endurance and adhesion. These oligomers are distinguished with a high content of butoxymethyl groups
(1618%) and methylene bridges (3.24.1%) at a comparatively low content of the oxymethyl groups within the range of 6.110% and dimethylene oxide bridging linkages of
1.02.3%. Herewith, the residual content of free phenols in individual specimens was about
8% and had no negative effect on the quality of the coatings.
It follows from these data that variation of the structure of phenol oligomer within sufficiently wide limits of the functional groups and bridging linkages does not make it possible to produce lacquer coatings, which would combine a high chemical endurance with
mechanical properties. When designing compositions, it is necessary to take into account
which characteristics of coatings are preferable for a particular purpose composite or
stamped containers, aggressiveness of the product stored.
6.6
Structure and properties of coatings based on epoxy oligomers
Protective and decorative polymer coatings are distinguished by a diversity of properties

depending on their purpose and performance conditions. Their specific features are that
they are formed as thin films on the surface of solid bodies (rigid and soft supports). Depending on the purpose, polymer coatings should satisfy various mechanical, adhesive,
thermophysical and electrophysical properties, and in some cases also such specific parameters as the sensitivity to a definite radiation range, bactericidal and fungicidal properties,
certain porosity, thermal stability, incombustibility etc. A combination of these properties
is achieved mainly by synthesizing polymers with certain functional groups and chain structure, molecular and supramolecular structure, as well as the result of their physical and
chemical modification.
Depending on the chemical composition of film formers, the nature of the functional
groups and formation conditions, the coatings produced can have a linear, branched and network structure.
The decorative properties of coatings are changed and the protective properties are increased also by adding organic dies, mineral pigments and reinforcing fillers. The properties of coatings can be regulated within broad ranges by their physical modification with
the aim to form a homogeneous structure.
To develop the physicochemical bases of forming polymer coatings, it is necessary to
CHAPTER 6
217
study the peculiar features of structure formation and properties of various types of film
formers, their effect on the specific features of structural transformations at various stages
of polymer coatings and their properties formation.
The process of forming coatings is accompanied with the emergence of local bonds
between the most active groups of macromolecules and other structural elements, and has
much in common with the mechanism of gel formation. When conducting these studies,
special attention was paid to the effect of the nature of the support on the structure and properties of coatings and interphase layers, as well as to the process of their formation. Manifestation of the special properties of the boundary layers, determined by the orienting effect
of the support, particles of the filler or fibrous reinforcing materials, is not restricted by the
bounds of one or several molecular layers, but significantly affects the structure and properties of the coatings on the whole. The specific features of polymer coatings are that they
are formed as comparatively thin films on the supports that adhere well to polymer, so the
surface phenomena play an important role in the formation of their structure and properties.
The structure of coatings from epoxy resin ED-20 obtained on a glass support at 80C
was studied. It has been found that a sharp change in the structure of the layers is observed
in the layers bordering with the support and the air. Away from the border (100200 nm)
the structure of middle layers is stabilized and does not change significantly in passing from
one layer to another. At the interface with the support, the structure was homogeneous and
globular owing to the adsorption interaction of the film former with the surface of the support and a sharply slowed-down mobility of the structural elements. Away from the interface with the support, owing to the increase of the mobility of structural elements, they are
observed to aggregate to form more complex structures up to 100200 nm in size.
The inhomogeneity of the structure of coatings is preserved during their formation at
various supports and under different hardening conditions. Addition of active fillers to the
system increases the inhomogeneity of the structure. The authors studied the structure of
various layers of coatings 200 mm thick from epoxy resin ED-20 formed on a glass support
at 150C. It has been shown that in surface layers bordering the air the polymerization is
the most rapid, and a thin homogeneous structure is fixed, which coincides by its size with
the associates observed in the initial oligomer. The largest aggregation of structural elements, which accompanies the formation of a complex secondary supramolecular structure,
is observed in middle layers of the coatings. The change of the nature of the support renders
a specific effect on the structure of individual layers of the coatings, not eliminating its inhomogeneity by the thickness of the film. From the data on the structure of epoxy coatings,
but formed on block copper, it follows that in layers bordering with the support there occurs
a structure, which reflects the granular texture of the support. In the surface layers, structural elements are observed to aggregate to form more complex secondary structures. At
the introduction of active fillers, in particular 4 wt. % rutile, the structural inhomogeneity
of these coatings is significantly increased.
A substantial feature of polymer coatings is that surface phenomena have a significant
effect not only on the character of the structural transformations, but also on the rate of relaxation processes and the properties of coatings. The retardation of relaxation processes in
the formation of coatings, which is due to local links between structural elements and adsorption interaction of the film former with the surface of the support, is accompanied by a
sharp increment of internal stresses.
Internal stresses are determined by the shrinkage of gels produced in the formation of
coatings; they start to manifest themselves after the coatings are formed owing to the
inhibition of the relaxation processes. In this connection, internal stresses in coatings are
218
affected by the factors determining the rate of the gel formation process. These factors, besides the concentration of the initial solution, also include the effect of the nature of solvent
and various texturing agents.
One of the ways of decreasing internal stresses is regulation of the relaxation processes
at the polymersupport and polymerfiller interfaces, which enables creating a homogeneous ordered structure in coatings.
Internal stresses emerging in the formation of coatings have a significant effect of the
mechanical, adhesion, electrophysical, thermophysical and other properties of coatings and
are a criterion, which determines their durability. In this connection, of special importance
are studies of the effect of various physicochemical and technological factors on the value
of stress in the formation and ageing of polymer, in particular, epoxy, coatings.
The value of internal stresses is significantly affected by the molecular mass of molecules of a film former; it has an effect on their flexibility, conformation and structuremechanical properties of the system, as well as the number and nature of bonds, the character of their distribution in the system.
One of the features of polymer coatings is that their structure and properties are inhomogeneous along the thickness of the film and depend on it. The cause of this phenomenon
is due to the uneven hardening of coatings along the thickness of the film and to the effect
of adsorption interaction of the film former with the support. The work presents the data on
the study of the supramolecular structure of various layers of epoxy coatings 50, 200 and
400 m in thickness. The greatest differences in the structure along the thickness of the film
are found for coatings of 50 and 200 m in thickness. As the thickness of epoxy coatings
increases up to 400 m, the inhomogeneity of the structure along the thickness of the coating is preserved, but the size of the structural elements in middle layers ana those bordering
with the air decreases from 300 to 3040 nm, as the result of which the structure becomes
more homogeneous along the thickness of the coatings than for coatings of smaller thickness. A decrease of the size of structural elements, apparently, leads to an increase of the
intermolecular interaction. This is accompanied with an increment of internal stresses with
the increase of the film thickness and decrease of the thermophysical parameters.
Rheological, thermophysical, physicomechanical and structural studies have shown
that at the first stage of coatings formation from oligomer systems local bonds are formed
within the limits of a small number of molecules or between individual associates. The process is accompanied by the formation of supramolecular structures or aggregation of the
available structural elements. At the second stage, links emerge between these structures,
which lead to a sharp inhibition of relaxation processes and increment of internal stresses.
This character of structure formation was observed in the development of the threedimensional network from epoxides and solutions of epoxides.
In production of coatings from solutions of polymers and oligomer systems, to prevent
the formation of an inhomogeneous structure consisting of large aggregated structural elements, at the initial stage of their formation film formers were modified by texturing agents.
These agents contain functional groups capable of chemically interacting with molecules
of the film former and with the surface of solid bodies used as supports and fillers.
-Aminopropyltriethoxysilane (AGM-9) was used as a structural additive to improve
the properties of epoxy coatings. Introduction of a texturing agent in an optimal amount
(0.070.25%) to epoxides was shown to contribute to the decrease of internal stresses in
the system at a simultaneous increase of strength, adhesion and durability of the coatings.
At a large concentration of a modifier (more than 1%), other properties were noted to worsen together with the decrease of internal stresses.
CHAPTER 6
219
One of the ways to decrease internal stresses in the formation of coatings is the action
of a magnetic field on the system. Under optimal conditions, the magnetic field plays the
role of a dispersant preventing the aggregation of structural elements and contributing to
the formation of a homogeneous three-dimensional network from associated macromolecules. The effect of a magnetic field on structure formation in solutions of epoxy oligomer,
the formation of coatings and their physicomechanical properties have been studied. A
homogeneous globular structure with globules 1520 nm in size was found to be formed
at the action of a magnetic field with the optimal parameters. It was concluded that the action of a magnetic field under these conditions is related not to the orientation of structural
elements along the direction of the force lines, but to the fixation of associates in the oligomer system and to the elimination of the effect of their aggregation in the process of hardening. This character of structure formation contributes to the sharp decrease of internal
stresses, a significant (1.53-fold) increase of adhesion and strength of coatings.
The effect of structuring of the system under the action of a magnetic field, which prevents the aggregation of structural elements in the process of their hardening and contributes to the significant improvement of the physicomechanical characteristics is observed
both for unfilled systems and for systems filled with ferromagnetics and diamagnetics.
6.7
Technology of producing protective polymer coatings
The process of producing polymer coatings consists of main and auxiliary operations. The
former include processes determining the quality of coatings produced: preparation of the
surface of an article prior to the application of material, application of material, hardening
(drying) of material. The auxiliary operations include additional processes improving the
decorative properties of some coatings. For instance, grinding of intermediate layers and
polishing of the upper layers of coatings formed.
Preparation of the surface of an article largely determines the service life of the coatings. Lacquer-and-paint material of even the best quality would not provide for the protection of metal from corrosion, if it is applied to an unprepared surface.
Preparation of the surface of an article for painting is the first operation in the process
of producing coatings.
Performance properties of coatings largely depend on the method of preparation and
the purity of treatment of the surface. The more aggressive the medium in which the article
used is, the more thoroughly its surface should be prepared for painting.
Durability and other performance properties of coatings from the same lacquerand-paint material depend on the process of its production, which is due to the corrosion
resistance of metal, composition of corrosion products formed on the metal surface, technology of fabricating the articles (its shape, configuration, size) and preparation of the surface before painting.
Lacquer-and-paint coatings protect the surfaces of black metals (articles from rolled
steel, iron and steel castings) and nonferrous metals (items from galvanized and cadmiumplated steel; magnesium, aluminium, copper and their alloys).
Preparation of the surface consists in the removal of metal corrosion products (rust),
oxide scale, contamination by fats and conservation agents, by other accretions preventing
a good adhesion of metal to material applied.
The preparation method is chosen depending on the metal from which the item is fabricated, its size and design, the initial state of the surface, the requirements to the class of
coatings and performance conditions of the item.
220
In industry, for items from black metals, use is made of mechanical, thermal and chemical methods of surface preparation. For surfaces from nonferrous metals, treatment with
thermal and partially mechanical methods is totally ruled out. Chemical methods of surface
purification of metal items include degreasing, etching, removal of old coatings, as well as
methods of rust removal and phosphatizing.
An important operation in the coating production process is application of material.
Only the use of advanced, automated methods of application makes it possible to completely realize all the potential possibilities inherent in material itself, and also to prevent the loss
of material, which is especially important in the current deficit of lacquer-and-paint materials.
Progress in the chemistry of high-molecular-mass compounds contributed to the commercial production of various oligomers and polymers and led to the development of
high-quality lacquer-and-paint materials and polymer coatings on their basis. The improvement of the quality of materials and expansion of their range was accompanied with the improvement of the existing and development of new application methods. From manual
methods, such as using brushes, swaps, the industry moved to modern methods: pneumatic,
electrostatic and airless spraying, jet glazing, electrodeposition.
Application of fluid lacquer-and-paint materials on a solid surface is based on:
(a) their conversion to aerosols followed by deposition and coagulation in a thin layer;
(b) wetting of the surface (adsorption);
(c) deposition (sedimentation) of a substance from the liquid medium (solution or dispersion) at the action of an electric current, heating;
(d) adsorption from the gaseous or vapour phase.
The most frequently used method of applying lacquer-and-paint materials is spraying.
Depending on the type of dispersant, there are the following dispersion methods:
pneumatic or aerodynamic spraying without or with heating; in this case, material is
atomized by a jet of compressed air;
hydraulic or hydrodynamic spraying at low and high pressure, with or without heating; in this method, material is supplied under a high pressure via the nozzle of a sprayer as
the result of a sharp pressure differential;
electrostatic spraying, which leads to the formation of aerosol due to the action of
electrical forces.
The second group of methods are dipping, glazing; painting by rolls, in drums, by
brushes and other manual implements. Their performance requires a direct contact of the
solid surface with the liquid lacquer-and-paint material and as complete as possible interaction (wetting).
The recent years witness a noticeably increased interest in the roller method due to the
sharply expanded production of painted sheets and rolls. The roller method compares
favourably with other methods by its high performance, a high coefficient of utilization of
lacquer-and-paint materials, a relatively good quality of coatings (even thickness, absence
of chagrin). Application of materials by this method is an automated process performed on
special roller-type machines.
The electrodeposition method is used to apply water-base lacquer-and-paint materials:
water-borne and water-soluble.
One of the stages of the production of coatings, which determines their quality, is the
hardening of the applied lacquer-and-paint material, which in practice is called drying.
Drying is the process of converting a liquid material into a solid state to form a film.
The state of a lacquer-and-paint coating depending on the duration and temperature of
CHAPTER 6
221
the drying is characterized by the extent of dryout. By the mechanism of coatings hardening, film formers are divided into two classes. The first class includes film formers, the formation of films from which occurs without chemical reactions due to the physical
dryout determined by the evaporation of the liquid phase. One of the main conditions of
producing coatings based on film formers of the first class is the slow increment of the viscosity of the system. At a rapid evaporation of the solvent, not only surface defects of the
film can be possible in the formed coatings but also large internal stresses, which lead to a
significant decrease of the physicomechanical characteristics of coatings. Besides, in rapid
evaporation of the solvent the different viscosities of the surface and internal layers contribute to the formation of unstable supramolecular structures in the film, which stipulate a
decrease of the physicomechanical and protective properties of coatings. Lacquer-and-paint
materials hardened by the mechanism of physical drying include coatings based on solutions and dispersions of polymers of various chemical composition, cellulose ethers and esters, and other film formers.
The second class of materials hardened by chemical drying includes film formers,
the formation of coatings from which occurs due to the chemical interaction of the systems
components. The hardening process of such coatings is a rather complex phenomenon, as
along with the removal of solvent, it involves chemical reactions contributing to the formation of a spatially crosslinked polymer. This class includes materials based on reactive oligomer, oil-containing film formers and other materials coatings from which in most cases
represent spatially crosslinked polymers.
When choosing the kind, method and regime of coatings hardening, the factors to be
mainly considered are the type of lacquer-and-paint material, type of support, size and configuration of articles, performance and energy intensity.
There are two types of coatings hardening: natural and artificial. In natural hardening,
coatings are dried in the open or indoors at an ambient temperature of 1225C and relative
humidity of no more than 65%. Advantages of natural hardening are the possibility to form
a coating on large-sized articles, simplicity of equipment and low power consumption; however, natural drying is, as a rule, long-term and can not be used commercially for
alkyd-melamine, epoxy, phenol-formaldehyde and other film formers; it also totally rules
out the possibility of automation of the process.
Artificial hardening of coatings is the impact of heat, light, radiation on the material;
they provide for the conversion of liquid material to the solid state prior to the formation of
the film. Depending on the method of impact, the following methods of coatings hardening
are to be distinguished: thermal, ultraviolet light, radiation. Production of aluminium canning strip includes the following process operations: casting of ingots in an electromagnetic
crystallizer, machining of the ingots, heating of the ingots, hot rolling to produce rolled
products, cutting of the side edge, cold rolling, stretch flattening, anodizing and lacquering,
longitudinal cutting of the strip or transverse cutting for sheets, packaging of the final material. The quality of the surface of aluminium plays the main role in its use for fabrication
of canning containers. If the surface of aluminium does not correspond to the imposed requirements, all advantages of its use lose importance. Therefore, cold-rolled metal is subjected to a special surface treatment, as the result of which the natural oxide film is
substituted for the artificially created one, with a certain structure and properties. This is
achieved by the method of anodic treatment.
Formation of the anodic film is the result of two simultaneous processes: electrochemical formation of the film and its chemical dissolution. At the initial stage, when current
passes through the electrolyte in which aluminium serves as an anode, negatively charged
222
oxygen ions move to the anode, where they discharge by coupling with aluminium. As the
result of this reaction, a thin continuous film of aluminium oxide is formed on the surface.
Under the dissolving action of the electrolyte, this continuous film is converted to a porous
film. Oxygen ions penetrate through the porous film, and a continuous film again is formed
under it. Thus, in the anodizing process the porous film gradually becomes thicker to form
a cellular structure.
The thin film under the pores is also called the barrier layer and is a protection from
corrosion. To increase its protective functions, the pores are to be occluded. The pore occlusion process is called consolidation and is achieved by a special treatment or application
of a lacquer-and-paint coating.
Anodizing of the aluminium canning strip is performed on a complex continuous line,
where the anodizing and lacquering processes are carried out consecutively.
Depending on the purpose of canning aluminium, one or both sides of the strip are lacquered. In the two-side process, the lacquer is applied simultaneously on both sides of the
continuously moving strip by means of rubber rollers. The thickness of the lacquer film is
regulated from 2.5 up to 6 m. The thin coating is applied on the side, which will be outer
after the cans are fabricated. The thickness of the applied layer is determined by many parameters: the gaps between the rollers, the ratio of the peripheral speeds of rotation of the
rollers and the transport of the covered surface, the distribution of the lacquer-and-paint material between the surfaces after the gaps are passed.
Drying of the lacquer is performed in a convection-type tunnel drying furnace. As lacquer is applied simultaneously on both sides, when passing through the furnace the strip is
not supported but is held due to the tension. The maximally admissible sag of the strip and
the strength of metal determine the length of the drying furnace, and, therefore, at a fixed
velocity of the strip transport equal to 60 m/min, the drying time, which is 3040 sec. Special lacquers prepared based on epoxy, phenol and vinyl resins and capable of being dried
at a temperature of 250350C, are used for coatings of canning containers. When choosing
the type of lacquer, one should take into account the performance conditions of the coatings.
6.8
Specific features of forming epoxyphenol coatings for canning

containers
Introduction of aluminium alloys in canning industry instead of tinplate opens wide possibilities for manufacturers of cans. Such, for instance, as fabrication of cans of various configurations by stamping, decrease of their weight, increase of the productivity of stamping
automatic machines, due to the fabrication of cans directly from rolls, development of new
types of closure, in particular easily opened lids. However, aluminium alloys, in contrast
with, for instance, hot-dipped tinplate, could not be used in canning industry without a protective lacquer-and-paint coating.
Compositions used the most for protection of canned food containers are epoxyphenol
lacquers. A combination of epoxy oligomer and phenol-formaldehyde oligomer in these
lacquers enables production of coatings with high adhesion to the support and good physicomechanical properties, inherent in epoxy materials, and high protective properties characteristic of phenol-formaldehyde lacquers.
Until recently, epoxyphenol compositions were made up mainly empirically, because
the processes occurring in the interaction of epoxy and phenol-formaldehyde oligomers
were studied insufficiently. Up to the present, the scientific bases of creating compositions
from epoxyphenol systems and protective coatings resistant to biochemically active media
CHAPTER 6
223
b.10, MPa
2
3
1
10
4 , min
Figure 6.1 Effect of the ratio of the epoxy and phenol components on internal stresses: 1,
EO/OAPFO = 75:25; 2, EO/OAPFO = 70:30; 3, EO/OAPFO = 80:20.
have not been developed. In this connection, epoxy and epoxyphenol lacquers for chemically stable protective coatings produced in this country are characterized by a low stability
to biochemical media, in particular, to solutions of organic acids (acetic, lactic, malic), to
enzymes, amino acids and other components of food media. Interaction of epoxy and phenol oligomers has been shown to be of a complex character due to the presence in them of
various functional groups, which can react one with another. Herewith, the probability of
some or other reactions, and, therefore, the properties of coatings depend both on the initial
composition and on the conditions of coatings formation: the presence of catalysts, plasticizing additives, application and drying of lacquer compositions, type of solvent, character
of the support (Fig. 6.1).
Most often, epoxy lacquers are produced based on high-molecular-mass epoxy dianic
oligomer. It has been shown that the optimal set of coatings properties is provided for by
~ 3500. Herewith, it has been
the use of epoxy oligomers (EO) with the molecular mass Mn
found that the elasticity of coatings increases with the rise of molecular mass of EO, but
their chemical endurance to acidic media decreases.
Coatings based on low- and medium-molecular-mass (molecular mass up to 2000) EO
proved to be non-acid-resistant. Only introduction of high-molecular-mass oligomer (Mn

~ 3500), but in the amount of no more than 40%, provided for a sufficient acid resistance
of the coatings. It has also been shown that introduction of high-molecular-mass EO into
epoxyphenol compositions based on low-molecular-mass EO leads to an increase of the adhesion strength of the coatings.
As a rule, PFO of resol type are used to produce can varnishes. Minor amounts of
cresols, xylenols, naphthols are used as the phenol component. Introduction of PFO on substituted phenols, for instance, p-tert-butyl phenol, to epoxyphenol compositions contributes
to the increase of the physicomechanical properties of coatings. However, chemical endurance and the depth of hardening of the coatings increase at the increase of the content of
unsubstituted phenol in PFO. With the increase of the share of EO in the system, the elasticity of the coatings was found to rise; and as the share of PFO increased, chemical endurance increased, which is of special importance in production of canning strip.
224
5
1
b.10, MPa
2
3
1
4
0
10
10
20
30
, min
Figure 6.2 Kinetics of the change of internal stresses in hardening of epoxyphenol compositions: 1,
EP-5118 without fc; 2, EP-5118 with fc; 3, EPC based on OAPFO with fc; 4, EPC based on OAPFO
without fc.
In most cases, to produce lacquers, initial EO and PFO are mixed at a given ratio and
are subjected to a preliminary heating forcondensation. The purpose of forcondensation
is to improve the compatibility of EO and PFO, which are poorly compatible at the usual
temperature. It has been noted that a preheating improves the properties of coatings of even
well compatible oligomers, decreases internal stresses (Fig. 6.2). A relationship between
the processes of structure formation in solutions and the structure and properties of coatings
has been established. It has been shown that the structural features and performance properties of coatings based on epoxyphenol compositions are determined to a significant extent
by structural transformations, occurring at the stage of matching EO and PFO solutions
their forcondensation.
In diluted solutions (in ethyl cellosolve) of EO and PFO and compositions on their basis, the primary structural formations are associates of molecules. The affinity to association
is sufficiently pronounced in such solutions owing to the high molecular mass and polarity
of the initial components.
As the molecular mass of EO rises, the extent of structuring of solutions considerably
increases. The structures emerging in concentrated solutions of epoxyphenol compositions
have the character of a fluctuation network from associates of macromolecules.
Forcondensation leads to the change in the character of interaction in solutions of epoxyphenol compositions, which is due to the accompanying chemical and physicomechanical processes. It has been found that in forcondensation owing to intensive thermal motion
of macromolecules and mechanical impact on the solution, there occurs the dispersion of
macromolecule associates, which is accompanied with a decrease of the viscosity of the solution. Disruption of the structure in the process of heatup also leads to the change of the
composition of associates.
An increase of the structural inhomogeneity of forcondensates heated under optimal
conditions leads to an increase of the uniformity of the distribution of the structural
CHAPTER 6
225
6
1
3
2
in, MPa
5
4
3
2
1
0
1.0
3.0
2.0
Forcondensation time, h
4.0
Figure 6.3 Dependence of the ultimate values of internal stresses in coatings from epoxyphenol
forcondensates heated at 100C (1), 120C (2) and 130C (3), on the duration of forcondensation.
elements in hardened coatings, which, in turn, contributes to the decrease of internal stresses
and an improvement of performance characteristics of coatings. Evidently, the formation
of a homogeneous small-globular structure, where the formation of chemical and physical
bonds is maximally realized, provides for the rigidity and stability of the spatial structure
of a highly crosslinked polymer. This, in turn, determines the high strength and protection
properties of coatings.
The further heating leads to the aggregation of structural elements to larger associates,
as the result of which a defect network is formed. Internal stresses in such coatings are twice
as large as in coatings with the homogeneous small-globular structure, which can be due to
the emergence of large structural elements, at the interface of which an internal stress is concentrated (Fig. 6.3).
Thus, the properties of coatings can be regulated by changing the size of the structural
elements in solutions of forcondensates. Optimal from the point of view of achieving the
homogeneity of solutions, and, therefore, hardened coatings, is the heating at 120C for
1.52.0 h depending on the molecular mass of the EO used; its increase leads to the increase
of the optimal time of forcondensation (Fig. 6.4).
The choice of the forcondensate hardening regime is of great significance. It is known
that the correct choice of the temperaturetime conditions of forming coatings would make
it possible to produce coatings with an optimal supramolecular structure, which provides
for their high performance properties. In this connection, the authors studied the effect of
the hardening regime of epoxyphenol coatings on their structural features and physicomechanical characteristics. It was found that the process of forming coatings was considerably
accelerated with the rise of temperature and at the hardening at higher than 300C occurred
within several seconds (3040 sec). The completeness of the coatings hardening was controlled by the content of the gel fraction. The most complete hardening of the system is
achieved at 280300C (the content of the gel fraction, 7580%). Within the temperature
range above 300C, thermooxidative destruction of polymer begins; it is accompanied with
an intensive loss of the mass, and with the increase of the content of EO in the composition
the thermodestruction onset temperature slightly decreased.
226
5
4
1
4
in, MPa
2
3
2
1
3.0
4.0
2.0
Hardening time, h
1.0
5.0
6.0
Figure 6.4 Change of internal stresses in the formation of coatings from epoxyphenol compositions
heated at 100C (1), 110C (2), 120C (3) and 130C (4), Thard = 200C.
1
2
4
in, MPa
4
3
2
1
1.0
2.0
3.0
5.0
4.0
Hardening time, h
6.0
Figure 6.5 Change of internal stresses in the hardening at 200C of coatings produced from: 1, A
mechanical mixture of epoxy and phenol-formaldehyde oligomers (E-04Kr:FKoF-4 = 80:20 wt. %);
2 4, forcondensates heated for 0.5 h (2), 1.0 1.5 h (3) and 3 6 h (4); 5, forcondensation without catalyst, hardened with H3PO4.
We also showed how the change of the temperature regime of formation affects the
structural features of coatings. It was concluded that the high-temperature hardening of epoxyphenol coatings (at 350390C) is undesirable, as intensive destruction processes lead
to a worsening of the performance properties of coatings. The conclusion was made that the
optimal formation temperature of epoxyphenol coatings is 250300C (Fig. 6.5).
As we already said, coatings are formed based on a preliminarily obtained forcondensate by heating a mixture of alcohol solutions of oligomers at 100120C for several hours.
Due to the diversity of combinations of functional groups in epoxyphenol compositions, the chemical reactions occurring in forcondensation and hardening are rather diverse.
Herewith, the probability of this or that reaction depends both on the composition and
CHAPTER 6
227
conditions of these processes their temperature, duration, presence and type of catalyst.
Studies carried out at the Chair of the Chemistry and Technology of Lacquers, Paints
and Coating Compositions, D.I. Mendeleyev University of Chemical Technology,
Moscow, made it possible to establish the main schemes and kinetic regularities of the reactions proceeding in forcondensation and hardening of such compositions.
It has been shown that under conditions of acid catalysis in forcondensation there is
no chemical interaction between epoxy and phenol-formaldehyde oligomers. Epoxy oligomer reacts to the catalyst orthophosphoric acid by the scheme
OH
CH
CH2 + HO
OH
O
CH
CH2O
OH
OH
(I)
OH
OH
CH
CH2 +
O
CH
CH2
OH
OH
OH
CH
CH2O
O
O
CH
CH2O
OH
O CH2
CH
OH
(II)
OH
O
CH
CH2 + HO
O
(O
CH2
OH
CH)2
OH
(CH
CH2O)3
(III)
OH
Herewith, all three hydroxyl groups prove to be reactive with respect to the a-oxide
groups of epoxy oligomer.
Phosphate groupings formed by reaction (I)(III) in the presence of orthophosphoric
acid and partial organic phosphates are readily subjected to hydrolysis, owing to which
a-oxide groups of epoxy oligomer turn to glycol ones.
The presence of orthophosphoric acid and partial phosphates also contributes to the
interaction (proceeding at a sufficiently high rate) of a-oxide groups of epoxy oligomer with
the dissolving alcohol (ethyl cellosolve or n-butyl alcohol introduced into the reaction mixture together with phenol-formaldehyde oligomer):
CH
CH2 + HOR
CH(OH)CH2OR,
(IV)
where R is C2H5OCH2CH2 or HC4H9 .

Phenol-formaldehyde oligomer in the presence of orthophosphoric acid is subjected
to etherification by the same alcohols.
OH
OH
(V)
+ HOR
CH2OH
CH2OR
228
Forcondensation under conditions of the basic (in particular KOH) catalysis, efficient
for the reaction of a-oxides with alcohols, leads to the formation of epoxyphenolformaldehyde copolymers. In this case, there also occurs condensation of methylol groups
of resol oligomer
HO
CH2
(VI)
OH + CH2O + H2O
CH2OH
and their etherification, predominantly by ethyl cellosolve

OH
OH
(VII)
+ HOCH2CH2OC2H5
CH2OH
CH2OCH2CH2OC2H5
The features of hardening of the epoxyphenol composition are determined by the nature and ratio of the functional groups remaining after forcondensation, as well as the hardening conditions (temperature, type and concentration of the catalyst used). In industry,
epoxyphenol coatings are usually hardened at high temperatures. Thus, for instance, can
varnishes on tinplate are hardened at temperatures of 473523 K (200250%) for 10 min;
and on aluminium, at 633 K (360C) and higher for 3040 sec.
As a hardening catalyst of epoxyphenol compositions, orthophosphoric acid is used
the most often.
The study of the hardening process (T = 473 K) has shown that in this case a-oxide
groups of epoxy oligomer react with phenol hydroxyl groups:
CH
CH2 + HO
CH
CH2
(VIII)
OH
and with secondary hydroxyl groups:

CH2
CH
CH2 + CH2
O
CH
CH2
CH
CH2
CH
(IX)
CH2
OH
Besides, secondary hydroxyl groups enter into a re-etherification reaction with phosphate groupings formed in the reaction of orthophosphoric acid with epoxy oligomer at the
stage of forcondensation. However, the greatest rate in the hardening is with the reactions
of methylol groups of resol between one another and with etherified methylol groups:
2 HO
CH2OH
HO
CH2OCH2
OH
(X)
CHAPTER 6
HO
CH2OH + ROCH2
HO
CH2OCH2
229
OH
(XI)
OH
All reactions with participation of methylol groups are catalyzed by orthophosphoric

acid and its partial esters.
Besides, it has been found that under conditions of high (473 K) temperatures the hardening can not occur due to the interaction of secondary hydroxyl groups with methylol ones,
because the groupings formed in this reaction are unstable at temperatures higher than
175C and are subjected to further conversions as follows:
CH2
CH
CH2
CH2
CH
OH
+
CH2OH
OH
OH
CH2
CH2
CH2
(XII)
Products of further
conversions
(oxidation, polymerization)
As a catalyst of hardening of epoxyphenol compositions, the most frequently used

agent is orthophosphoric acid, whose introduction accelerates the hardening process. This
is supported by experimental data. Thus, introduction of an additional amount of catalyst
orthophosphoric acid increases the content of the gel fraction in the hardened film. However, the amount of orthophosphoric acid added should be minimal as far as possible, because in this case lacquers are distinguished by a better stability, and their hardening
(especially under high-temperature conditions, at 360C) would be complicated to a smaller
degree by undesirable oxidative side reactions of phenol-formaldehyde oligomer, which deteriorate the quality of coatings.
It is noted that the considerable change of the properties of epoxyphenol coatings can
be achieved by introduction of minor amounts (35%) of oligomer modifiers into initial
compositions. Introduction of such additives makes it possible to create an ordered structure
in epoxyphenol systems and coatings on their basis and to improve significantly their properties. The structural transformations occurring in epoxyphenol compositions depend on the
type and functionality of the modifying oligomer, as well as on the ratio of viscosities of
oligomers and their matching conditions.
230
7
7.1
Ways of Increasing
the Protective Properties
of Coatings for Canning
Containers
Coatings with enhanced adhesion to aluminium and its alloys
It is much more difficult to obtain a coating with a high adhesion to aluminium and its alloys
than to most other metals, because at other equal conditions adhesion of polymers decreases
in the sequence: nickel, steel, iron, copper, brass, aluminium, tin, lead.
Special attention is paid to the possibility of producing coatings, which satisfy the
stringent requirements for adhesion, water resistance and capability of hardening under
conditions of comparatively low temperatures up to 120C. One of the major ways to increase adhesion and water resistance of coatings based on epoxy compositions is modification of oligomers or introduction of various additives, improving adhesion and water
resistance, into compositions. To improve the adhesion properties, it is proposed to introduce up to 20% modifying polymers, which possess a lower surface tension as compared
with the main polymer, as well as various organosilicon compounds in the amount from
0.01 up to 20%. Among other substances, modifying polymers include (CH2)3Si(OCH3)3,
Br2C6H3Si(OCH3)3, (CH3)2N(CH2)3Si(OCH3)3.
It has been shown that minor amounts of polymethyl silazan significantly improve adhesion, water resistance and other performance parameters. As active thinners, it is recommended to add glycidoxysilanes. The effect of increasing adhesion to metals, especially to
aluminium and its alloys, as well as an improvement of water resistance is revealed in modification of epoxy compositions by epoxysilane in the amount of 0.15%; this modification
increases the strength of coatings.
Silicon-containing compounds are used as modifiers of epoxy oligomers; herewith,
mixture compositions are used. Good results are observed in introduction of 3070% of
epoxy oligomer modified by siloxane compounds.
An increase of adhesion to aluminium and resistance of coatings to the action of boiling water and 5% alkali liquor is observed in modification of epoxy coatings by epoxyurethane oligomers or polyurethanes with terminal isocyanate groups, which are produced by
the interaction of various diisocyanates with diols having molecular masses up to 200, at a
ratio of diisocyanate to diol from 1.2:1 up to 1.75:1. These compositions are recommended
as primers with increased adhesion to aluminium. For this purpose, epoxyurethane oligomers, containing aliphatic epoxy oligomer were developed.
232
Polymers, which are products of combined modification of epoxy oligomers with acrylates and diisocyanates, were found to have similar properties. These compounds contain a
set of active groups, such as carboxyl, hydroxyl, epoxy, methylol, amide and amine ones.
Polyisocyanates are capable of hardening at room temperature to form coatings with
high mechanical properties and adhesion to metals, as epoxyurethanes with a three-dimensional structure are formed in the process of their hardening. From the comparison of potentially possible ways of introducing urethane groups into epoxy oligomer as the result of
their modification and hardening of epoxy compositions by polyisocyanates, the former
should be recognized to be the best approach, because it is not associated with the use of
toxic isocyanates in preparation of lacquer compositions. In this case, the application process is harmless and yields compositions stable in storage and air moisture-resistant. A
promising way is to use as hardeners compounds with urethane groups, containing no free
isocyanate groups. In this case, the reaction of hardening is provided for by the presence of
other functional groups capable of reacting with epoxy oligomer in the hardener. Coatings
of this composition are hardened at room temperature for seven days and are distinguished
by good adhesion and mechanical properties and low water absorption. Similar parameters
are characteristic of coatings from epoxy oligomers with hardener Versamide A-115.
Epoxy coatings hardened by compounds in which the silicon atom is bound to amino
or aminosubstituted groups, as well as compounds of the type of alkoxysilyl propylamine
have been shown to have high performance properties. These compositions are used for protection of metal surfaces in contact with hot water. Their structure is
R1
H2N
R2O
Si
R2
NH2,
R2
where R1 (CH3)n , C2H5
, C3H7 , C6H5, R 2
(CH2)x
, x = 2 4; n = 1 30.
An increase of adhesion of coatings to aluminium was achieved by a special treatment

of metal before lacquering. For this purpose, use is made of primers based on products of
the interaction of oxyalkyl(meth)acrylates with anhydrides of dicarboxylic acids. They are
best to be applied to the metal surface before lacquering.
The formulation of similar compositions often includes silicon-containing compounds, such as epoxysilanes and aminosilanes. These additives make it possible to increase two times the adhesion of coatings to aluminium. Application of these compounds
improves the properties in painting metals with compositions based on other polymers.
7.2
The role of solvent in the formation of the properties of coatings for

canning containers
Polymer compositions based on epoxy oligomers are widely used in production of protective and decorative coatings on canning containers. Along with a rich set of properties (high
adhesion and cohesion strength, resistance to alkali liquors), they possess an insufficient
chemical endurance to organic acids (acetic, lactic, tartaric etc.), stamping, as well as instability of the performance properties. It has been shown that the instability is due to the emergence of internal stresses owing to the slowdown of the relaxation processes in the
formation and operation of coatings. A significant effect on the value of internal stresses
and the kinetics of their increment is rendered by the specific features of the structure
CHAPTER 7
233
formation in oligomer systems. This is stipulated by the fact that dilute and concentrated
solutions of oligomers are strongly associated systems.
It has been found that the structure of associates, their size and morphology depend on
the chemical composition of oligomer, the nature of solvent, the conditions of coatings formation and other physicochemical factors. In particular, a significant effect on structural
transformations in epoxy compositions, as well as on the structure and properties of coatings, is rendered by the nature of solvent.
The effect of the nature of solvent on structure formation in epoxy and epoxyalkyd
compositions, as well on the structure and properties of coatings on their basis, used for canning containers to improve their performance properties, was studied.
Compositions were produced on the basis of epoxy oligomer E-33 and its mixture with
alkyd oligomer at a ratio of 70:30. Orthophosphoric acid was used as a catalyst of hardening. Coatings were applied using 50% solutions in solvents widely used in industry and distinguished with the affinity to oligomer systems: xylol, tributyl phosphate, ethyl cellosolve,
carbitol, butyl glycol.
The rheological properties were studied on a Shvedov-type instrument with coaxial
cylinders. The structure of coatings was studied by the method of electron microscopy by
taking carbon-platinum replicas from the surface of coatings subjected to oxygen etching
in the optimal mode. The adhesion strength of coatings to aluminium was determined by
the detachment method. The stressstrain parameters were studied on an Instron instrument.
The gloss of coatings was assessed on a goniophotometer. The coating-formation process was studied by comparing the kinetics of increment of internal stresses with that of polymerization and release of the solvent at various stages of hardening. The quality of the
solvent was assessed by the rheological properties of the solutions of oligomers.
From the data on the dependence of viscosity on shearing stress for solutions of epoxy
oligomer in various solvents and in mixtures of tributyl phosphate with butyl carbitol (BC)
and butyl glycol (BG) at a ratio of 1:2, it follows that all solvents are in practice semistructured systems or Newton-type compositions. The lowest viscosity was observed for solutions of oligomer in butylene glycol. Solutions of oligomer in tributyl phosphate (TBP) and
carbitol (C) are distinguished with a much higher viscosity. Herewith, the initial solvents
are semistructured systems, which differ little one from another by the character of the rheological curves.
In accordance with the HildebrandScatchard theory, the quality of a solvent with respect to a polymer can be assessed by the similarity of the values of their solubility parameters; it is the square root of the cohesion energy density. When assessing the affinity of a
solvent to a polymer, it is also desirable to take into account the contribution to the cohesion
energy density of intermolecular forces of diverse nature (dispersion, polar, hydrogen, association interaction). The interaction of each of these types is taken account of by determining, respectively, parameters d, p, h, a).
The characteristics of epoxy compositions studied and solvents used are presented in
Table 7.1.
By the proximity of the parameters of solvents solubility and epoxy composition, all
systems can be arranged in the sequence: butylene glycol, ethyl cellosolve, carbitol, tributyl
phosphate, xylol.
Butylene glycol and ethyl cellosolve, along with dispersion interaction, also exhibit
other types of intermolecular interaction characteristic of a film former. This is indicative
of a better quality of these solvents as compared with others.
234
Table 7.1 Solubility characteristics of epoxy oligomer and solvents.

Compounds
Epoxy composition
Butylene glycol
Ethyl cellosolve
Carbitol
Tributyl phosphate
Xylol
Solubility parameters (MJ/m3)1/2
Thard, C
230
130
202
177
138
23.5
23.0
24.1
22.4
18.6
17.8
17.3
15.9
16.0
15.4
11.2
5.7
9.3
11.2
15.7
14.3
15.9
16.7
17.4
16.3
17.2
The quality of a solvent was also assessed by the rheological properties of the solutions
of oligomers. From the data on the dependence of viscosity on shearing stress for solutions
of oligomers in various solvents and in mixtures of tributyl phosphate with carbitol and
butylene glycol at a 1:2 ratio, it follows that all solutions represent semistructured or
Newton-type systems. It could be suggested that solutions of oligomer in a good solvent
would form coatings with the finest and homogeneous structure and, respectively, with a
greater density of the three-dimensional network and better physicomechanical characteristics. However, the obtained experimental data on the effect of the nature of solvent on the
network density, structure and properties of coatings failed to confirm this suggestion. By
the method of electron microscopy, it has been found that coatings from solutions of oligomer in tributyl phosphate are distinguished by the most homogeneous structure with the size
of morphologically anisodiametric structural elements of 1015 nm. With the quality of the
solvent improved, structural elements are observed to aggregate to form a nonhomogeneous
globular structure. The size of aggregates increases in passing from carbitol to butylene glycol and xylol up to 0.20.5 m.
To elucidate the causes of this phenomenon, the process of coatings formation from
solutions of oligomer in various solvents was studied by comparing the data on the kinetics
of the release of solvent and the kinetics of polymerization of compositions with the change
of internal stresses in the process of hardening. From the kinetics of increment of internal
stresses in the formation of coatings at 180C from solutions of oligomer in various solvents, it follows that the least internal stresses are observed in the formation of coatings
from solutions of oligomer in tributyl phosphate, as well as in its mixture with other solvents. With the quality of the solvent improving or worsening, internal stresses increase;
what is more, spontaneous delamination of coatings is observed for coatings from solutions
in xylol. From the data on the kinetics of the release of the solvent in the formation of epoxy
coatings under the same conditions from solutions of oligomer in various solvents, it follows that the solvent is eliminated the most rapidly in the formation of coatings from solutions of oligomer in butylene glycol. With the quality of the solvent worsening, the time up
to its equilibrium concentration in the system increases and the rate of its evaporation sharply slows down. This indicates that the chosen solvents interact with oligomer differently,
though its boiling temperature is the same as the boiling temperature of butylene glycol.
When studying the effect of the nature of the solvent on the polymerization kinetics of
compositions, a significant part of chemical bonds has been found to emerge after the solvent is released. This indicates the occurrence of polymerization in the solid phase, i.e., after
the solvent release. With the release rate increasing, the incompleteness of the relaxation
processes also rises, which is accompanied by a sharp increment of internal stresses.
CHAPTER 7
235
Similar regularities were obtained in studies of structure formation in solutions of

epoxyalkyd compositions filled with rutile dioxide. From the data on the dependence of viscosity on shearing stress for solutions of an epoxyalkyd composition in various solvents, it
follows that by the absolute value their viscosity is larger than that of epoxy oligomers.
However, the regularities of the effect on the nature of the solvent on the rheological properties of compositions remain the same. Solutions of compositions in a good solvent are distinguished with the lowest viscosity. With the worsening of the quality of a solvent, the
viscosity increases. Similar regularities are also observed in the kinetics of solvent release
in the formation of epoxyalkyd compositions.
From the data on the effect on the nature of solvent on the kinetics of increment of internal stresses in the formation of coatings from epoxyalkyd compositions, it follows that
the lowest internal stresses emerge in coatings from solutions of oligomer in tributyl phosphate and its mixture with other solvents. The disturbance of the law of additivity in the
change of internal stresses in coatings from mixture compositions based on butylene glycol
and tributyl phosphate is due to the worsening of adhesion properties of coatings and their
spontaneous delamination.
Coatings from compositions with an optimal affinity of oligomer to solvent and the
rheological properties are characterized by the highest strength parameters and adhesion
strength, which was used in the development of systems for canning containers (Table 7.2).
Table 7.2 Effect of a solvent on tensile strength (p), adhesion strength (A) and gloss of epoxy
alkyd coatings.
Solvent
TBP
C
TBP:BK (1:2)
BG
TBP:BG (1:2)
A, MPa
p, MPa
Gloss, %
1.0
2.3
3.8
4.0
3.6
29
27
27
15
20
80
60
65
5
30
To improve the quality of epoxyphenol coatings, it is recommended to subject the mixture of solutions of oligomers in ethyl cellosolve to forcondensation, i.e., heating at
373393 K for several hours. Epoxy and phenol-formaldehyde oligomers do not interact
in the course of forcondensation.
The changes occurring in ethyl cellosolve in the process of forcondensation were studied with the view to establish the relation between the optimal duration of forcondensation
and the properties of initial epoxy oligomers and to elucidate the causes of coatings properties worsening at a prolonged forcondensation exceeding the optimal value. No changes
occur in epoxy oligomers heated without solvents, whereas in phenol-formaldehyde oligomers changes are in principle possible due to their large reactivity. As an object of study,
use was made of a mixture of epoxy oligomer E-05k (molecular mass, 20003000) in ethyl
cellosolve. Changes occurring during the heating of this system were studied by calorimetry
and by the method of dielectric characteristics measurements. Changes in ethyl cellosolve
during the heating were determined by the spectroscopy method.
A sharp decrease of heat liberation at the final stage of forcondensation for solutions
of epoxy oligomer in ethyl cellosolve, absent in pure solvent, implies the emergence of an
additional endothermic process superimposed on the exothermic process of regrouping of
the elements of the ethyl cellosolve structure. This phenomenon is explained by that the
236
time of disaggregation of associates depends on the initial structure of epoxy oligomer.

Using the fractionation method, a fraction containing mainly large structural elements was
isolated in epoxy oligomer as the lower phase. Between two phases close by their molecular
mass distribution and chemical structure, the solvent was distributed differently. The content of nonvolatiles in the lower phase exceeds the concentration in the upper phase approximately sixfold, whereas for other specimens only 1.6-fold. This indicates that the
associated lower phase is in fact matched with a smaller amount of solvent than the initial
oligomer, which requires a larger heating time to disaggregate the structure. For the other
phases, the affinity to the solvent differs insignificantly. The suggestion on the effect of the
redistribution of the solvent between two phases on forcondensation time is confirmed by
the fact that for lacquers, obtained separately from the lower phase or upper phase, the
optimal time of forcondensation does not exceed 2 h irrespective of the optimal time of
forcondensation for the initial oligomer.
After the endothermic process, calorimetric studies fail to find the existence of any
exoprocess, which could be treated as a disaggregation of associates. It is assumed that the
extreme character of the dependence of the coating quality on forcondensation time can be
explained by an antiplasticizing, association-contributing action of the phenol formaldehyde oligomer.
7.3
Effect of the nature of epoxy oligomers on the properties of coatings
Possessing a high resistance to various aggressive canned media, coatings based on epoxy
resins etherified by fatty acids of various plant oils as well as isocyanates are insufficiently
stable to organic acids (acetic, etc.), so they can not be used for protection of canning containers from corrosion.
Hardening of epoxy resin-based can varnishes by phenol-formaldehyde forcondensators is accompanied with a number of reactions (interaction of methylol and butoxyl groups
of phenol condensate with epoxy and hydroxyl groups of epoxy resin, which affect the quality of the final product). The choice of the optimal ratios of the components and regimes of
hardening of compositions presents significant problems and is in many cases empirical.
To produce acid-resistant coatings, high-molecular-mass epoxy resins are used, with
molecular masses higher than 12,500 and alcohol-soluble resols (phenol resols or cresol
resols), both butanolized and non-butanolized. As phenol resols, Novolac resins and 100%
reactive resins can be used. For better hardening of epoxyphenol compositions, 12% phosphoric acid is added. Epoxy-phenol lacquers dry up at a temperature of 180200C for
2030 min. To increase the quality of epoxyphenol coatings, the mixture of resin solutions
is subjected to forcondensation under optimal conditions.
In Czech Republic, epoxyphenol compositions are used for coating tinplate sheets.
Compositions have been developed, which dry up at 200205C for 15 min. The properties
of coatings based on low-molecular-mass epoxy resins E-40 and E-41, as well as mediumand high-molecular-mass epoxy resins, obtained from fusing low-molecular-mass resins
with diphenylol propane (resins E-44 and E-49) and emulsion condensation of diphenylol
propane with epichlorohydrin (resins E-15 and E-0.5) have been studied.
Modified and non-modified resol resins were used as phenol-formaldehyde resins.
Each epoxy resin as a 50% solution in a solvent matched with one of the phenol resins at
70:30, 60:40, 50:50, 40:60 and 30:70 ratios. The complete match of the resins was assessed
by the transparency of the film after the drying at 150160C of the mixture of resins
applied to glass.
CHAPTER 7
237
It has been found that at room temperature low-molecular-mass epoxy resins match
with phenol resins, as cresol-formaldehyde resin K-212-01 with the softening temperature
of 6266C matches with the content of methylol groups 5.05.5% and with the 100% phenol formaldehyde resin No 101 with the similar softening temperature and with the 80%
content of methylol groups (produced based on n-tert-butyl phenol), as well as with phenol
formaldehyde butanolized by condensate modified by Chinese wood oil (resin No 241).
With these resins, low-molecular-mass epoxy oligomers almost do not match. The complete match of these components is achieved only after their heating at 120125C for 1.5
h. Medium- molecular-mass epoxy resins match at room temperature with all phenolformaldehyde resins at given ratios. High-molecular-mass epoxy oligomers E-49 and E-0.5
match with resins K-212-01 and No 101 at all ratios at room temperatures, and with resin
No 241 only after a heating up to 100125C for 1.52 h. With resin based on xylenol-formaldehyde butanolized KF and the product maximally butanolized with phenol-formaldehyde condensate MBP, high-molecular-mass epoxy resins match both at room
temperature and after heating at 120130C, but not at all ratios. At ratios of these components of 70:30, 60:40 and 30:70, the matching occurs at room temperature, and at ratios of
50:50 and 40:60 they do not match even after heating.
To produce coatings, lacquers were applied by the pouring or dipping method on
hot-dipped or electrolytic tinplate preliminarily degreased by a solvent and calcined at
180C for 1530 min. The thickness of the film was 46 m.
Chemical endurance of coatings was determined by boiling lacquer plates in a 3%
solution of acetic acid, 3% cooking salt, 2% solution of tartaric acid. Additionally, the coatings were held in these solutions in autoclaves at 121C and pressure from 2.5 atm for 1 h.
Those coatings, which had no blisters, delamination or leadiness after boiling in acetic acid
were considered to be chemically stable.
Coatings having an impact strength of no less than 50 kgcm (a U-1 instrument), an
elasticity no less than 6 mm (an E press), a pendulum hardness no less than 0.8 and a bend
no more than 1 mm, were considered to be mechanically strong.
It has been found that all these epoxyphenol compositions form water-resistant coatings. Acid-resistant proved to be only coatings based on compositions with high molecular-mass epoxy oligomer in the amount of no more than 40%.
Coatings based on low- and medium-molecular-mass epoxy oligomers are non-acidresistant. The greatest stability was shown for coatings based on resins E-0.5 in a combination with KF at a ratio of components 40:60, 30:70; resins E-0.5 and K-212-01 at a ratio of
30:70; E-49 and KF at a ratio of 40:60, 30:70. The results of storage of preserves with acid
media for 1 year have shown that coatings based on an epoxyphenol composition possess
much higher protective properties as compared with oil-based materials.
7.4
Water-base compositions for protection of canning containers
The inner and outer surfaces of metal canning containers are protected using ecologically
benign lacquer-and-paint materials: powder, with a high content of nonvolatiles, aqueous,
of radiation hardening.
Special attention is given to canning containers with protective coatings based on
water-base systems. The priority in this field is with the USA, where the demand for aqueous materials in production of canning containers increases annually by more than 19%. In
the years coming this parameter is assumed to reach 100%. The major reasons for the increasing demand of aqueous compositions is a decreased content of organic solvents
238
(2025% less as compared with traditional lacquers), lower toxicity and fire hazard, simplicity and accessibility of application methods. The world market offers a wide range of
water-base materials. However, only the systems, which satisfy the specific requirements
to materials in contact with food products, are suitable for protection of canning containers.
The major of them is inertness of coatings with respect to a canned product, the stability in
storage for no less than 12 months, the processibility, a high adhesion of coatings to the metal surface, the stability to the effect of hot water and acids, the stability to sterilization and
pasteurization. Coatings based on water-base systems should be of high quality, and their
performance properties and efficiency should not be worse than those of traditional lacquer
coatings.
Water-base compositions based on epoxy, acryl, epoxyacryl, vinyl etc. film formers
satisfy these requirements to different degrees. The choice of material is determined in each
particular case by the type of metal used, container fabrication method, type of canned product. The most widespread film formers for water-base canning materials are carboxylcontaining epoxy oligomers and epoxyacrylates. Various methods are used for their synthesis. The simplest of them is the interaction of epoxy oligomers with dibasic acids or their
anhydrides. The drawbacks of these methods are the process difficulties related to the
two-stage synthesis, a large duration of the process and a high cost of the product.
Aqueous materials having a high stability and processibility are obtained in the reaction of epoxy oligomer with aromatic amino acids; oligomers formed possess an increased
stability.
A promising method of the synthesis of carboxyl-containing epoxy oligomers with a
nonhydrolyzing ester bond is the interaction of phenol-containing epoxy oligomers with
formaldehyde and amino acids. Epoxy oligomers modified by polyfunctional phenols are
used as a phenol component. The reasonable cost and a sufficiently large choice of epoxyphenol oligomers open wide possibilities for producing film formers with a diverse set
of properties. In combination with hardeners from amino-, urea- or phenol-formaldehyde
resins, such oligomers are used in formulations of water-base materials for protection for
the internal surface of canning containers. Compositions are hardened for 212 min at
200215C to form coatings resistant to pasteurization and sterilization, the action of acids,
alkali and solvents. In industry, use is made of water-base materials based on epoxy oligomers modified by acrylates. One of the most widespread types of epoxyacrylic film formers
for aqueous systems is a mixture of epoxy oligomer and carboxyl-containing acrylate. Compositions are hardened in the presence of amino-aldehyde resin at 150370C to form a
high-quality coating resistant to the action of acids. Aqueous materials based on mixtures
of epoxy oligomers with acrylates do not always satisfy manufacturers of canning containers by their water and chemical resistance and other properties. Coatings based on epoxyacrylates with carboxyl groups in the side chains possess better performance parameters.
Water-base canning materials are produced using epoxyacrylates obtained by the reaction of epoxy oligomers or modified epoxy oligomers with carboxyl-containing acrylic
systems, in particular, film formers containing products of interaction of dianic epoxy oligomer with the mixture of methacrylic acid, styrene and epoxyacrylate. The dispersion is
hardened in the presence of hexamethoxymethyl melamine at 188C for 60 sec. The coatings are distinguished by high adhesion to aluminium and the resistance to hot water.
Carboxyl-containing epoxy oligomers and epoxyacrylates are of interest as potential
film formers for electrophoretic materials. In the USA, water-base compositions have been
developed, intended for anaphoretic coatings of the internal and external surfaces of cans.
The composition contains the reaction product of epoxy oligomer with carboxyl-containing
CHAPTER 7
239
acrylic copolymer. For hardening, phenol-formaldehyde resin or nitrogen-containing resin

are used. After neutralization by tertiary amines of the type of pyridine, morpholine, methyl
pyrrole etc., the composition is used for coating of drawn cans or rolled metal to be used
for the fabrication of composite cans. Coatings are distinguished by an increased elasticity.
A special place among water-base materials is occupied by compositions based on epoxy oligomers modified by phosphoric acid. Protection of canning containers by such materials makes it possible to provide for chemical and water resistance, strength and other
properties of coatings based on epoxyphenol lacquers. Hardeners for phosphorus-containing epoxy oligomers can be melamine-formaldehyde resins or their mixtures. Catalysts of
hardening are usually not used, because phosphoric acid present in the film former plays
the role of an inner crosslinking catalyst. Water-base epoxyphosphate compositions are applied to a metal support in one or two layers of the total thickness 0.002 mm and hardened
at 200C. The coating has a high resistance to hot water and solvents. Water-base materials
with the content of nonvolatile components up to 35%, based on phosphorus-containing epoxy oligomer having OPO(OH)2 groups, are used for protection of canning containers.
The coatings are distinguished by an increased resistance to sterilization and pasteurization.
The assortment of phosphorus-containing film formers for aqueous compositions is expanded due to the phasing in of epoxyphosphate oligomers modified by acrylates or their
mixture with other unsaturated monomers.
For painting canning containers, use is made of epoxy oligomers modified with polyesters and polyurethanes. Aluminium and steel beer cans are recommended to be painted
by an aqueous dispersion; the composition includes 70 95% of carboxyl-containing polyester based on trimellitic anhydride, adipic acid and 530% epoxy dianic oligomer. After
the neutralization with ammonia, the dispersion is applied to the inner surface of cans and
is hardened for 10 min at 200C. The coatings do not affect the taste qualities of the packaged product.
Epoxypolyurethane water-base materials for painting of the inner surface of beer cans
contain epoxy oligomer and polyurethane forpolymer, which is obtained by the interaction
of a mixture of polyester polyol and carboxyl-containing oligomer with polyisocyanate;
polyisocyanate plays the role of a crosslinking agent. Coatings are distinguished by chemical endurance, elasticity and good adhesion to metal.
Water-base materials based on acrylic resins are of interest for production of canning
containers with high durability, light permanence and heat resistance of coatings. However,
due to the negative effect on the taste qualities of products, pure acrylates are used mainly
for painting of the outer surface of containers and as coating lacquers for protection of lithographic printing. Compositions based on alkyl acrylates, methacrylic acid, methacrylate
and vinyl acetate are widely used for this purpose. Coatings based on these copolymers are
hardened at 200220C for 12 min.
Coatings based on vinyl materials are distinguished by a high corrosion resistance and
elasticity. However, owing to the insufficient thermal resistance they are unsuitable in the
cases when products are subjected to prolonged heat treatment. As film formers in vinyl
systems, use is made the most frequently of copolymers of vinyl chloride and vinylidene
chloride with acrylate or other monomers. Stable aqueous dispersions for protection of the
inner surface of metal cans for beer and drinks are obtained based on copolymer of vinyl
chloride and vinylidene chloride with vinyl monomers, which contain carboxyl or sulfonyl
groups. The most frequently used formulation of this type is based on copolymer from
3085% vinyl chloride, 1050% methyl acrylate, 0.120% acrylic acid and 0.57% vinyl
sulfonic acid. The inner surface of metal cans is protected by a water-base composition
240
based on a film former obtained by radical copolymerization of acrylic acid, ethylacrylate

and styrene in a mixture with cyclohexanone with butyl cellosolve, containing vinyl copolymer and epoxy oligomer.
Aqueous pigmented materials serve for exterior painting and lithography of cans. As
film formers, use is made of alkyd, polyester, acryl or epoxyphenol oligomers. Water-base
compositions for this purpose are obtained based on hydroxyl-containing polyester, which
represents the product of polycondensation of a mixture of fatty alcohols with a mixture of
cycloaliphatic, aromatic or aliphatic 1-, 2-, 3-basic carboxylic acids.
Water-base materials intended for painting of canning containers are applied to the
surface using rolls or by spraying. The choice of the application method is determined in
each particular case by the type of container and its fabrication process. In production of
multiply-drawn composite or two-piece cans, use is made of rolls or sheet metal painted
preliminarily on the standard equipment. Before formation of cans, the metal surface is
coated with a layer of lubricant, which facilitates the fabrication and protects the coatings
from deterioration. If necessary, one or two layers of material are applied by spraying on
the inner surface of composite cans. Two-piece cans fabricated by the ironing technology
are decorated from the outside and painted by spraying using two-nozzle sprayers or sprayers with nozzles displaced relative to each other, which makes it possible to apply a twolayer coating.
7.5
Modification of polyvinyl chloride compositions by thermoplastics
The use of regular-structure compounds as modifiers makes it possible to improve significantly the performance properties of coatings in biochemically active media. To improve
the performance properties of perchlorovinyl coatings, we studied the effect of various
physicochemical factors on the properties of block copolymers based on styrene and butadiene for their subsequent use to increase the adhesion and protective properties of perchlorovinyl systems for protection of canning containers.
The effect of the concentration of styrene in block copolymers on the properties of
coatings has been studied (Table 7.3).
Table 7.3 Effect of the concentration of -methyl styrene on the properties of coatings.
Concentration of
-methyl styrene
31.5
34.5
42.5
44.5
52.0
DMST-35
50
100
200
300
E0 /E,
E = 100%,
I = 1 min
1.47
1.87
2.55
2.21
5.37
2.18
1.60
1.98
2.59
2.35
5.29
2.17
1.76
2.12
2.70
2.65
6.04
2.21
2.04
2.52
3.47
3.74
8.95
2.59
4.76
4.76
3.71
3.85
2.70
4.55
Stress (MPa) at elongation, %
Maximum swelling
in isooctane,
%
132
136
105
110
81
126
Stresses characterizing the stressstrain properties of systems have been studied at

different degrees of strain. The maximal swelling of specimens in isooctane enables a
judgement of the density of the three-dimensional network of block copolymers. The rigidity of specimens was assessed by the relative change of the initial modulus to the value of
its change at a relative deformation of 100% for 1 min. It has been shown that, as the
241
CHAPTER 7
concentration of -methyl styrene in the block copolymer DMST increases, the rigidity of
specimens is observed to rise monotonically and the rate of the relaxation processes to decrease. The deformation properties of specimens are characterized by the value of stress at
a fixed elongation determined from the curve of the dependence of stress on the values of
strain. The rate of the relaxation processes was assessed by the inverse value of the relative
drop of the modulus in the process of relaxation at a constant elongation of 100% for 1 min.
Thermoelastoplastic specimens were swollen at room temperature in isooctane. The maximal swelling was achieved in 34 days.
These results are agree with the regularities in the change of internal stresses, from
which it also follows that as the concentration of -methyl styrene in block copolymers increases, internal stresses rise 23 times. A decrease of swelling of specimens is determined
by the increase of the density of the three-dimensional network with the increase of the methyl styrene content.
To study the particular features of structure formation in regular-structure polymers
depending on their chemical composition, use was made of the method of electron microscopy. Films were prepared from solutions of specimens in benzene at a concentration of
0.003 g/mm. Films were contrasted in vapours of osmium tetroxides.
Analysis of the data obtained indicates that thermo- and elastoplastics are two-phase
systems. Owing to the significant rigidity of polystyrene blocks, they interact one with another to form domains with parallel orientation of anisodiametric-type chains. With the concentration of styrene blocks rising, the size of the domains increases. The thickness of
polystyrene domains in the concentration range from 30 up to 50% is 3035 nm. Polystyrene domains interact to form networks, the cells of which comprise the elastomer part of
the compositions. The optimal properties of block copolymers, enabling their use as modifiers of perchlorovinyl compositions, are observed at 3035% polystyrene in the chain.
7.6
Effect of the structure of the block copolymer chain on the properties

of coatings
Thermoelastoplastics with the regular structure of the chain are characterized by higher
physicomechanical properties. The strength of films from thermoplastic DMST-35 in tension was 23.0 MPa, relative breaking elongation was 860%, the modulus at 50% was 2.1
MPa, p = 1.0 MPa.
Thermoelastoplastics with a similar ratio of irregular-structure components even after
introduction of a Zn atom into their chain and using various hardeners were distinguished
by lower physicomechanical properties (Table 7.4).
Table 7.4 Effect of the nature of the hardener on the physicomechanical properties of Zn-TEP.
Hardener
Initial composition
Altax+paraquinone dioxyl
Sulfur+chloxyl
Sulfur+santokur
Chloxyl
Diazo amino benzene
Deformation strength
f50, MPa
f100, MPa
10.6
9.5
10.5
9.8
9.1
13.7
14.3
12.4
12.6
12.0
p,
MPa
p, %
Adelam
20.0
18.8
16.4
13.8
18.0
16.8
202
195
188
95
246
229
3.3
0.6
0.7
1.1
0.9
0.9
242
It is seen from the table that for films from irregular-structure thermoelastoplastics the
values of elasticity, adhesion strength and breaking strength are considerably decreased.
Use of various oligomers (epoxyphenol, epoxyphenol acryl) and compositions on their
basis as modifiers makes it possible to increase the elasticity of coatings without significantly changing the strength parameters. Table 7.5 presents the data on the effect of various
modifiers on the mechanical properties of coatings from thermoelastoplastic Zn-TEP.
Table 7.5 Properties of modified thermoplastics.
Modifier
EF
EF1
EF2
EFA-2
EFA-2 + 5 wt.% acetur
EFA-2 + 10 wt.% acetur
EFA-2 + b-cyanoethyl acrylate
FP-326
f100, MPa
f200, MPa
fn, MPa
p, %
12.2
8.7
9.0
9.8
8.3
7.0
10.2
8.9
16.7
12.4
12.8
13.2
11.1
9.8
13.6
11.3
16.7
16.2
17.8
15.3
14.5
12.9
16.9
13.9
210
270
460
287
375
365
370
450
From the analysis of the table data, it follows that modification of butadiene styrene
compositions by epoxyphenol compositions makes it possible to improve the physicomechanical properties of coatings (strength, elasticity). However, the adhesion strength of
irregular-structure copolymers is more than 3 times as low as for block copolymers with
the similar ratio of regular-structure components.
For this reason, further studies were carried out using regular-structure block copolymers as modifiers.
7.7
Development of the method for improving the protective properties

of polyvinyl chloride compositions by modification with block
copolymers
Block copolymers are widely used in developing polymer materials of various purposes.
This is due to the fact that they are characterized by a single-phase ordered structure. The
size of structural elements, their morphology, and, therefore, the properties of polymers can
be regulated within broad ranges by changing the length, chemical composition, molecular
mass of particular blocks.
In this connection, we used regular-structure block copolymers as modifiers to improve the biochemical resistance of perchlorovinyl (PVC) coatings.
A characteristic feature of perchlorovinyl coatings is that they possess a high weatherability, resistance to the action of acids, strength and plasticity. At the same time, they
dissolve poorly in organic solvents, which is accompanied by the formation of an inhomogeneous imperfection structure and low strength of adhesion to various materials. To improve the structure and properties of the coatings, 1025% solutions of PVC are
supplemented with plasticizers and various modifying additives.
The most widespread components in fabrication of compositions are mixtures of various solvents: ethyl acetate and butyl acetate, ketones, chlorinated lower aromatic and aliphatic hydrocarbons.
CHAPTER 7
243
Dibutyl phthalate, tricresyl phosphate, sovol (polychlorobiphenyl) are used as plasticizers. An increase of the heat resistance of protective coatings is performed by way of introducing various stabilizers, in particular, epoxidized oils (soybean, sunflower), lowmolecular-mass epoxy oligomers. They serve as acceptors of HCl, which is evolved in the
decomposition of a polymer.
For regulation of the structure and properties of polyvinyl chloride coatings, used was
made of divinyl styrene thermoelastoplastics, which are distinguished by the nature of the
end groups (styrene and -methyl styrene), the structure (linear and branched), by various
contents of polystyrene blocks, as well as the ones with different molecular masses.
Coatings were formed both from solutions of PVC compositions and from powder systems.
The characteristics of thermoelastoplastics used in the formation of coatings from
powder systems is given in Table 7.6.
Table 7.6
Characteristics of thermoelastoplastics.
Melt
Hardindex
ness
f0 T = 90C,
Tensile
Relative
216 H,
strength, elongation,
g/10 min
MPa
%
Name
Chemical formula
Content
of polystyrene
Divinyl--methyl styrene
DMST-30L
Divinyl--methyl styrene
DMST-30-R
Divinyl styrene DST-30L1
DST-30L2
Divinyl styrene DST-20-R
P-2MS-PB-P--MS
30
31.5
890
68
51.5
Si-PBP-2MS
30
28.5
855
65
39.0
PS-PB-PS
PS-PB-PS
28
28
20
144.0
255.0
159.0
935
847
760
66
66
50
48.0
24.0
31.0
DSG-30-R
DST-50-R
(PS-PB)4Si
(PS-PB)4Si
31
50
211.0
105.0
910
765
70
89
37.0
48.1
Si
Physicochemical
characteristics
Based on the performed studies, it has been found that the best set of performance
properties is observed in modification of perchlorovinyl compositions using as modifier
-methyl butadiene styrene DMST-30L or DMST-35L in the presence of plasticizer
PPA-7.
Table 7.7 presents the physicomechanical properties of coatings produced at various
ratios of the main components polyvinyl chloride (PVC), block copolymer thermoplastic
DMST-35L and plasticizer (polypropylene glycol).
The stressstrain properties of films from mixture compositions were studied at an extension rate of 25 mm/min.
It is seen from Table 7.7 that the dependence of breaking strength on TEP concentration is nonmonononic. First, as the concentration of TEP is increased up to 50%, it goes
down sharply, and then at a further increase in the content of TEP it increases, staying lower
than the strength of the initial PVC and TEP components. The elasticity modulus increases
with the increase of the concentration of PVC. The ratio of the ingredients in the composition has a significant effect on the value of internal stresses. The results of the study are
presented in Table 7.8.
244
Table 7.7 Deformation/strength properties of modified polyvinyl chloride films.

Composition
TEP
PVC
PPA
0
25
25
50
50
50
50
50
50
50
70
100
100
75
75
50
50
50
50
50
50
50
30
0
0
0
25
0
10
20
25
30
50
70
0
0
E at = 50%, GPa
p, MPa
p, %
9.8
14.6
12.0
10.8
9.6
5.3
4.9
5.3
2.1
55.4
15.7
15.9
5.9
6.8
6.1
6.2
5.2
2.9
2.4
15.7
23.0
52
22
132
366
77
157
157
128
113
105
1070
860
Table 7.8 Effect of the ratio of individual ingredients on internal stresses in the formation of films
from mixture compositions.
p, MPa
Composition
TEP
PVC
PPA-7
0
25
25
50
50
50
50
50
50
50
70
100
100
75
75
50
50
50
50
50
50
50
30
0
0
0
25
0
10
20
25
30
50
70
0
0
18.0
10.5
0.9
2.4
2.1
1.1
1.0
0.9
0.9
0.7
1.1
0.9
It is seen from the table that significant internal stresses occur in films from PVC. Introduction of thermoplastics decreases them more than 1.5-fold at a TEP content of 2%. The
most sharp decrease of internal stresses, more than 8 times, is also observed at an increase
of the concentration of TEP up to 50%.
The further decrease of internal stresses was performed by introducing the plasticizer
PPA-7.
Also noteworthy is a sharply increased adhesion of coatings from modified PVC,
which was 180200 MPa, whereas films from nonmodified PVC peel off at critical internal
stresses of 1.41.6 MPa.
As the concentration of the plasticizer in the mixture is increased, internal stresses go
down. For films from a mixture composition with the PVC to TEP ratio of 50:50, internal
245
CHAPTER 7
stresses decrease by about 2 times at a plasticizer concentration of 20%. The further increase of plasticizer concentration has no significant effect on the value of internal stresses.
Their sharp (3-fold) decrease is found to occur at a plasticizer concentration of 70%.
The effect of the plasticizer concentration of the adhesion properties of compositions
was studied by the peeling method at a testing rate of 575 mm/min.
Table 7.9 presents the data on the adhesion strength of coatings with the 50:50 ratio of
the components (PVC:TEP) as a function of the concentration of plasticizer (PPA-7).
Table 7.9
PVC/TEP ratio
Content of plasticizer PPA-7, wt. %
Adhesion strength, MPa
50/50
50/50
50/50
TEP
20
30
0.445
0.350
0.345
0.221
It is seen from the table that introduction of a plasticizer up to 2030 wt. % has no
significant effect on the adhesion strength of modified polyvinyl chloride specimens.
The change of the ratio of the ingredients renders a significant effect not only on the
rate of the relaxation processes in the formation of coatings from mixture compositions, but
also on the relaxation processes in formed coatings in their operation.
The rate of the relaxation processes in formed coatings from mixture compositions was
assessed at different temperatures by the change of the elasticity modulus at a constant load
in 10 and 100 sec. The relaxation coefficient
E ( 10 sec ) E ( 100 sec )
K = ------------------------------------------------------------- 100% .
E ( 10 sec )
The results of the study are presented in Table 7.10, E in 103 MPa.
Table 7.10 Effect of the ratio of PVC and TEP in mixture compositions on the film relaxation
constant at different temperatures.
TEP/PVC
100/0
70/30
50/50
Parameters
E = 30%
Kp
E = 30%
Kp
E = 30%
Kp
Temperature, C
20
30
40
50
60
43.5
9.0
90.9
13.2
191.0
14.4
40.5
10.7
82.2
16.4
172.0
16.3
37.7
13.4
74.9
20.4
156.0
21.0
34.8
20.2
66.8
26.4
143.0
29.0
29.8
19.1
57.1
36.2
122.0
37.8
It is seen from the table that the rate of the relaxation processes increases for films from
all compositions with the temperature increasing. At the same time, the rate of the relaxation
processes also significantly rises with the increase of the content of PVC.
Comparison of these data with the results of the study of internal stresses as a function
of the concentration of PVC in mixture compositions indicates the absence of their
246
correlation, because internal stresses increase significantly due to the retardation of the relaxation processes in the formation of coatings with the content of PVC increasing.
Using the method of electron microscopy, it has been found that the specific change
of the relaxation characteristics depending on the ratio of ingredients in mixture compositions is due to the features of structure formation in the fabrication and operation of coatings.
In studies of the structure of coatings from PVC by the method of electron microscopy
it has been found to be inhomogeneous by the size of globules, which change within the
range of 3080 nm.
The structure of the block copolymer of -methyl styrene thermoplastic is characterized by the occurrence of domain-morphology structural elements with the domain width
of 20 nm.
At a 30% content of PVC, the composition is found to have a more homogeneous globular structure with the structural elements of 2550 nm in size. An increase of the concentration of PVC up to 50% significantly increases the inhomogeneity of the structure. The
structural elements of PVC are distributed in the film unevenly in the form of aggregates
0.20.3 m in diameter. A further increase of the concentration of PVC up to 75% increases
the inhomogeneity even more. Separate regions of structural elements characteristic of PVC
and TEP are observed.
The distribution of ingredients in mixture compositions was regulated by introducing
a plasticizer.
Thus, at a PVC to TEP ratio of 30:70, one observes a good match of ingredients on the
level of their supramolecular structure. Production of coatings with the homogeneous structure and a good match of ingredients on the level of supramolecular structures can be done
in the presence of a plasticizer at a PVC to TEP ratio of 50:50.
It follows from these results that the rise of the relaxation constant for films from mixture compositions with the PVC concentration increasing is due to the worsening of the
compatibility of components on the supramolecular level and the formation of a defect
structure more readily destroyed under the action of an applied load.
Based on the results of these studied, compositions containing 50% PVC and 50%
thermoelastoplastics with an optimal concentration of the plasticizer were chosen, which
provide for the fabrication of coatings with the best protective properties.
7.8
Studies of the relaxation properties of coatings from polyvinyl chloride

compositions modified by thermoplastics
The relaxation properties of coatings were assessed by studying the temperature dependence of the stressstrain properties of compositions at an optimal ratio of PVC/TEP =
50:50 and different contents of plasticizer PPA-7. The tests were carried out at an extension
rate of 25 mm/min within the temperature range of 2080C.
The results of the study are presented in Table 7.11.
Figure 7.1 presents a temperature dependence of strength and relative breaking elongation on the testing temperature. Analysis of these results suggests that the resistance to
rupture and breaking elongation decreases at an increase of temperature for nonplasticized
specimens.
For plasticized specimens, p changes nonmonotonically depending on the concentration of plasticizer. An exception is the initial composition, for which the maximum in the
change of p is not observed.
247
CHAPTER 7
70
p, %
60
1
p10, MPa
50
400
40
300
30
4
200
20
4
10
10
30
100
50
70
10
90
30
50
70
T, C
90
T, C
Figure 7.1 Dependence of strength (a) and relative elongation (b) on testing temperature for specimens plasticized with PPA-7 and nonplasticized specimens of coatings. a: 1, no PPA-7; 2, 10 wt. %
PPA-7; 3, 20 wt. % PPA-7; b: 1, no PPA-7; 2, 10 wt. % PPA-7; 3, 20 wt. % PPA-7; 4, 30 wt. %
PPA-7.
Table 7.11 Effect of the testing temperature and the concentration of plasticizer on the
physicomechanical properties (tensile strength p, ultimate elongation p).
Concentration of
PPA-7, wt. %
Properties
p, MPa
p
p, MPa
p
p, MPa
p
p, MPa
p
10
20
30
Testing temperature, C
20
35
50
65
80
5.9
370
6.8
93
6.1
180
5.2
146
5.3
340
5.6
134
3.8
250
3.0
142
4.2
352
3.1
283
2.3
246
2.0
175
3.3
277
1.0
245
1.1
214
0.9
156
1.7
134
0.5
165
0.6
155
0.5
143
To elucidate the mechanism of interaction of the components in a modified polyvinyl

chloride system, the activation energy of the breakdown process was calculated.
It is known that the tensile stress calculated for the real transverse cross section of a
specimen at the moment of rupture [p = Pp (E + 1)] changes for many polymers, depending
on temperature, according to an equation similar to the Arrhenius equation:
p = BeU/RT,
where p is the rupture stress, B is a constant, R is a gas constant, T is temperature in degrees
Kelvin and U is activation energy.
248
logp
2.6
2.2
2
1.8
3
4
1.4
1.0
2.8
3.0
3.2
3.4
1000/T, K
Figure 7.2 Dependence of breaking stress in the logarithmic coordinate on inverse temperature for
specimens with different concentrations of plasticizer PPA-7 obtained from solutions. 1, 0 wt. %
PPA-7; 2, 10 wt. % PPA-7; 3, 20 wt. % PPA-7; 4, 30 wt. % PPA-7.
In (log p 1/T) coordinates, this dependence has the shape of a straight line, whose
slope to the abscissa axis is proportional to the activation energy.
Figure 7.2 presents a dependence of log p on 1000/T for four systems studied. This
dependence is seen to be not linear but to present a jogged line in the temperature range
studied (2080C). The inflection points of these lines are in the temperature range of
4550C. An exception is the initial system, for which this point is at 60C.
The fact that the dependence of log p on inverse temperature for the compositions
studied is a jogged line suggests that, depending on the temperature range of studies, the
breakdown of modified polyvinyl chloride compositions is determined by different mechanisms characterized by their own activation energies. In turn, these regularities are determined by the different character of structure formation and the level of match of the
components at the impact of temperature.
Table 7.12 gives the results of calculating the activation energy for the systems studied.
Table 7.12 Effect of the concentration of plasticizer on the activation energy of modified polyvinyl
chloride compositions at different testing temperatures.
Concentration
of plasticizer
0
10
20
30
Testing temperature range within which the dependence

log p 1/T is linear
2050C U1, kcal/mol
5080C U2, kcal/mol
2.29
1.22
3.23
6.01
8.85
8.92
6.16
6.38
It is seen from the table that at higher temperatures (5080C) the activation energy
is larger than at decreased temperatures (2050C).
249
CHAPTER 7
The differences in the activation energies are smoothed with temperature increasing,
and at 30 wt. % of plasticizer the values of U1 and U2 are almost equal. Similar regularities
in the change of activation energy depending on the testing temperature were observed for
specimens obtained not by forming films from solutions, but by calendering a mixture of
PVC with modifier TEP.
The results of the tests of the mechanical properties of this composition are presented
in Table 7.13.
Table 7.13 Mechanical properties of PVC modified by TEP.
Parameter
Testing temperature, C
20
f30, MPa
p, MPa
p, %
7.26
9.90
90.0
30
5.71
8.39
106.0
40
3.97
6.39
126.0
50
2.55
4.56
143.0
60
1.65
3.08
123.0
70
1.16
2.10
118.0
80
0.80
1.36
116.0
It is seen from the table that for this batch of specimens, also with the testing temperature increasing, the resistance to rupture decreases monotonically, and the breaking elongation passes through a maximum revealed at approximately 50C.
The processing of experimental results with the view to determine the activation energy of the breakdown for this composition again showed a similar character of the dependence of log p on inverse temperature in the shape of a jogged line, whose inflection is at
about 45C (Fig. 7.3). The values of the activation energy calculated by the slope of, respectively, the gradual and steep segments of this jogged line are 2.7 and 10.3 kcal/mol.
From the analysis of the results of the studies, it follows that the formation of modified
perchlorovinyl compositions at a temperature of 4060C is accompanied with a significant increase of the intermolecular specific interaction between structural elements and an
improvement of performance properties of coatings.
7.9
Modified perchlorovinyl coatings with increased shelf-life
Coatings based on perchlorovinyl compositions are characterized by a valuable set of properties. The most important of them are weatherability and the possibility of preserving the
protective properties in operation under conditions of the action of organic and inorganic
acids.
However, under operation conditions, owing to the imperfection and inhomogeneity
of their structure, the service life of coatings does not exceed 23 years.
To improve their protective properties and to increase durability, structure formers are
proposed to be used as modifiers; they increase the adhesion strength and stability of adhesion of coatings to metal in contact with elements, water, and high-humidity atmosphere.
To increase the adhesion/cohesion strength and protective properties of coatings based
on perchlorovinyl compositions, use is made of modifiers containing coordination organic
compounds with plane-oriented structure and coordination ions of various metals in macromolecules. These compounds increase the adhesion strength 23-fold and simultaneously improve the protective properties of coatings in aggressive media.
However, due to the complexity of their synthesis, they have not found wide use in
industry. Because of this, compounds with various functional groups are used as modifiers
250
log p
2.6
2.2
1.8
1.4
3.0
3.2
3.4
1000/T, K
Figure 7.3 Dependence of the logarithm of the breaking stress on inverse temperature for TEPmodified PVC specimens obtained by calendering of the mixtures. 1, U = 2.7 kcal/mol; 2, U = 10.3
kcal/mol.
contributing to the increase of the adhesion strength of coatings from resin based on chlorinated polyvinyl chloride resin PSKh-LS and its stabilizers in operation in liquid media.
The adhesion strength was measured by the method of irregular peeling of coatings
applied to plates from low-carbon steel 08kp, at a peeling rate of 2.4 mm/min.
Holding of coatings in a medium significantly reduces their adhesion strength. After
their removal from a medium, specimens were held for 24 h at 20C, and their adhesion
was measured. At a small exposure in the medium, the adhesion of coatings is partially restored. An irreversible decrease of adhesion strength is due to the uneven distribution of
adhesion bonds in the boundary layers of the coatings due to the inhomogeneity and imperfection of their structure, which leads to the development of corrosion processes.
The level of the recovery of the adhesion strength is significantly affected by modifiers. Owing to the larger surface energy and the presence of active functional groups, modifiers are adsorbed in the boundary layers of coatings to improve their physicomechanical
properties. Modifiers were introduced in an optimal amount of 12% to the resin prior to
the application of coatings. Table 7.14 presents the data on the effect of the time of exposing
Table 7.14
Medium
Distilled water
HCl, 5%
H2SO4, 5%
Exposure, min
0
10
40
60
0
15
30
0
15
10
Adhesion, g/cm
initial
after exposure
recovered
% of recovery
333
333
333
333
304
304
304
312
312
312
92
31
0
36
0
12
10
185
59
0
157
96
99
53
55
17
0
51
31
31
16
CHAPTER 7
251
coatings to different media on the adhesion strength of the initial coatings after holding
them in media and the restored strength.
The effect of modifiers on the adhesion strength of perchlorovinyl coatings was studied. As additives, used was made of alkoxysilanes A-2 and ASOT-2 containing various
functional groups, additions of MHU and PMHU containing hydroxyl and ester groups,
regular-structure aromatic stabilizers with active radicals of CPA.
The results of studies of the adhesion strength of perchlorovinyl coatings are presented
in Table 7.15.
Table 7.15
Modifier
A-2
CPA
MHU
PMHU
ASOT-2
Adhesion strength, g/cm

310
680
325
295
295
550
35
15
75
15
15
25
It is seen in the table that additions of CPA, MHU, PMHU change little the value of
the adhesion strength of perchlorovinyl coatings. Additions of MHU, PMHU decrease the
adhesion strength as compared with this parameter for nonmodified coatings.
Modifiers A-2 and ASOT-2 increase approximately twofold the adhesion strength of
initial coatings prior to the action of aggressive media on them. However, after keeping the
coatings in liquid media, probably, due to the ability of alkoxysilanes to be hydrolyzed under these conditions, the adhesion strength of the coatings decreases.
At the action of electrolytes, the highest adhesion strength is observed for perchlorovinyl coatings modified by antioxidant CPA.
252
8
8.1
Ways of Modifying the

Properties of Metallized
Packaging Materials
Purpose and fields of application
Articles from plastics, ceramics and composite materials with metallized surface are used
at present in many industries and are widespread in households. The low specific mass,
good mechanical parameters, the absence of corrosion problems make it possible in a number of cases to give them the preference over traditional metals.
Abroad, metallized film materials are widely used in fabrication of various packagings
in food industry and other industrial spheres. This is due not only to the improved decorative
properties of packaging materials in metallization, but also a significant (several orders of
magnitude) reduction of vapour permeability and an increase of the barrier properties of
combined films.
New applications of synthetic materials (automotive industry, production of household appliances and electronics, etc.) put forward increased demands to their appearance
and service life. In this connection, a topical problem are the specific properties of the surface of such materials, whose purpose is to conceal the formation defects, to increase the
resistance to cracking, scratching, as well as atmospheric and chemical endurance, to improve the decorative properties. There are two ways of finishing nonmetal materials metallization and painting with lacquer-and-paint materials.
Metallized dielectrics, whose surface is partially or totally coated with a metal, possess
an increased resistance to the action of organic solvents, moisture, boiling and high temperatures; have high physicomechanical and decorative properties, as well as can endow articles with specific properties (for instance, metallized coatings in electronics are used to
shield the bodies of equipment from interference noise, for elimination of statics, protection
from the impact of various short-wave radiations). For metallization of dielectrics, such
metals are used as aluminium, copper, nickel, platinum, tin, lead, zinc, iron etc., as well as
metal alloys. The choice of a metal is determined by the purpose of a metallized item and
the technological features of the metallization method.
In finishing the surface of dielectrics with lacquer-and-paint materials, there are a
number of problems related to the adhesion strength of coatings to plastics, a relatively low
resistance of plastics to the action of increased humidity, high temperatures and organic solvents, as well as to the provision of the required decorative, physicomechanical and adhesion properties.
To endow articles from nonmetal materials with high decorative and performance
254
properties, a promising way is to combine two methods of surface finishing to produce a

combined coating: by applying a metal layer and by colour printing. In this case, besides
the decorative properties, metal endows an article with an increased resistance to the action
of high temperatures, moisture, organic solvents, as well as hardness and wear resistance.
A lacquer-and-paint material can not only be used to provide for high decorative and
performance properties, but protect the metal film from oxidation. Besides, a metallized
coating enables the use of electrodeposition for painting various dielectrics (polymer films,
plastics).
Electrodeposition of water-base lacquer-and-paint materials is one of the most widespread methods of producing single-layer and primer coatings on metal articles under conditions of large-series production. This method conforms the most completely to the
requirements imposed on the modern conditions and processes of chemical technology, is
a practically closed technological cycle with total automation and mechanization of the production process.
However, many problems associated with the use of the electrodeposition method for
painting of metallized dielectrics have not been solved. The particular features of forming
coatings on a metallized sublayer have not been sufficiently studied in painting by the
electrodeposition method, the chemical nature of the surface of the metal support and the
structure of the surface of the metallized layer have a significant effect both on the technological regimes of the process and on the structure and properties of protective coatings.
Recently, to increase the corrosion resistance of steel, Western companies in various
machine-building industries make use of steel workpieces with various kinds of galvanic
coatings, mainly zinc nickel, zincaluminium, nickelcadmium, chemical or galvanic
nickel followed by the application of protective lacquer-and-paint materials.
A large cycle of works is under way in solving the problem of decreasing the hardening
temperature and time of materials manufactured by Russian industries. The main waterbase compositions, which can be applied to metallized film materials, harden at 180C.
Works in this field are carried out in several directions based on the introduction of
hardening catalysts, special low-temperature hardeners, into film formers, as well as by synthesizing bonding adhesives with the low temperature of hardening.
Such additives include siccatives of metals, organic accelerators, modifiers based on
epoxy and isocyanate oligoesters. Usually, a significant drawback of such additives is a decrease of the stability of performance properties of the working solutions of polymer compositions prior to their application and, respectively, a deterioration of the properties of such
coatings.
8.2
Methods of forming metallized layers on polymer materials
The performance properties of metallized polymer materials with a protective lacquer-and-paint coating should be determined first of all by the adhesion of the metallized
sublayer to the polymer film and protective coating to metallization.
At present, three groups of methods are used for metallization in Russian and Western
industries:
mechanical (conformal coating, hot embossing);
physical (gas-thermal deposition of melted metal and metallization under vacuum);
chemical (chemical and chemico-galvanic metallization).
Some results of using various methods of metallization in this country are given in
Table 8.1.
CHAPTER 8
255
Table 8.1 Effect of the method of metallization on adhesion of coatings.

Metallization method
Chemical
Chemico-galvanic
Vacuum
Metallized dielectrics
Type of coating
Almost all kinds of plastics,

ceramics
ABS plastic, polystyrene,
polypropylene, polysulfone,
glass fibre
Polyamide, aminoplastics,
epoxides
Copper, nickel,
silver
Copper,
chromium, nickel,
lead, silver, tin
Aluminium,
copper
Total thickness Adhesion

of coating, m
0.0110
Good
3065
High
0.11
Low
Under conditions of series production, the most widespread methods of metallization

of complex-shape items are chemical methods.
The method of chemical metallization by precipitation from solution consists in the
formation of a metal coating on the surface of a polymer material owing to the autocatalytic
chemical reactions at the interface. Before metallization, articles are subjected to activation
with the view to apply the catalyst of the reduction reaction of the base metal on the surface
of the support.
The process of chemical metallization is used the most frequently in coppering and
nickeling. The use of other metals is limited by the low stability of their solutions.
Activation can be performed according to two protocols: sensitization and direct activation. In sensitization, articles are first subjected to treatment in acidic, alkaline or alcoholic solutions of divalent tin salts. After the treatment, the surface is activated by solutions
of salts or complex compounds. Usually, acidic solutions of palladium chloride or alkaline
solutions of silver nitrate are used for this.
For direct activation, use is made most often of combined solutions containing tin and
palladium salts and solutions of accelerators. Accelerators used the most are solutions of
mineral acids, alkali and salts of alkaline metals.
The process of chemical metallization proper is performed in solutions containing the
salt of applied metal, the reducer, the complex former for binding ions of reduced metal into
a complex, buffer additions to regulate pH of the solution, stabilizers, gloss formers, etc.
For coppering, use is made of solutions containing copper sulfate, a complex former
(potassiumsodium tartrate, glycerol, etc.), a reducer (formaldehyde).
Nickeling is performed in acidic or alkaline solutions of nickel chloride or sulfate; layers of reducer 0.0110 m thick are usually applied, which are then reinforced by applying
a thicker layer of metal by a galvanic method.
Deficit and high cost of precious metals were the reason for developing the activation
processes without using palladium or with its decreased content in activating solutions.
To decrease the concentration of palladium in solution, it was proposed to treat the surface in sols based on silicon or iron oxides before the activation stage.
This treatment results in the creation of a developed surface, which significantly decreases the energy of the formation of active sites of palladium and its consumption. This
process is used in the metallization of printed circuit boards.
A method was developed of forming a catalytically active copper film by reducing its
hard-to-dissolve compound on a metallized surface by such efficient reducers as formaldehyde and hydrazine. The process proceeds in two stages: first the copper(I) oxide is formed
in a hydrazine medium, then a catalytic copper film is formed in a formaldehyde medium.
256
A method has been proposed of activating dielectrics in solutions, which represent a

stable colloidal system consisting of salts of basic metals with complexons. Reduction of
sorbed ions is performed using boron hydrides of alkaline metals or their derivatives.
Methods have been developed of substituting activated solutions based on palladium
for solutions of sodium boron hydrides containing organic solvents (monobasic alcohols,
hexachloroethane, dimethylformamide etc.) for chemical nickeling of small items with increased adhesion of applied coating.
To increase adhesion of copper to polymers, the surface is activated by application and
subsequent thermolysis of copper hypophosphite. The surface is first treated with a solution
of thermosensitive copper salt. The subsequent heat treatment at 100140C leads to the
formation of metal copper particles, which are initiators of chemical precipitation of copper
from solution instead of palladium particles.
Chemico-galvanic metallization of dielectrics is widely used in formation of currentconducting layers of a sulfide coating. The method consists in the subsequent treatment of
the surface in a solution of copper salts and in a solution of a sulfonating agent, for instance,
sodium sulfide. Treatment with water leads to the hydrolysis of the copper salt and to the
sorption of partially soluble hydrolysis products on the surface. In the subsequent treatment
in a solution of the sulfonating agent, the copper-salt hydrolysis products are converted to
copper sulfide.
Electrical conductivity of copper-sulfide layers can be regulated by their multiple application, after which the cycle is repeated several times.
An increase of electrical conductivity of the coating is also achieved by adding copper
salts, zinc salts, metal copper or monovalent copper compounds to the solution.
To provide for the subsequent application of nickel by the galvanic method, the electrical resistance of the current-conducting sulfide layer should not exceed 103 Ohm/m.
A significant advantage of this method is the stability of solutions and properties of
the produced current-conducting layers due to the use of separately stable solutions of copper salts and the sulfonating agent, as well as to the removal of hydrolysis products (copper
salts), not bound to the surface, by washing.
The metallization process of dielectrics and the quality of metallized material are affected by the surface preparation. The quality of metallized material is determined by the
strength of adhesion of the metal coating to the polymer film, so the process is carried out
under conditions providing for the maximal and uniform strength of adhesion interaction.
Several theories explain adhesion of the metal layer to polymer. The theory of mechanical engagement pays main attention to the geometry of the surface. Adhesion is associated
with the number of micropits on the surface of well-etched polymers, into which deposited
metal penetrates. This theory explains well the formation of a strong bond of metal to heterogeneous-structure polymer, from the surface of which one of the phases is easily removed during the etching. For ABS block copolymers, these are globules of polybutadiene;
for polypropylene and polyethylene, the amorphous phase. In accordance with these views,
the force of adhesion of metal to polymer depends on the content of the phase easily removed in etching and its strength on the whole.
Chemical theory assumes the influence of the nature and concentration of functional
groups, for instance, the adhesion of a sulfite coating to chemically iodified polystyrene.
Wettability theory (surface-energy theory) considers adhesion as the adsorption process, in which the forces of attraction depend on the distance between two plane bodies,
i.e., the complete mutual wettability specifies a better adhesion.
Diffusion theory assumes an increase of adhesion as the result of the diffusion of one
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257
substance into the other. The diffusive character of the formation of the copper sulfide layer
enhances its adhesion properties.
According to electrostatic theory, adhesion is also affected by electrochemical reactions occurring near the interfaces between the polymer and working solution in the process
of metallization.
Thus, adhesion of the metal coating to the polymer film is affected by the state of the
surface and the strength of the polymer film, the presence of active functional groups on its
surface, its roughness, the nature and conditions of precipitation of the metal coating.
An optimal state of the surface of the polymer film before metallization depends both
on the method of processing the polymer into the film and the production of combined materials, and on the surface preparation processes, which include mainly degreasing and etching.
Degreasing is the initial stage of surface preparation to remove all organic impurities
possessing a large affinity to polymer. Most polymers are not wetted by water; therefore,
depending on the physicochemical properties of polymers, degreasing is done using organic
solvents or solutions of surfactants. Pure organic solvents are used rarely, because most of
them cause swelling of polymers, make the process more expensive and are harmful for the
environment. Commercially, aqueous emulsions are used the most; their compositions include organic solvents and synthetic emulsifiers. For degreasing, acidic or alkaline solutions of the type of KM-1 are also used. Besides the removal of contamination, this
treatment causes a change of the structure of the surface layers of polymers owing to their
partial dissolution and swelling. This increases the etching capability of polymer and makes
it possible to increase adhesion of coatings.
Most polymers are etched using chrome mixtures. The regime and composition of
etching solutions for particular polymers are found experimentally, taking into account the
grade of polymer, fabrication conditions, roughness and other factors.
Processes occurring on the surface of ABS resins during the etching in a solution of
chromic anhydride and sulfuric acid have been studied. Under the action of etching solutions, butadiene is oxidized by the double bonds to form carboxyl groups at a depth of several micrometres. Herewith, butadiene dissolves to form pits of the shape of spherical
micro- and macrocavities.
An important role is also played by the composition of the polymer matrix. Owing to
the presence of acrylonitrile in the structure of ABS polymer, a better hydrophilicity of the
surface is achieved than in polystyrene, which has no polar component in its structure.
Another etching mechanism is observed using organic solvents. For this block copolymer, particles of polybutadiene are embedded into the structure of styrene acrylonitrile and
swell to a greater extent than styrene acrylonitrile. Precipitation of metal occurs by the defects emerging under the action of internal stresses determined by the different extent of
swelling and deformation of separate fragments of the polymer chain in the block copolymer.
During the metallization of modified polypropylene subjected to etching, the quality
of the metal coating was shown to depend on the value and character of the distribution of
stresses in the surface layer, the extent of crystallization and size of supramolecular structures before and after the etching.
The use of minor amounts of finely dispersed additives and special surfactants has an
effect on the structural transformations during the etching, the stressed state on the surface,
amount and distribution of the amorphous phase, makes it possible to provide for the high
quality of coatings.
258
Processes of etching some polymers in solutions containing no chromium compounds

have been developed. To ensure adhesion of the metal coating to polyamide, the material
is subjected to etching in aqueous solutions of organic bases (ethylene diamine and monoethanolamine), and then is treated in a solution of potassium hydroxide.
Polyethylene and polyamides are recommended to be etched in acidic or alkaline solutions of potassium permanganate.
In view of more rigorous ecological requirements, there is a tendency of using more
ecologically pure methods of modifying the surface of polymers, such as plasma etching,
corona discharge treatment, oxidative action of ozone and UV radiation.
In the preparation of the surface of polyethylene for metallization, it is efficient to use
combined methods, for instance, etching with a chromium mixture or with an acidic solution of potassium permanganate followed by the treatment with an electric discharge. High
adhesion of metallization in this case is explained by a favourable combination of the chemical and microgeometrical structures of the film surface.
The effect of the nature of the support with the general tendencies preserved has its
own features for various polymer film-forming systems. There is no data in the literature
on the effect of the nature of metallized support on polymer coatings formation. In this connection, for the development of polymer compositions and processes of their application to
metallized film materials, it is necessary to carry out studies to understand the mechanisms
of forming polymer coatings on metallized film materials and to develop methods of increasing the adhesion strength of coatings to nonpolar and weakly polar film materials.
Polymer systems have a low adhesion strength to nonpolar or weakly polar film combined packaging materials. Such materials also include metallized combined films.
A way of protecting the metallized layer from powdering under the action of a mechanical load and boiling is to form a thin polymer coating several micrometres thick on its
surface. To create such coatings, it is necessary to develop the physicochemical methods of
producing protective layers with high adhesion strength and resistance to sterilization.
The aim of the present work was to develop methods of modification of polymer compositions with high protective properties for metallized combined materials.
8.3
Protective coatings for metallized materials
High adhesion properties and resistance to the action of aggressive media are characteristic
of coatings based on low-molecular-mass epoxides ED-16 and ED-20. In this connection,
the epoxy bonding adhesive is chosen as the main component in developing a lacquer composition for protection of metallized packaging materials.
Studies of the regularities of forming the structure of epoxy network polymers contribute to the rational approach to monitoring the technological process for production and processing of polymer materials on their basis, because the formation of these polymers occurs,
in contrast with linear ones, in the hardening of coatings.
Network (cross-linked, three-dimensional) polymers, according to the definition given
well back by Schtaudinger, are high-molecular-mass compounds, in which the constituent
chains are linked in three directions by chemical bonds, from which, however, covalent
bonds are capable of forming a three-dimensional network structure.
Other types of interaction (ion, coordination, hydrogen or intermolecular) introduce a
significant and sometimes even prevailing contribution to the formation, structure and properties of the polymer network.
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259
The occurrence of chemical bonds specifies a distinctive feature of network polymers

their insolubility in organic solvents and infusibility. The significant role of physical
bonds in the formation of the three-dimensional network of thermoreactive polymers is indicated by the reversible change of the properties in repeated heating and cooling.
Based on the performed studies, it has been found that real network epoxy polymers
represent systems inhomogeneous by the size of structural elements, by the distribution of
chemical and physical bonds.
Epoxy oligomers consist of structural elements of globular morphology already in the
liquid phase. During the hardening, their polymerization proceeds first inside the globular
structures, which represent complex supramolecular formations consisting of more fine
structural elements.
Then links between these structures are formed. Chemical and physical bonds are distributed in the system unevenly. About 70% of them are formed inside the supramolecular
structures, which are characterized by a denser packing and orientation of polymer chains.
With this taken into account, the physicomechanical and protective properties of network polymers are by several orders of magnitude lower than their calculated values obtained with account for the strength of chemical bonds evenly distributed in the system.
Data of electron-microscopy studies of structure formation in hardening of network
polymers, including epoxy ones, also support the formation of an inhomogeneous defect
structure of the network, in which aggregates of colloidal size are separated by a structure
of lower-molecular-mass fractions.
Analysis of experimental data of the structure of epoxy coatings indicates that the
structural organization of polymers should be divided into three levels: molecular, topological and supramolecular.
The molecular level of the structure reflects the chemical architecture of polymer, the
stereochemical organization of the chain, the character of the attachment of links one to another. All parameters characterizing the molecular level of the structural organization can
be unambiguously related to the conditions of synthesis. The topological structure of polymer describes the organization and structure of the chain as a whole. The supramolecular
level of organization of the polymer system reflects the character of intermolecular interaction of macromolecules and the extent of order in their mutual arrangement.
It is established at present that all polymers both amorphous and crystalline possess
an extent of order determined both by the molecular structure of polymer and the methods
of its production and reprocessing.
Studies of epoxy coatings have shown that the structure is formed already in initial oligomer in the process of their synthesis. Similar data have been obtained by Catrell. He has
found that the structure emerges prior to the time of the loss of fluidity and is then fixed in
the process of hardening owing to a sharp decrease of mobility of the structural elements.
Studies of the formation specifics of coatings based on oligomers, solutions and dispersions of polymers have shown that the mechanism of this process is related to the transition of the system to a gelated state owing to the formation of local physical or chemical
bonds between structural elements and the inhibition of relaxation processes leading to the
emergence of internal stresses. Herewith, a view has been put forward and experimentally
substantiated that the formation process of epoxy coatings consists of two stages:
formation of local bonds within the limits of a small number of macromolecules,
which is accompanied with the formation of a supramolecular structure;
emergence of links between these structures and formation of the three-dimensional
network.
260
At the first stage, despite a significant number of groups involved in the formation process, an induction period is observed on the kinetic curves for the change of the physicomechanical properties of coatings; the induction period is characterized by low physicomechanical properties and internal stresses in coatings. At the second stage, a sharp slowdown of the relaxation process and the emergence of internal stresses are observed. This
character of structural transformations is common for network polymers and is found in
studies of the hardening of coatings based on oligoester urethanes, epoxides, phenol formaldehyde, organosilicon and other polymers.
By the method of NMR, it has been shown that, depending on the chemical composition of oligomer, folding of macromolecules into supramolecular structures can be different, which, in turn, determines the distribution (on their surface) of active groups involved
in the film formation process and in the interaction with the support. To realize the largest
number of functional groups in the formation of adhesion and cohesion bonds, it is necessary to develop in oligomer systems ordered structures of anisodiametric or clustered type
from unfolded molecules.
Electron-microscopy studies of polymers showed the morphology of sparsely crosslinked polymers to differ little from the character of structural elements for linear polymers.
The major structural elements can be all morphological types (globules, spherolites,
crystallites, fibrillae, etc.) characteristic of linear polymers.
For densely crosslinked epoxy polymers obtained from oligomers with the static distribution of the functional groups, the main structural element are globules.
Variation of the structure of the initial reagents (oligomers, hardeners, solvents),
change of the formation conditions or the effect of thermal or mechanical fields on the already formed polymer do not change the morphology of the structure of a densely
crosslinked polymer: in all case, it remains globular, only the size of globules and the density of their packing do change.
Oligomers with the regular structure of the chain form associates of anisodiametric
shape from macromolecules of unfolded conformation, as well as highly organized crystals
of various morphologies. The number and size of globules change depending on the hardening conditions.
Hardening of epoxy coatings at low temperatures is accompanied with the development of large globular formation in the structureless matrix.
The subsequent heating of coatings up to 343353 K at the second stage of hardening
leads to the emergence of small globular formations and an increase of their number. Herewith, chain and band structures are formed in epoxy coatings, which is indicative of the destruction of some bonds between structural elements and their regrouping into more
complex structural elements.
According to the data by Catrell, formation of supramolecular structures is determined
both by hardening temperature and rate. At a large rate of hardening, the size of globules
formed is 2010 6 m, whereas the slow hardening at low initial temperatures is accompanied with the formation of globules of up to 9010 6 m.
8.4
Methods of modifying the structure and properties of epoxy coatings
Coatings used for protection of metallization should have a high resistance to the action of
water in boiling. The performance properties of epoxy coatings significantly depend on the
nature and concentration of hardeners. The resistance of coatings to the action of aggressive
media is significantly affected by the ratio between the value of internal stresses and adhe-
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261
sion strength of coatings. In this connection, the issues related to the development of physicochemical way of decreasing internal stresses are of great scientific and practical
significance. One of the ways to decrease them is to develop methods of modifying compositions in the process of their synthesis. Internal stresses emerging in the formation and
performance of coatings are a measure of imperfection of their structure. In this connection,
targeted synthesis of oligomers with a regular structure of the chain or their modification
by special additives make it possible to significantly reduce internal stresses in coatings.
The effect of the structure of epoxy oligomer molecules on the protective properties
of coatings based on oligomer ED-20 was studied by using compounds of various chemical
compositions and molecular structures as hardeners. Along with polyethylene polyamine,
which makes epoxy oligomers harden as the result of copolymerization by epoxy and amino
groups by way of opening the oxide rings and substituting hydrogen atoms of hydroxyl
groups, ester acids with different chain structures were used as hardeners.
Regularities in the change of internal stresses depending on the main factors, which
determine the film formation process (formation conditions, film thickness, strength of interaction at the polymersupport interface, etc.) proved to be common for coatings based
on various oligomer systems.
The rate of increment and the value of internal stresses in the formation of epoxy coatings depend on the hardening conditions. At 20C, internal stresses rise comparatively
slowly and reach an ultimate equilibrium value in 2030 days.
As the formation temperature rises, the internal stress increment rate goes up, especially significantly in the range equal to or greater than the glass-transition temperature.
When comparing the kinetics of using the functional groups of epoxy oligomer in the
formation of coatings with the internal stress increment rate, it was found that there was no
symbasis in their increment. The rate of using the functional groups in the formation of the
three-dimensional network is much faster than the rate of increment of internal stresses.
The number of epoxy groups entering into the polymerization reaction was assessed
by IR spectroscopy from the change of intensity of the absorption bands in the region of
918 and 1247 cm 1, characteristic of epoxy groups; and 3350 cm 1, for amino groups.
The structure of epoxy coatings was studied by the method of electron microscopy by
taking carbon-platinum replicas at various stages of coating formation.
The regularities obtained suggest that at 20C more than 50% of all functional groups
enter into interaction for 57 h; in 1020 h, the polymerization process is totally complete;
herewith, 5075% of epoxy groups enter into the reaction. Internal stresses under these
conditions of hardening reach the ultimate value in 2530 days.
At 80C, the number of functional groups involved in the interaction increases up to
85%, and the polymerization process ends up in 6090 min of coating formation. Internal
stresses under these formation conditions reach an ultimate value in 1012 hours of hardening.
Despite the small value of shrinkage of epoxy coatings in hardening (not more than
12%), they feature significant internal stresses up to 1015 MPa which at a film thickness of 300400 m induce a spontaneous peeling and cracking of coatings.
Internal stresses were decreased by changing the nature of hardener for epoxy systems.
The dependence of internal stresses and other mechanical properties of films on the
amount of hardener in the composition is nonmonotonous and exhibits a maximum corresponding to the formation of the largest number of crosslinks, therefore the decrease of internal stresses by changing the amount of hardener is accompanied with the worsening of
the other mechanical properties.
262
14.0
1
12.0
b10, MPa
10.0
2
3
8.0
6.0
4
4.0
2.0
400
800
1200
h, m
Figure 8.1 Dependence of internal stresses on the thickness of coatings from composite epoxides
hardened by polyethylene polyamine (1), glycerol trisuccinate (2), glycerol triadipinate (4) at 120C,
as well as glycerol tricebacinate at 200C (3).
To improve the mechanical properties of coatings, use was made of ester acids with
different chain structures as a hardener. The properties of coatings from epoxy oligomer
ED-20 changed depending on the nature of trifunctional ester acid. As the length of ester
acid branchings increased, the elasticity of coatings increased too.
Coatings were formed from 6085% alcohol-acetone solutions of epoxy oligomer
and, respectively, 70% acetone solutions of glycerol trisuccinate, triadipinate and tricebacinate at a ratio 1:1. Coatings were hardened at 120C. If coatings based on glycerol tricebacinate were hardened not at 120C but at 200C, their elasticity was smaller than for films
based on triadipinate formed at 120C. This is due to the fact that at this temperature, along
with the reaction between carboxyl groups and epoxy groups, there is probably a side reaction of carboxyl and hydroxyl groups, which, in turn, leads to an additional crosslinking.
From the data on the kinetics of increment and relaxation of internal stresses, the
changes of hardness in the formation of coatings from these compositions at 120C and subsequent operation of coatings at 20C, it follows that compositions based on glycerol trisuccinate and triadipinate harden well under these conditions, and compositions with glycerol
tricebacinate harden very slowly, so that the formation of coatings from them can be performed only at 200C.
The largest internal stresses emerge in coatings hardened by glycerol trisuccinate.
These data indicate that, as the length of branchings in ester acids, which harden the epoxy
oligomer, increases, internal stresses decrease, and elasticity of coatings goes up. If the
length of branchings is higher than the optimal value, which takes place in the introduction
of glycerol tricebacinate, the hardening of the composition at 120C is not observed. With
CHAPTER 8
b, MPa
6.0
263
5.0
4.0
3.0
2.0
1.0
10
, h
12
Figure 8.2 Kinetics of increment of internal stresses in the formation of epoxy coatings with glycerol trisuccinate (1), glycerol triadipinate (2) at 120C, with glycerol tricebacinate (3) at 200C.
E .10, MPa
0.5
1.0
3
4
1
0.4
0.8
0.3
0.6
0.2
0.4
0.1
0.2
Hardness, arb. u.
1.2
5
2
10
15
20
25
30 , h
Figure 8.3 Kinetics of increment of the elasticity modulus (13), hardness (46) in the formation
of epoxy coatings with glycerol trisuccinate (14) and glycerol triadipinate (25) at 120C, with
glycerol tricebacinate (36) at 200C, amounts of E in GPa.
the formation temperature increasing up to 200C, coatings based on this composition reveal the highest physicomechanical properties.
Coatings from a composition with a hardener based on glycerol trisuccinate and triadipinate under conditions of hardening at 200C spontaneously break down due to their
high embrittlement. Figure 8.1 presents a dependence of internal stresses for coatings of different chemical compositions on the thickness of the film. It is seen in the figure that coatings based on glycerol trisuccinate and triadipinate (hardened under optimal conditions),
are characterized by a high adhesion strength within a wide range of film thicknesses.
Figures 8.2 and 8.3 present the kinetics of internal stresses, elasticity modulus and
264
hardness in the formation of coatings based on epoxy copolymers with various hardeners.
It is seen that the formation of coatings at 120C ends up practically in 56 h, when the
physicomechanical characteristics reach their ultimate maximal value.
Table 8.2 presents the data on the effect of the nature of hardener on the maximal internal stresses, elasticity modulus, tensile strength and adhesion strength of coatings.
Table 8.2
Hardener
b, MPa
E, MPa
p, MPa
A, MPa
6.0
1.5
2.5
0.9
0.4
1.2
15.0
5.0
35.0
13.0
10.0
15.0
Glycerol trisuccinate
Glycerol triadipinate
Glycerol tricebacinate
A specific feature of coatings based on glycerol tricebacinate is that at a high adhesion

strength, hardness, tensile strength they reveal comparatively small internal stresses.
8.5
Protective coatings from copolymers of regular structure
To improve the performance properties of coatings to decrease internal stresses in them

at a simultaneous improvement of the other physicomechanical characteristics (adhesion,
strength) techniques have been developed to produce regular-structure epoxy copolymers.
The effect of the structure of macromolecules on the structure and properties of coatings from polyester-epoxy and silicon-containing polyester-epoxy polymers of irregular
(III) and regular (I, II) structure has been studied.
Polyester-epoxy oligomers were synthesized according to the following scheme:
O
O
C[CH2OC(CH2)nCOOH]4 + 2CH2 CHCH2ORCH CH2
C CH2OC(CH2 )nCOCH2CHCH2OROCH2CHCH2OC(CH2)nCOCH2
O
OH
OH
As the diglycidyl component, use was made of hydroquinone diglycidyl and diphenylol propane diglycidyl. Organosilicon polyester amidoepoxy polymers of regular structure
were produced in two stages. At the first stage, pentaerythrite tetraadipinate was condensed
with bis-(phenyl aminomethyl)tetramethyl disiloxane:
[CH2OC(CH2)4COOH]4 + 2HNCH2Si(CH3)2OSi(CH3)2CH2N
CH2OC(CH2)4C N CH2Si(CH3)2CH2N
O
H2O
C(CH2)4COCH2 C
O
The produced copolymers, which contained phenylamino methyl xylyl and carboxyl
groups, were converted to copolymers with the regular distribution of carbon atoms in the
network by the interaction with diglycidyl esters.
CHAPTER 8
130
265
b10, MPa
100
80
60
40
3
4
20
12
18
24
30
36 , h
Figure 8.4 Kinetics of internal stresses in the formation of coatings at 160C from copolymers I (2),
II (3), III (4) and epoxy oligomer (1).
We investigated the performance properties of coatings based on copolymers of the

following chemical composition:
O
C
OH
CH3
CH2OC(CH2)4COCH2CHCH2O
C
CH3
OH
OCH2C
CH3 CH3
CHCCH2OC(CH2)4COCH2C
CH2 OC(CH2)4CNCH2SiOSi
CH3 CH3
CH2NCH2CHCH2OROCH2CHCH2C(CH2)4OCH2C
OH
OH
Copolymer III represented a product obtained by the condensation of pentaerythrite

with adipic acid and diglycidyl ester of diphenylol propane at a simultaneous charging of
the components, and was distinguished by an irregularity of the structure.
To elucidate the effect of the composition and structure of polymers on the properties
of coatings, the kinetics of increment of internal stresses and other characteristics in the
hardening of compositions was studied.
From these data, it follows that the ordering of the structure of regular-structure oligomers contributes to a 23-fold decrease of internal stresses in the formation of coatings as
the result of relaxation processes prior to the formation of adhesion bonds in the formation
of coatings. Coatings from regular-structure copolymers are also distinguished by the stability of the properties (Figs. 8.4 and 8.5).
266
Hardness, arb. u.
E .104, MPa
0.6
24
0.4
16
0.2
5
6
10
15
20
2
3
25
, h
Figure 8.5 Change of the elasticity modulus (1 3) and hardness (4 6) in the formation of coatings
from copolymers I (1, 4), II (2), III (3, 6) at 160C.
From the analysis of the results on the kinetics of increment of the elasticity modulus
of these same films in the formation of coatings, it follows that the elasticity modulus reaches an ultimate value in 1015 hour of formation.
Films from copolymer II harden the most rapidly at 160C. The character of the dependence of internal stresses on the thickness of films for coatings from compositions of
various chemical compositions is linear.
Along with small internal stresses, coatings from regular-structure copolymers are
characterized by a high adhesion strength. From the comparison of the properties of coatings obtained from various copolymers based on oligomer ED-20, it follows that internal
stresses in coatings from compositions 1 and 2 are 4 to 10 times less than in coatings from
the initial epoxy oligomer hardened with polyethylene polyamine. Herewith, coatings
based on ED-20 peel off at a comparatively small thickness of 400 m. Films based on copolymers peel off at the same value of internal stresses at a thickness larger than 2500 m.
This is indicative of a much larger adhesion strength of coatings from copolymers as compared with coatings from the initial epoxy oligomer.
Table 8.3 presents the data on the physicomechanical characteristics of coatings from
regular-structure copolymers.
Table 8.3 Effect of chemical composition on the physicomechanical properties of coatings.
Film-forming
component
Copolymer I
Copolymer II
Copolymer III
ED-20
p, MPa
E, GPa
b, MPa
A, MPa
Margin of cohesion
strength
25.2
34.3
21.5
60.0
1.5
2.4
1.2
2.4
1.4
0.7
2.2
7.0
150
150
130
18
49
9
8
The tensile strength of films from regular-structure copolymers is 2050% larger than
for irregular-structure films, but 1.52 times smaller than the strength of films from ED-20.
However, in view of the small magnitude of internal stresses for coatings from regular-structure copolymers, their cohesion strength is 26 times higher than that of films from
oligomer ED-20. As the result, coatings from regular-structure copolymers are more durable than coatings from ED-20.
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267
Based on the regularities obtained, a composition based on epoxy oligomer ED-20 was
developed and a hardener with the regular structure of molecules; the composition hardens
for several minutes to form coatings with a high adhesion strength to metallized combined
materials from polypropylene and lavsan.
8.6
Combined metallized materials for dairy produce packing
8.6.1 Combined material based on polyethylene, paper and aluminium foil

Combined material consists of five layers, each of which has its own functionality:
the first (outer) layer from polyethylene; it is intended for protection of the paper base
from moisture and contamination;
the second layer from base paper of pure cellulose; density, 200250 g/m2. This layer is the load-bearing structure of a packaging to provide its good rigidity and to give it a
geometrically constant shape. These characteristics are obtained owing to long fibres, from
which paper consists. Besides, paper is a protective layer;
the third layer from polyethylene; it serves for glueing the paper base and aluminium
foil;
the fourth layer from aluminium foil 9 m thick. It is the most essential barrier for
the action of atmospheric agents and gases. Even at this thickness, there are almost no
microholes on the surface of foil. This layer also protects well the contents of a packaging
from the light, thus preserving for a long time the primary organoleptic characteristics of
products. Besides, the plasticity of this layer makes it possible to bend the edges of a package and its angles without flaws. This layer is required for induction heat sealing;
the fifth (internal) layer from polyethylene. Its thickness is much larger than that of
the first and third layers. It consists of two sublayers: the adhesion oxidized sublayer and
the unoxidized sublayer, which is in contact with the product. The main aim of this layer is
to enhance the protective barrier and to facilitate the sealing (longitudinal and two transverse ones).
Fabrication of a five-layer combined material includes the following operations: unwinding of the base paper, gas-flame treatment of the base paper, coating of the external
side of the paper with decorative printing and a layer of polyethylene, corona treatment of
aluminium band, application of the intermediate polyethylene layer between aluminium foil
and base paper, application of the bilayer inner coating from the melt of polyethylene on
the side of aluminium foil, cutting of edges, winding of ready material to rolls.
When elaborating the process regimes for production of combined material, the main
parameters of the lamination process were varied: temperature by the extruders zones,
working speed of the base sheet, temperature of cooling water at the input to the pressure
rollers of the laminators, frequency of rotation of augers at the startup, melting temperature
of polyethylene in the flat-die drawhole of the extruders, pressure of the melt of polyethylene before the package of the filtering meshes, working pressure of gas and air fed to the
burners of the gas-flame station, unit force of the laminators at the winding and unwinding
units, parameters of corona treatment of the surface of the base.
The parameters of the process were chosen such that to provide for good adhesion of
all five layers of combined material, to achieve the required mass of the polyethylene coating in an area of 1 m2 at a high rate of the process, to exclude the oxidation of the inner
polyethylene coating in contact with the product.
268
The following regime of the technological process for fabrication of combined material was established and used in production of pilot batches at the Enterprise for Production
of Packagings and Containers of the Kuban Agroindustrial Complex:
the temperature of the polyethylene melt applied to the base paper and foil is within
305312C for the external coating; 305318C, for the intermediate layer; 303324C,
for the oxidized layer; and 275281C, for the unoxidized layer of the internal coating;
the speed of travel of the base sheet, 10010 m/min;
the number of blocks on the corona discharge units, 4345;
the ratio of air and gas pressure in the installation, 37%;
the temperature of cooling water at the output to the pressure rolls of the laminators,
22C.
Good quality of the combined material is one of the essential conditions for the stable
operation of automatic filling machines at dairy plants. It provides for minimal losses of
packaged dairy produce in its transportation, storage and sales. Therefore, the correct choice
of the main parameters for the output control at the combined-material manufacturing
plants and the input control at the dairy enterprises is one of the major issues in the
producerconsumer chain.
When phasing in to the optimal regime of production, making it possible to produce
combined material of required quality, specimens from 22 pilot batches were chosen and
their physicomechanical tests carried out. The following parameters were taken into account: the mass of 1 m2 of polyethylene coatings (layer-by-layer), the thickness of combined material, adhesion of the polyethylene layers to the paper base, resistance to peeling
(aluminium foilpolyethylene).
Control of the mass of 1 m2 polyethylene coatings and bonding layer is required for
the correct monitoring of the production of combined packaging material based on paper
(paperboard) and aluminium foil and is of great significance for production of packaging
material of required quality.
A method of determining the mass of a 1 m2 polyethylene layer in the combined material based on paper and aluminium foil has been developed; the method was submitted as
the application for an invention and became the basis of a new methodology of determining
the mass of the polyethylene layer.
Simultaneously with the physicomechanical tests, the sanitary and chemical assessment of pilot batches of combined material was carried out in accordance with the Instruction and Recommendations of the Ministry of Health. Distilled water and a 0.3% solution
of lactic acid were used as model media. Extracts for studies were obtained under conditions
close to the operational conditions of packaging material. Model media were poured into
packs from the investigated material of 1 litre capacity. Upon filling, packs were hermetically sealed on a laboratory sealing machine at the regimes similar to the conditions of sealing in commercial automatic machines. Extracts were kept for 1 and 3 days at room
temperature. The organoleptic assessment of aqueous extracts was carried out by the method of extended triangle by the five-point scale at room and elevated temperatures
(4060C).
Sanitary and chemical investigations of test specimens of the material were also carried out with the aim to determine the extent of migration in extracts of low-molecular-mass
substances. The oxidizability of aqueous extracts was determined by the dichromate method. The content of brominated substances in aqueous extracts and lactic extracts was found
by the method of volumetric iodometry. The content of formaldehyde was assessed by the
method of thin-layer chromatography.
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The results of the studies have shown that in specimens of the final test batches of combined material the total migration of low-molecular-mass substances is insignificant; the
presence of formaldehyde was not found. The regimes at which the final batches were produced, satisfying the requirements of dairy industry by the sanitarychemical and performance properties, have been entered into the technical documents for the production of
combined material.
Thus, the effect of the process parameters on the quality parameters of combined material has been studied; the method of determining the mass of 1 m2 of the polyethylene layer has been determined; the nominal values of the parameters and tolerances for them have
been found; sanitary-chemical studies of the test specimens of combined material have been
carried out; the technological regulations for the production of combined material has been
developed; the technical specifications for a combined material based on paper and aluminium foil for packaging milk and dairy products have been developed and approved.
8.6.2 Hermeticity of polymer packaging
One of the main conditions for preserving the quality of a packaged product and preventing
its losses is the air-tightness of the packaging, which should not be disturbed on the way of
the product from producer to consumer.
At present, the air-tightness of various kinds of consumer containers from polymer materials in dairy industry enterprises is controlled visually. This control fails to provide an
objective assessment of quality and leads to losses of milk and dairy products during the
storage, transportation and sales.
Based on the literary and patent data in the field of nondestructive methods of control,
it is proposed to use the filled-system and optical methods of leakage detection for the assessment of the air-tightness of consumer containers used for packaging milk and dairy
products. These methods are informative, do not require complex equipment, are simple
and provide express information.
Two instrumental methods of operational air-tightness control have been developed:
the method of determining the air-tightness of consumer containers capped with foil with a
thermolacquer coating (the method of TL measurements) and the method of determining
the air-tightness of polyethylene packets of the type of Elecster and Finnpack using a photoelectric colorimeter (the method of PC measurements).
The essence of the TL method is to create a certain vacuum in a hermetically sealed
chamber with a capped (unfilled) consumer container. Due to the pressure difference inside
and outside the tested package, its shape and size change (it swells). If the package is
air-tight, after the removal of vacuum it acquires its initial shape. If the air-tightness of the
package is disturbed, no change of size is observed under the action of vacuum. When the
integrity of the package is violated during its exposure to vacuum, the leakage is determined
visually (breakdown, peeling and other defects) or (if there are microdefects) the package
is compressed after the vacuum is removed.
Tests of the consumer containers capped with foil with a thermolacquer coating were
carried out in a vacuum exciccator and in a vacuum cabinet at a maximum vacuum of 0.09
MPa. To determine the optimal conditions required for the assessment of the air-tightness
of consumer containers of 250 g capacity, the value of vacuum was varied within the range
of 0.0650.015 MPa, exposure time was from 1 up 10 min (Table 8.6.1). The result of the
experiment was taken to be the share of packages with violated air-tightness in percent.
At a vacuum of 0.0630.065 MPa, practically 100% of the specimens break down.
270
The vacuum of 0.0630.065 MPa for this type of packagings is critical and can be used as
a characteristic of strength of sealed thermoformed containers. It should be noted that the
parameter depends on the kind and quality of raw materials used to produce polymer sheet
materials (granulated polymer), on the geometric size and shape of the package, on the correct observance of the process regime of the fabrication of consumer containers.
Table 8.6.1 Data on the air-tightness of polystyrene containers.
Vacuum, MPa
Non-airtightness, in %, at exposure time (in min)
0.065
0.063
0.060
0.055
0.050
0.040
0.030
0.025
0.020
0.015
10
100
100
81.25
25
37.5
20.5
6.25
0
0
75
18.75
6.25
12.5
18.75
12.5
6.25
37.5
25
12.5
18.75
6.25
6.25
12.5
94
68.75
37.5
50
12.5
12.5
12.5
43.75
31.25
18.75
12.5
12.5
Note: The result was taken to be the mean arithmetic test of 16 specimens.
Analysis of the dependence of the share of non-air-tight containers on the value of vacuum at different exposures (Fig. 8.6.1) and that of the share of non-air-tight containers on
the exposure time at fixed values of vacuum (Fig. 8.6.2) made it possible to find the optimal
exposure time of specimens to be 5 min and the value of vacuum, 0.0150.04 MPa.
N, %
100
1
80
60
40
3
20
5
7
10 , min
Figure 8.6.1 Dependence of the share of unsealed containers (N) on exposure time. Residual pressure, MPa: 1, 0.06; 2, 0.05; 3, 0.04; 4, 0.03; 5, 0.025; 6, 0.02; 7, 0.015.
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271
N, %
100
80
60
40
3
20
1
4
0
0.01
0.02
0.03
0.04
0.05
P, MPa
Figure 8.6.2 Dependence of the share of unsealed containers (N) on pressure. Exposure time, min:
1, 10; 2, 5; 3, 3, 4, 1.
The final conclusion on the optimal characteristics was made based on the determination of the maximal load acting on a package in transportation, storage and sales.
To monitor the air-tightness of Elecster- and Finnpack-type packages, it was proposed
to test the optical method of nondestructive control. The method is based on the determination of traces of milk in water by the results of optical-density changes of water, in which
packs with milk were kept under a load. This approach makes it possible to reveal the presence of microdefects in milk packages in the case when it does not appear possible to assess
the absence of air-tightness visually. To reveal the presence of milk in water, use was made
of refractometers of RPL-3 and IRP-4 type (measurement of the refractive index), and also
a FEK-M photocolorimeter (measurement of optical density).
It has been found that the refractometric method can not be used for these purposes,
because the experimental data are within the error of the experiment.
Positive results were obtained using a FEK-M photocolorimeter. The maximal sensitivity of the instrument in this range of concentrations is observed when using cuvettes with
the working length of 3 cm and a yellow light filter.
The elaboration of the proposed method of monitoring the air-tightness was carried out
on 500-ml Elecster packages filled with milk; the packages were fabricated from imported
black-and-white bilayer coextruded polyethylene film. A washed and dried package with
milk was placed into a bath, into which 1 litre of water was poured; after that a load was
applied to the package, under which the specimen package was held for a certain time. Then
the package was removed from the bath, a sample of water was taken and its optical density
was determined on an FEK-M. It proved that for determining the optimal conditions of using the leakage-search method developed it is expedient to use packages with microdefects.
To determine under optimal condition the air-tightness of Elecster-type packages of 500
cm3 capacity, the load was varied within the range of 30 up to 70 N; exposure time, from
0.5 up to 2 min (Table 8.6.2).
272
Table 8.6.2 Results of the air-tightness control of Elecster-type packs (with microdefects).
Load, N
Exposure time, min
Optimal density
Content of milk in water, %
30
30
30
50
50
70
70
70
0.5
1
2
0.5
1
0.5
1
2
0.02
0.087
0.02
0.03
0.089
0.11
0.11
0.11
0.003
0.014
0.003
0.006
0.015
0.02
0.02
0.02
Note: In all cases the solution was clear.
Analysis of the experimental data and their recalculation for an additional load emerging in transportation, would enable making the optimal conditions of monitoring the
air-tightness of polyethylene milk packages of the type of Elecster and Finnpack more concrete.
These parameters were used to develop the protocol for determining the air-tightness
of polyethylene bags of the type of Elecster and Finnpack using a photoelectric colorimeter.
The developed methods of monitoring the air-tightness passed the metrological certification and were assigned the state register numbers.
The methods considered were included in The Book of Methods of Input and Production Control of Packaging Materials and Consumer Containers developed by the Laboratory of Packaging, All-Russian Research Institute of Dairy Industry (VNIKMI).
8.6.3 Coextruded polyethylene films for packaging dairy produce and
their quality indices
A widespread method of packaging milk at present is using disposable containers, which
became an integral part of the production process. The development and improvement of
the kinds of packaging is aimed mainly to preserve the quality and nutritive value of the
product.
The modern milk packaging should satisfy a whole range of requirements: it should
be harmless for man; to protect milk from spoilage, contamination and the effect of external
factors, such as moisture and foreign smells; to provide for the preservation of the product
in transportation and storage; to have a small mass and area; to have an attractive appearance; to be cheap and easy to handle.
One of the widespread methods of packaging milk is its production in soft polyethylene packs. Polyethylene film as a packaging material conforms to all the above requirements. Such of its properties as nontoxicity, strength, elasticity; vapour, water and gas
impermeability; chemical inertness, relative simplicity of the production process stipulated
the wide use of this material in dairy industry. Besides, polyethylene film is the cheapest as
compared with other packaging materials.
In this country, packaging of milk and dairy products is performed using filled polyethylene film produced by coextrusion from low-density polyethylene (LDPE), mainly of
grade 17504-006, with addition of 3% titanium dioxide and 0.08% slip additive Armide O.
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Titanium dioxide used as a filler is imported. In this connection, an important task is modification of coextruded films with the view to exclude or reduce the content of titanium dioxide.
The possibility of increasing the volume of production of this film and its modification
with the view of expanding the range of packaging materials has been studied.
Analysis of the home raw-material base and process equipment for production of films
made it possible to pinpoint the real directions of modification. Reduction of the consumption of materials in production of the film without deteriorating its properties is possible owing to the use of the features of the coextrusion method of production. The bilayer
polyethylene film produced by the extrusion method has no drawbacks characteristic of individual films; the use of this method reduces the probability of random defects. Also, it
makes possible the protection from the light due to the introduction of pigment into the outer
layer of the film.
Considering the above-said, and also based on the analysis of the existing range of
grades of LDPE compositions permitted for use by the Ministry of Health, new constructions of films have been proposed.
Test batches of films were produced at the Borisov Plant Polimiz on the Finnpack
equipment of the firm Tuomo Halonen (Finland) and Rotex 40 D (Germany). Four types of
coextrusion polyethylene film were produced (2, transparent; 2, semitransparent); LDPE
(base grade 17504006) and its compositions for them were fabricated by the Novopolotsk
Industrial Association Polimir (see Table 8.6.3).
Table 8.6.3 LDPE compositions for manufacturing coextrusion films.
LDPE grade
Content, %
titanium dioxide
Armide O
3.0
0.08
0.08
17504006
175132
175225
Regimes for the production of the films were identical for all their types (Table 8.6.4).
The types of the films are given in Table 8.6.5.
Table 8.6.4 Regimes of production of coextruded polyethylene films.
Specimen no
1
2
3
4
Equipment
Finnpack
Rotex 40D
Finnpack
Finnpack
Temperature at exit
Auger
from auger head, C rotation frequency,
rpm
190
190
190
190200
6010
400500
6010
6070
Extrusion rate,
m/min
282
2226
282
2530
It is known that the possibility of phasing in novel packaging materials intended for
contact with food products depends on a range of conditions. They include the results of
studies of the quality of films with the aim to assess their effect on the human organism, the
determination of the physicomechanical characteristics and the possibility of their use on
274
the packaging equipment. In this connection, the Laboratory of Packaging, All-Russian Research Institute of Dairy Industry (VNIKMI) conducted the sanitary-hygienic and physicomechanical tests of pilot batches of films.
Table 8.6.5 Design of experimental films.
Specimen no
1
2
3
4
Design of films
Transparent (no additives) / transparent

(no additives)
Transparent (with slip additive) /
transparent (with slip additive)
Transparent (no additives) / white
(with slip additive and titanium dioxide)
Transparent (with slip additive) / white
(with slip additive and titanium dioxide)
Polyethylene grade
for inner layer
for outer layer
17504006
17504006
175132
175132
17504006
175225
175132
175225
The sanitary-hygienic studies were conducted in accordance with the methodological

recommendations and the Instruction for Sanitary-chemical Study of Articles Fabricated
from Polymer and Other Synthetic Materials Intended for Contact with Food Products.
They included organoleptic and chemical studies of extracts of model media specimens of
a test bilayer coextruded polyethylene film, whose conditions corresponded to the
temperaturetime regimes of packaging from filled films with increased severity. Model
media were 0.3% distilled water and 3% lactic acid. The ratio of the inner surface of a pack
and the volume of the model medium was 1:1. Extracts were held at room temperature in
hermetically sealed packages for 1, 3 and 10 days. After exposure, the appearance of the
extracts was studied and their organoleptic assessment was performed.
Studies of the appearance of extracts showed them in all cases to be nonturbid and contain no residue. According to the results of an organoleptic assessment, at all temperature
time conditions of the experiment the intensity of smell of aqueous extracts did not exceed
1 point, i.e., the organoleptic properties of the film were stable.
Chemical studies of model media have been conducted with the view to investigate
migration of low-molecular-mass compounds in them. Migration of oxidizable and brominatable substances into model media was insignificant; no formaldehyde was found.
The strength characteristics were determined on an Instron tensile tester. The breaking
strength and relative breaking elongation were determined according to the State Standard
(GOST); the strength of the heat seal, in accordance with the procedure. Tests were carried
out in longitudinal and transverse directions. The static coefficient of friction was determined by the method of inclined plane.
Analysis of the obtained experimental data made it possible to assess the quality of the
bilayer coextruded polyethylene film in pilot batches and to give recommendations on the
changes to be introduced into the technical specifications.
To solve the issue of the suitability of unfilled (both transparent and semifilled) polyethylene film for filling milk and dairy products, it was tested in dairy enterprises. Based
on the results of integrated studies, recommendations were issued to use for packaging milk
and fermented milk drinks the unfilled (transparent) polyethylene film with sliding additive
in both layers and the semifilled polyethylene film with sliding additive in both layers and
titanium dioxide in one layer. These films combine the required physicomechanical and
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275
sanitary-hygienic properties and can be used in the dairy industry on M6-ORZE and Finnpack automatic packaging machines.
276
9
9.1
Technology of Forming
and Modifying Multilayer
Metallized Packaging
Materials
Purpose and production of multilayer materials
Packagings from composite plastics, including metallized plastics, find ever wider use in
meat and food industries. Often they are given the preference over traditional articles from
metal and plastics owing to their low specific mass, high mechanical strength and corrosion
resistance. Metallized polymer materials are dielectrics. They possess an increased resistance to the action of moisture, organic solvents, high temperatures, gas and vapour permeability during the boiling of packagings, as well as endow materials and articles with
specific performance properties resistance to the action of bacteria and molds, protection
of food products from ionizing radiation. To obtain a metal layer, use is made of such metals
as aluminium, copper, nickel, platinum, tin, lead, zinc, as well as metal alloys. A topical
problem is protection of the surface of these materials, the purpose of which is to decrease
the number of formation defects, to increase the resistance to cracking, scratching, as well
as atmospheric and biochemical resistance of materials, to improve the decorative properties. One of the promising and non-traditional ways of solving this problem is to develop
polymer composite materials with high adhesion to the metallized layer, resistant to the action of sterilization. This makes it possible to simplify the technological process of fabricating multilayer packaging materials as the result of reducing the number of layers and,
respectively, stages of extrusion lamination and adhesive bonding of film materials with foil
or the metallized layer, as well as to rule out the labour-intensive and expensive treatment
of the surface of substrate with a metallized layer and to reduce the treatment temperature.
The use of a lacquer layer for protection of combined packaging materials makes it possible
to develop systems, which can successfully compete with foiled packagings by their properties, technical and economic parameters and fields of applications. Calculations based on
the data by Russian enterprises show that transition from the production of combined materials based on foil to metallized packagings ensures a significant economy of raw materials.
In Russia, fabrication of packaging materials for food products had not received due
development, and sharply decreased in the recent years. At the international symposium
Food Packaging in Russia reports of experts on the TACIS program A strategic review
278
of packaging food products were discussed. It was noted that a significant drawback of the
Russian packaging branch of food industry was the absence of stable links in the raw-materials manufacturerpackaging manufacturerconsumer chain. The disruption of these
links is one of the main causes of the growing import of packaging materials and the low
level of home packaging production.
Domestic packagings were assessed from the point of view of their correspondence to
the main functions they should perform: integrity in transportation and storage, as well as
quality appearance to attract attention of consumers. Analysis of the statistical data on the
industrial-branch and regional level has shown that none of the regions in Russia produces
a sufficient quantity of packagings. Glass is predominant in fabrication of packagings for
food products (55% of the total volume), whereas in Europe and the USA its production
occupies only the third place in the packaging nomenclature. Plastic packagings and those
from corrugated paper make only a minor percentage in Russia, whereas in Europe and the
USA they occupy the first place. In Russia as compared with these countries, tin cans are
manufactured 4.5 times less; steel cans, 55 and 47.5 times; aluminium cans, 18.6 and 5.3
times less; films, 21.3 and 7 times; glass containers, 4.7 and 4.8 times; corrugated paper, 90
and 55 times; plastic packagings, 14 and 21 times less, respectively.
The volume of production of the main packaging materials in Russia, thousand tons:
polyesters, 67; thermoshrinkable polyethylene terephthalate, 2.9; thermoplastics, 20.3; materials from polystyrene, 17.5; A-grade paper for granular products, 10.6; base paper for
laminate used for milk and dairy products, 9.6; pergamyn, 3.7; supergomin, 4.4. Over the
recent years, there was a further decline in the production of packaging materials by about
30% per year.
Restoration of the production of packaging materials in Russia should be done by the
priority manufacturing of the most competitive and ecological packagings, which include
metallized materials. A number of industry-specific research institutes analyzed the major
directions and prospects of using polymer packaging materials, coatings and polyfunctional
layers. In the Russian state sector, the share of packaged meat foods is only 2.7%. By the
estimates of experts, losses of cattle and poultry meat due to the low level of packaging are
in Russia 1.6 mln tons, which exceeds their imports two times. A similar situation is observed for other kinds of foodstuffs.
Among polymer packaging materials, one of the most promising groups are metallized
packagings. They are economical: consumption of aluminium for their production is by two
orders of magnitude lower than for production of foil; they provide high protective and marketing characteristics, are maximally adapted both to modern food technologies and to processes of household culinary treatment of packaged products, for instance, in microwave
ovens. Herewith, the cost of the most expensive packagings does not exceed 58% of the
cost of packaged product, which is significantly lower than the cost of the losses of unpackaged products. In countries with the developed processing and chemical industries, the demand in metallized multilayer materials is permanently greater than the volume of their
production. This is due to the orientation of the processing industry to produce ready-prepared food products, for which metallized packagings provide optimal properties, such as
high barrier characteristics, excellent decorative properties and economic efficiency.
One of the largest potential consumers of containers with the coating based on modified polymer compositions is canning industry. At present, due to the general drop in production of foodstuffs, the output of canning containers decreased approximately two times.
Though sheet tinplate production is in Russia only 700800 thousand tons, in the USA
3600 thousand tons and in Western Europe 3500, it is still considerable and will increase
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279
with the stabilization of the economy. With this in mind, the issue of the development and
use of modified polymer compositions for metal containers is rather topical. Analysis of the
major technico-economic and ecological parameters of the production of modified compositions as compared with base systems and containers with these coatings shows that, at the
corresponding hardening conditions (rate and time) of the developed compositions, the basic expenses for production of containers shall differ from the base version only by the expenses for raw materials, which can be brought down by reducing the number of applied
layers. Herewith, containers with the developed types of coatings shall have higher decorative and performance characteristics.
The above-said supports the necessity and topicality of developing efficient methods
for protection of meat semifinished and ready-prepared products. Only by the wide use of
the practice of the developed industrial countries, it is possible to reduce the losses of foodstuffs during their delivery to the consumer by 5066%. An expansion of the output of such
types of polymer packagings as aseptic, sterilized, with preset barrier properties etc., would
make it possible to introduce progressive technologies of manufacturing food products of
high degree of preparedness and long-time storage; fast-frozen, freeze-dried, ready-to-eat
meals. Besides, this provides for the preservation of high consumer properties and reduction
of the mass of meat foods at the stages of their output, storage, use in public catering and
housekeeping.
More advanced processing of raw materials, realization of ready-to-use products and
with extended shelf life are considered in the West as the major direction of development
of food industry. Expenses for the production with extended shelf life are considered to be
5 times as low as for perishable products. It has been found that capital investment to prevent losses of mass of products are 23 times as low as those required to expand production
in the volume equal to the losses to be eliminated.
The possible increase of foodstuff reserves due to increased production of foods is limited. It is determined not only by the volume of resources directed to agricultural production, but also by limitations in environmental management. This stipulates to a significant
degree a lower dynamics of agricultural production as compared with industrial production.
For packaging of meat products, including frozen foods, use is made of consumer containers in the shape of trays from polyurethane foam, polystyrene foam, polyethylene foam,
polyvinyl chloride foam. Consumer containers from gas-filled foamed plastics are distinguished with a low density not exceeding 1560 kg/m3, with an ability to withstand significant specific loads without residual deformation, with a damping ability, elastic properties,
moisture resistance, chemical inertness, good hygienic parameters and low cost. Such containers make it possible to protect products from shocks, mechanical damage, temperature
variations, penetration of moisture and microorganisms; they have a low weight, increased
durability and low cost. Containers form gas-filled materials are fabricated by injection
molding, pressing, extrusion. Economy of materials is 3040%. The surface layer of a
packaging can be monolythic and rather strong. These containers can be overprinted, covered with lacquers and paints, glued with various glues. Gas-filled sheet materials are used
for fabrication of trays for meat by methods of pneumatic and vacuum formation.
Combined polymer materials with paperboard, paper and aluminium foil found wide
use for fabrication of consumer containers and food-purpose packagings. By their protective and shock-absorbing properties, they exceed significantly containers from wood, cardboard and other materials. Combined consumer containers and packagings from sheet and
film materials based on polymers provide for the high preservation of products, as well as
good consumer properties. Skin packagings are used for packing meat, fish and other goods.
280
They represent a paperboard support, on which an article close-wrapped on all sides

by a thermoshrink polymer film 30120 m in thickness is put. In packaging, the ends of
the film are fastened to the support by heat sealing, staples or glue. For shrinkage and close
wrapping, the film is heated. Additional stretching of material is done by vacuumizing or
by creating a pressure difference on both sides of the film. For this packaging, use is made
of thermoshrink films based on polyvinyl chloride, polyethylene, cellulose esters, polyvinylidene chloride.
Food products are transported in shipping containers produced by injection molding,
rotational molding from polypropylene or polyethylene, as well as trays from the same materials with low walls. These containers are also used as returnables in transportation inside
plant premises and within stores. Containers of this type are widely used for transporting
meat and dairy products. For packaging and transportation of moisture-capacity and frozen
products, including meat, use is made of polymers from corrugated plastic board. Packaging
is chosen with optimal protective properties, which provide for the required shelf lives of
goods and do not lead to excessive expenses. When choosing packagings, a range of physicochemical factors is also taken into account: temperature difference, effects of solar radiation, biological and aggressive media (sulfur dioxide, chlorides, ozone, hydrogen sulfide),
the possibility of moisture getting into products, aggressive chemical substances in products
themselves, the action of oxygen and air, the loss of volatiles by products (flavouring
agents, acquirement of foreign smells owing to evaporation of solvents and absorption of
foreign substances).
Stringent hygienic requirements are imposed on materials in the development of packagings for food products. Account is taken of the state of the product (powder, paste, liquid,
flocks, granules), its chemical activity (pH of the medium; occurrence of solvents, esters,
alcohols), as well as the physical activity (evolution of vapours and gases, their sorption,
delamination, change of tissue structure) and ability to change properties under the action
of temperature, light, moisture, oxygen, air. When choosing the shape and size of containers, account is also made of the consumption of polymer materials and the packing factor
of the packaging. Polymers, depending on the stress strain characteristics, can be rigid,
with the elasticity modulus greater than 1000 MPa; semirigid, with the elasticity modulus
greater than 400 MPa; and elastic or soft, with the elasticity modulus, respectively, greater
or smaller than 20 MPa.
When solving the issues of the possibility of packaging various types of products and
their preservation in transportation and sales, account is taken of a set of chemical and physical characteristics of polymers, the technological regimes of processing with consideration
of the thermophysical parameters, biostability, inflammability and vapour permeability. In
most cases, a whole range of ingredients are introduced into the polymer composition
plasticizer, thermostabilizer, stabilizerplasticizer, modifier of shock resistance and reproducibility, fillers, inks, optical bleachers, flavouring agents, lubricants.
When fabricating polymer film materials, use is made of single films from polyethylene, polyvinyl chloride, multilayer polymer films, such as polyethylene with polyamide as
well as polymer combined film materials based on polymers, paper, aluminium. Combined
film materials provide for properties of polymers and traditional materials, which makes
possible their wide use for packaging of practically all consumer goods. By the utilization
capacity, the first place is occupied by polyethylene, which has good process and performance properties (shock resistance, low temperature resistance, processibility of the article
on common equipment, as well as the lowest cost as compared with other polymer materials
produced in large volumes). The second place is occupied by polyvinyl chloride owing to
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281
its stability of shape, possibility of obtaining highly transparent packagings, good adhesion
of paints to the surface. Their drawback is a comparatively high brittleness, especially at
low temperatures. Besides, processing of polyvinyl chloride requires special equipment.
Strong, thin-walled and economical packagings based on single- and multilayer materials
are produced from polypropylene; however, it is used on a limited scale due to a small
low-temperature resistance. Other polymer materials are used for production of packagings
to a much smaller extent.
Protective polymer coatings are used for protecting the surface of packaging from corrosion, for instance, in packaging of meat preserves and sausage filling. They protect metal
from erosion during the action of atmospheric conditions, contacting media, mechanical
impacts. The use of protective coatings makes it possible to prevent the destruction in the
metallization of packagings from multilayer materials. For this purpose, use is usually made
of compositions based on modified epoxides, epoxy elastomers, epoxyphenol and other
systems. Bactericidal coatings are of great interest for protection from the impact of the microflora of meat and other products. Chemical preservatives are used for this purpose, for
instance, those based on glutaric, sorbic, benzoic and nitrobenzoic acids, their salts and esters. Preservatives are introduced into the lacquer composition, which is applied to the packaging material. However, commercially produced food-purpose lacquer-and-paint
materials, when applied to multilayer or combined films, reveal a low adhesion strength and
fail to provide for the required performance parameters. Protective antimicrobial coatings
on food products are also obtained by introducing antibiotics (nisin, tetracyclin and its derivatives) and chemical preservatives in the form of a solution in ethyl alcohol and a polymer film former followed by the dipping of food products (meat articles, fish) into the
prepared solution.
To prepare antimicrobial preparations, ions of metals with bactericidal properties (silver, manganese, magnesium) are introduced into carboxyl and hydroxyl groups of grafted
homopolymers, for instance, those based on polyester acrylates; then coatings on food objects are formed. This method requires special metal-containing food-purpose polymers to
be synthesized, and failed to find wise use.
When producing multilayer and combined packaging materials, use is made of surface
pretreatment for fixing individual layers of polymer. Physical and chemical methods are
used for this purpose, such as chemical degreasing, etching and the treatment of the surface
of articles with solvents, oxidants and halogens, as well as the chemical modification of the
treated material during its production. The most widely used techniques are the physical
methods of surface preparation of polymer materials, treatment by ionizing radiations and
electric charges; flame, thermal and mechanical treatments. In activation by corona glow
discharge, the surface of articles remains active for several weeks at a temperature of 5
up to +60C. Chemical etching is done before metallization and painting of the surface. It
is carried out at normal and elevated temperature by oleum, halogens, ozone, chromic mixture, nitric acid and other reagents.
To prevent inflammation during the production of film materials, antistatic treatment
is carried out, which contributes to the formation of an antistatic layer with increased electrical conductivity on the surface of the film to prevent accumulation of static electricity
charges. As antistatic agents, special surfactants and metal chlorides are used. In many cases, they worsen the performance properties of containers. More efficient agents are
high-frequency induction radioactive neutralyzersionizers.
The physiological harmlessness of polymer packaging materials is provided for by
their inertness with respect to the product with which they are in contact; by the absence of
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a chemical interaction and nontoxicity of substances evolved by the polymer. To determine

the harmful components washed out of packaging materials, the most efficient methods are
chromatography and mass spectrometry. The toxicological tests are carried out no less than
on two types of warm-blooded animals. Under conditions of the hygienic assessment of
polymer materials for packaging meat and fish products, a 5% aqueous solution of sodium
chloride at 20C is used as a model medium. The duration of the tests of polymer materials
is 5 days.
9.2
Prospects of using metallized packaging materials
To impart articles from nonmetal materials with high decorative and performance properties, a promising approach is to use a combination of two methods of finishing to obtain a
multilayer combined coating: first the application of the metal sublayer, then of the lacquer-and-paint material or only a colour pattern. In this case, the metal layer confers the
article an enhanced resistance to the action of high temperatures, moisture, organic solvents,
hardness and wear resistance. The lacquer-and-paint coating provides for the required decorative and performance properties, protects the metal film from oxidation. Besides, the
metallized coating makes it possible to use advanced methods of applying coatings to dielectrics, for instance, the electrodeposition method, formation of coatings by spraying the
polymer in an electric field, i.e., the most advanced methods under conditions of large-scale
production.
The range of rolled coating materials to obtain air-tight capping of consumer containers is limited. In world practice, mainly materials based on foil are used. According to the
data by the European Aluminium Foil Association, demand in the member countries of the
Association is increasing, its annual rise for the last 30 years was more than 7%. In spite of
the retardation of the general economic growth in the European countries, consumption of
foil per capita constantly increases. Analysis of statistical data confirms the stability of the
market for aluminium foil, high barrier properties of this material, which is used mainly for
packaging food products, drinks; pharmaceutical, hygienic and tobacco articles.
In connection with the necessity of improving the ecological situation, campaigns are
run in many countries to reduce the weight of packaging materials per unit. In the USA, for
instance, by the beginning of 2000 the aim was to reach more than a 25% decrease of the
weight of packagings. These tendencies also affected the production of materials with aluminium foil; the thickness of laminate in the recent years was decreased from 9 to 7 m.
As aluminium foils becomes more expensive on the world market, and due to increased requirements of consumers and developers of new types of containers to the appearance, weight and shape of packagings, in recent years significant attention has been
paid to production of metallized film materials. In the USA, their annual output is over 9
mln tons. Metallization makes it possible to significantly increase the protective and decorative properties of packagings at a small consumption of aluminium (100 times less than
foiled materials). In Russia, metallized films produced are based on polyesters and polypropylene, which possess a high density, impermeability for vapours, water, gases, aromatic
substances, ultraviolet rays. They are used for packaging the most expensive food products,
integrated diets, which are stored under severe conditions and are warmed up in the packaging.
Laminated materials based on metallized films can successfully replace glass and metal containers for packaging products subjected to sterilization, as well as for packaging of
cold drinks and juices. Drawbacks of the existing metallized packaging materials are low
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adhesion of the deposited metal layer to the polymer base, as well as its rapid breakdown
during the sterilization of packagings. Of great practical significance is the development of
the method of protecting the metallized layer in combined packaging materials. In world
practice, a drastically new type of packaging materials is widespread at present; the materials are produced by vacuum evaporation and condensation of metal layers 0.020.03 m
thick on polymer film, paper, paperboard. Material aluminized in vacuum is a competitor
of traditional aluminium foil, which has been produced by the rolling method for over 70
years. Metallization of the film or paper in vacuum gives a large economy of aluminium.
Metallization of 10 m2 of paper requires only 33 g of aluminium. To produce the same
amount of foil, 2.9 kg of aluminium is required. The use of packagings from metallized material enables the economy of 99% of aluminium at the same area of packaging material.
To endow metallized materials with the barrier properties and rigidity of aluminium foil,
they are laminated. As the result, the permeability of water vapours is decreased 46 times;
of oxygen, 3040 times.
The use of metallized films has a number of advantages as compared with common
materials. Packaging of products with a high content of fat into aluminized polypropylene
films increases the storage time up to 20 weeks. The use of only polymer films for this purpose leads to the emergence of static electricity, which worsens the air-tightness of the
package seam; a thin aluminium layer applied in vacuum decreases the charge of this electricity. Consumption of metallized films for packaging purposes is constantly increasing.
In the USA, the share of this packaging material is about 21% of the total production of
similar materials. The largest amount about 53% of the total production of packaging materials is the manufacture of metallized papers; 15% is the share of oriented polypropylene; 6, polyethylene; 2, biaxially oriented nylon and 3%, other metallized materials.
In Western European countries, manufactured metallized materials are used to produce (approximately in %): polymer films, 72; cellophane, 5; paper and cardboard, 22.
Their greatest part (about 31%) is used for fabrication of soft packagings of food products
and up to 25% goes for labels. Metallized materials are used especially extensively for production of ready-to-eat meals and entrs.
By their appearance, metallized packagings resemble aluminium foil, but their cost is
much lower. In recent years, the tendency is to use metallized materials with high barrier
properties with respect to oxygen and ultraviolet radiation, which is achieved by a significant improvement of the metallization process with the aim to increase the resistance to
multiple bends, elimination of micropores and of the tendency to cracking. There is a tendency to increase the output of multilayer materials for packaging of food products, which
is stipulated by the diversity of the physicochemical and mechanical properties of polymer
packagings, simplicity of processing, reliability of the raw material base, low energy consumption as compared with production of packagings from other materials of similar capacity, for instance, glass containers. The small density of polymer materials from 0.9 up
to 1.5 g/cm3 makes it possible to save on transport expenses. The cost of packagings from
polymer materials is lower.
At present in Germany the consumption of multilayer packaging materials is about
27%; only the demand for glass is greater 39% with respect to the total volume of production of packaging materials. The most widely used are multilayer polymer materials,
90% of which is for packaging. This is due to the fact that single-layer films do not satisfy
the ever increasing requirements to packagings; in particular, the guaranty period of storage
of food products, the preservation of their taste qualities, reliability in transportation. To increase the storage times of meat products, the number of layers in packaging materials, met-
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allized materials including, is significantly increased. Multilayer films include from 2 up to

7 layers. The average thickness of one layer is about 10 m, including with the metallized
layer. The lower layer of the material about 20 m in thickness are mainly polyolefins
(polyethylene, more rarely polypropylene). For this layer, low-density polyethylene is used,
owing to its low melting temperature, capability of thermal treatment, reasonable cost. Multilayer materials with the lower layer from low-density polyethylene are used for packaging
products subjected to pasteurization at 85C. At the sterilization of packaged products at
100C and deep freezing, use is made of multilayer packagings with the lower layer from
medium-density polyethylene. Frozen products can be warmed up at 100C. High-density
polyethylene is used for the lower layer of multilayer packagings for preserved products,
sterilized at temperatures no less than 121C. The average thickness of multilayer films is
from 20 up to 1500 m. Depending on the purpose and properties of individual layers, multilayer films can be used within the temperature range of 60 up to +135C. They possess
a high strength of the heat seal, moisture resistance; fat and oil impermeability; resistance
to acids and alkali, solvents, microbial impermeability. For packaging of meat, meat products, semi-finished products and ready-prepared meals, the company Vipack, which is
part of the Finnish concern, manufactures multilayer polymer films. At the exhibition Interpack-90, Germany presented packagings for processing foods in microwave ovens; the
packagings are fabricated from pressed polyesters filled with nylon, polysulfone, polyacrylate, polyoxyphylene with polystyrene. Their surface is metallized with aluminium or alloyed steel. In such a packaging, a food product after its treatment in the microwave oven
acquires a crispy crust. Metallized multilayer packaging materials are used for packaging
and storing meat-and-vegetable preserves for 2430 months. For this purpose, use is made
of metallized materials based on polyamide and polypropylene, oriented polypropylene and
polyethylene films. They are characterized by high performance properties, their resistance
to delamination is 290196 N/m, the breaking strength 4934 MPa, relative breaking elongation greater than 10%, resistance to puncture greater than 9.8 MPa, strength of the heat
seal 15001200 N/m, resistance to delamination after sterilization in an aqueous medium
greater than 147 N/m, strength of the heat seal after sterilization in an aqueous medium is
1050840 N/m.
9.3
Polymer films as the base for metallization
Film materials used for packaging of food products require a set of the following characteristics: technical-grade strength in monoaxial and biaxial stretching, resistance to multiple
bending, to temperatures increased in sterilization of products and decreased in freezing
products; protective permeability for gases and vapours; radiation resistance; process factors resistance associated with the packaging process at a high-speed automated equipment with account for the friction coefficient, static coefficient, caking property, capability
of heat sealing; sanitary and hygienic factors extractability in various model media; extent
of toxicity; aesthetic factors appearance, overprinting capability.
The properties of films are determined by many factors and, first and foremost, by
compositions of initial polymer and of the composite as a whole, by processing conditions.
Usually, the film is produced from polymer by the method most efficient for the polymer:
from low-density polyethylene, by extrusion blowing; from polyvinyl chloride, by calendering; from rubber hydrochloride, by solution casting. Considering the peculiar features
of the structure and properties of film material, the most efficient method of creating a packaging material with a set of required performance properties is by combining. Combining
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films and coatings, it is possible to produce packaging materials with required properties,
which are impossible to obtain using one polymer in pure form. For instance, a coating from
a thin layer of lacquer considerably decreases the rate of removal of a plasticizer, increases
moisture resistance, can ensure heat sealability. Coextruded bilayer films for milk packaging are fabricated based on low-density polyethylene filled with titanium dioxide and carbon black. An advantage of multilayer film materials is their low weight. Containers from
them are 410 times lighter than metal containers and 20 times lighter than glass containers;
they withstand a rapid heating, easily open, are economical, are distinguished with small
energy intensity.
Containers and packagings should be air-tight and resistant to the action of preservatives, such as solutions of sorbic acid, sodium acid or potassium acid. Polymer containers
for freezing products from 12C to 40C and lower should withstand the heating before
the products are used. Polymer packaging material should satisfy some or other requirements depending on the packaging and the properties of products. Food industry consumes
about 50% of all polymer materials used for containers and packagings. Along with general
requirements (mechanical strength, chemical endurance to the action of food products and
the environment, physiological harmlessness), additional requirements imposed on them
are manufacturability, processibility on modern packaging equipment operated in speed regimes, resistance to sterilization and pasteurization, as well as capability of forming a strong
seam in heat sealing.
A promising approach is to use polymer packagings in combination with aseptic canning. This method is applicable for products and containers, which do not withstand a prolonged impact of high temperatures. To increase the storage times and obtain film materials
with the required set of properties, food products in polymer containers are treated using
high energies. Sometimes, a mixed treatment by irradiation with high-energy frequencies
and the action of temperature is used. For rapid warming-up of the product in a microwave
oven, metallized materials are used. The process is performed as the result of intensive absorption of electromagnetic energy by metal. The high melting temperature of polyethylene
terephthalate provides for the preservation of the strength of films. The same role is played
by this film in packagings of frozen products when they are cooked or warmed up in microwave ovens; herewith, a crispy crust is formed on food products, which is not observed
using polymer nonmetallized packagings. To produce similar products, use is made of combined packaging materials, on particular sections of which a different number of layers is
formed. Packaging materials intended for warming up meals in microwave ovens have high
barrier properties with a regulated layer, which determines the intensity of warming-up. The
packaging with a metallized layer, as compared with foil, protects the product better and
has higher decorative properties, as it does not crack or crease.
Films of metallized metapropylene are produced. Also, combined packaging material
is fabricated, using the method of coextrusion of metallized film with transparent polypropylene film. Both films form a strong heat-sealed seam. When fabricating packagings, metallized films are additionally coated with a layer of ink printing and are laminated with a
layer of transparent polypropylene film. In the USA, metallized laminated polymer packaging material for food industry has been developed, which possesses a high elasticity,
strength, is impermeable for gases and vapours, aromatic substances and UV rays. An advantage of this material is also its small weight.
Material in the form of one or two layers of polyolefin film with a metallized coating
is used for fabrication of canisters 320 litres in capacity. Materials produced by forming a
metallized coating on paperboard and other polymers are used for aseptic packaging of food
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products. For production of metallized materials, use is made of the method of transferring
metallization on paper and cardboard. First, the film support is coated with lacquer, on
which a layer of metal is applied by the vacuum method. Then the surface of metal is covered with a layer of glue, on the other side of which paper is rolled on. After that, the initial
film support is removed. This method is used for metallization of films, which can not be
decorated with metal using the usual vacuum method, or the preparation of the surface of
which requires significant expenses and auxiliary substances. The transfer method is used
to metallize materials of the type of pack in box for wrapping meat and products to be
warmed up in microwave ovens, as well as for packaging confections and coffee.
A method of producing metallized materials has been developed in Germany. The
method provides for spraying of a metal layer on one of the films of a multilayer material
formed; the films are then joined by glueing followed by thermoflattening of the multilayer
film.
To produce material with selective gas permeability, a layer of palladium is sprayed
onto the base under vacuum. The metallized coating is protected with a layer of organic
polymer, which possesses a selective gas permeability; the polymer is based on low- or
high-density polyethylene, polypropylene, copolymer of ethylene with propylene or with
ethylacrylate, polybutene-1, ionomer of poly-4 methyl pentane-1 and (or) polybutadiene.
Copper-foil film materials are produced by applying first a 280 m-thick layer of zinc on
the copper support by vacuum spraying, and then layers of silicon oxide or aluminium oxide. After that, copper with a two-layer coating applied to it is laminated with the film base.
The method provides for high adhesion of copper to the film base via an intermediate
two-layer coating. When producing the intermediate polymer film, glueing of the layers can
be done by sulfated copolyester containing an alkaline metal.
To protect films from UV rays, a stabilized transparent combined material has been
proposed, which is a biaxially oriented polyester film joined with a metallized film from
polyethylene terephthalate coated with colour lacquer.
Material capable of heat sealing represents a thermoplastic polymer layer and metal
foil or metallized flexible sheet.
Films from plasticized polyvinyl chloride 0.5 mm in thickness, used for packaging
food products, have a layer of primer with aluminium 50 m in thickness sprayed on it. To
protect the metal layer, use is made of polymer coatings from acrylic copolymers, modified
polyisocyanates containing inks, which harden at the action of UV radiation.
In packages from oriented polypropylene and metallized polyethylene terephthalate
film, food products can be stored for 68 months.
Materials subjected to metallization include crystalline polyolefins (oriented polypropylene, polyethylene), polyester films (polyethylene terephthalate). To improve the adhesion and decorative properties of metallized coatings, use can additionally be made of
various compositions applied directly to the coating, for instance, sulfated copolyester containing alkaline metals, colour lacquers.
Metallized polyester films widely used for various purposes are more resistant to friction and stretching, which provides for a high stability of shape of the packagings. The use
of these films makes it possible to increase the speed of overprinting and to reduce the consumption of ink by 30%.
The use of metallized polymer materials increases annually not only owing to good
decorative properties, but also due to the vapour and water impermeability, decreased heat
and light transmission, as the result of which the service life of food products, especially
meat and dairy, is significantly increased.
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Metallized materials are used in fabrication of containers for transporting the products.
An advantage of a thin metal layer is the absence of thermal conductivity outside the container owing to its small mass. Losses of heat are absent even in the contact of the metallized
surface with components of the outer walls of the container.
The metallized film proposed by the company Kraun Sellerbach (USA) is used for
packaging of food products. Its main part is a multilayer polyethylene film, which provides
for thermal insulation. Aluminium is applied to the base by vacuum metallization, which
prevents the penetration of moisture, gaseous and aromatic substances, as well as light. By
means of extrusion or adhesion, the metallized film is layered onto paper or films, for instance, polyester, nylon, cellophane or polyethylene ones depending on the requirements.
Such a film has various advantages, the major of which is its universal properties. For instance, if it is required to exclude the penetration of gaseous substances, the film can be
joined with cellophane. The use of only one layer of cellophane provides for the resistance
to the penetration of gas up to a level equal to 0.3 cm3 for 24 h at 40.5C and relative humidity 45%. Herewith, the moisture permeability does not exceed 0.03 g for 24 h for a surface area of 645 cm2 (100 square inches). Another example of the universal properties are
high thermal insulation parameters of the film, which is provided for by the introduction of
an additional thermal insulation material 0.025 mm in thickness, for instance, polyethylene,
films from latex or other resins. This characteristic was revealed in the tests of wrappings.
An insignificant time of contact of the thermal insulation with the metallized base at a productivity of 180 packagings per minute weakens the insulation on the edges. Addition of a
layer from the monomer eliminated this drawback.
The film possesses isolating properties characteristic of foil, thus preventing the passage of moisture, whose amount does not exceed 0.05 g per 645 cm2 of the surface for 24 h.
The penetration rate of oxygen is 10 cm3 per the given surface area at the deposition of this
material on paper and less than 4 cm3 at the deposition on film. The extent of penetration
of the light corresponds to 1%. The film can be easily bent. The metallized surface is between two layers, which protect the film from the emergence of holes and cracks at pressing.
A major advantage are constant insulation characteristics of the film at the action of pressure on it. The film is used for packaging of meat products.
Examples of packagings from the film by US companies for retail goods are bags lined
with paper, intended, in particular, for nonfat dry milk, packaged meat products, for solid
spice mixtures and fried potatoes. A laminated bag based on this film for packaging acidic
appetizer spreads received a highest award at an exhibition held in Moscow at the Red
Presnya Exhibition Centre. For a more attractive appearance, metallized bags are fabricated
in various colours (blue, yellow, red) and are overprinted with four-colour images of snacks.
The company also fabricated various packaging shapes for aroma drinks, ground coffee and
lining for boxes with articles from crushed grain.
The US food industry also makes use of metallized films: cellulose, coextruded
polypropylene and polyester. The metallized cellulose film has an excellent appearance, is
used for packaging meat and other products. The relative breaking elongation of metallized
polypropylene is 6575% (longitudinal) and 8090% (transverse); of metallized cellulose
film, 2025 and 5565%, respectively.
The low specific weight, good mechanical and protective properties stipulate the wide
use of metallized polymer film materials. Unlike plastics, they are characterized by a large
value of surface with respect to volume and a capability of adhesion interaction with applied
layers of other materials. The structure and properties of polymer films vary along the thickness and depend both on the chemical composition of the polymer and on their production
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process. These parameters have a significant effect on the structure and properties of polymer and metal coatings applied to the films. Regulation of the processes at the filmcoating
interface makes it possible to reduce significantly internal stresses, to improve the physicomechanical and other performance properties of materials.
Films used for metallization should satisfy a number of requirements. Thus, to obtain
high-purity metal coatings it is necessary to use polymer materials with an insignificant gas
evolution and as low as possible content of volatile components in the polymer. A necessary
requirement is also the high thermal resistance of films relative to the heat radiation from
the source of spraying, good adhesion properties to deposited metal, high strength.
The depth of vacuum, quality of film, formation of folds, displacement and density of
the roll in production of the film in metallization units with the rolling mechanism are affected by the nonuniform thickness of the film, friction coefficient, mechanical properties,
thermal resistance, conditions of charging with static electricity, as well as the dose of gas
separation. At a high gas evolution by the film, preliminary degassing or lacquering are
used, which prevent evolution of volatiles from the film in the process of metallization. Superthin films with a large surface area with respect to volume are in high demand. Polyethylene terephthalate films have the specific surface 600 m2/kg at a thickness of 2.5 m.
However, thin films are more difficult to process into articles. The processibility of the film
in rolling is greatly affected by its unevenness. Before its use for packaging, the film is powdered; the powder should be uniformly distributed along its surface, which provides for its
better winding as compared with smooth films.
Apart from the main physicomechanical characteristics, such as ultimate tensile
strength, relative breaking elongation, the films are also characterized by tear resistance and
tear propagation resistance, resistance to bends, elasticity, coefficients of thermal expansion
and swelling, extent of transparency. Special grades of polymer films are produced to fabricate quality metallized materials of particular purpose.
Stronger but less transparent films are used to fabricate coloured embossing foils. To
increase adhesion to lacquer and metal coatings, the surface of the polymer film is activated
mainly by corona discharge. Activation contributes to the increase of the surface tension of
films by 40% as compared with nonactivated films.
Practically all polymers capable of yielding solutions or passing into a viscoelastic
state in heating possess the film-forming properties. Films are usually produced by evaporating the solvent from the thin layer of a solution applied to the support (sometimes with
the separating layer to facilitate the removal of the film from the support), or from the melt
using a forming tool followed by cooling of the film.
Linear polymers are used to produce films. The minimal degree of polymerization, i.e.,
the number of homotypic links in the polymer chain, at which strong films are produced
from polyvinyl chloride, is 500700; from polyamides, 100200. With the decrease of the
intensity of intermolecular interaction and flexibility of the chain, stronger films are produced at a smaller molecular mass.
A significant increase of the extent of polymerization does not lead to any significant
increase of strength, but only hinders the processing of polymer owing to the low yield in
heating and poor solubility.
9.4
Methods of modifying the properties of films
Most film materials usually contain auxiliary substances: stabilizers, plasticizers, inks and
pigments, antistatic additives. The purpose of stabilizers is to preserve the properties of the
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polymer film invariable and to prevent the occurrence of chemical reactions under the action of the environment.
The role of other auxiliary substances is to impart the polymer film with additional
properties required for processing it into articles. Stabilizers are artificial nuclei of crystallization and significantly affect the structure of the film. Structural transformations are regulated by introducing surfactants into melts; surfactants decrease the rate of crystallization
as the result of a surface energy decrease at the spherolitemelt interface. This impedes the
growth of spherolites, but increases the rate of nucleus formation owing to the decrease of
the size of crystalline nuclei. The rates of these processes depend on the nature of surfactants and their concentration.
Of great practical importance are plasticizers. Plasticizers used are organic compounds
imparting polymers with plasticity and extending the range of their rubberlike state. They
increase the low-temperature resistance of polymer, resistance to impact loads; facilitate the
processing conditions. Introduction of plasticizers causes an increased mobility of polymers structural elements due to the decrease of intra- and intermolecular interaction. The
chemical nature and quality of plasticizer introduced render a significant effect on the structure, physicochemical properties, permeability of films to various vapours, liquids and gases; on the resistance to atmospheric conditions and microorganisms.
Migration of the plasticizer, owing to the impact of the external medium, also leads to
undesirable changes of the structure, especially of films, because they have a large surface
area and small thickness. In production of polymer films, polymers to be plasticized are
those that are used for fabrication of packagings, such as polyvinyl chloride, copolymer of
vinylidene chloride with vinyl chloride, cellulose and its esters.
Specific requirements to films for various purposes stipulate the choice of plasticizer.
The main requirements to all plasticizers are compatibility with polymer, small volatility,
high chemical endurance at various temperatures. The minimal temperature at which material preserves its performance properties characterizes its low-temperature resistance. The
presence of aromatic fragments in the plasticizer molecule negatively affects its own
low-temperature resistance.
Polymer plasticizers are oligomers with molecular masses from 1000 up to 8000 and
are polyesters of dibasic alcohols. They endow film materials with valuable performance
properties. Polymer cebacinates possess a good resistance to oils, water, detergents,; an insignificant yield, absence of migration, high dielectric properties, compatibility with polyvinyl chloride. However, they are expensive.
Adipinates are less expensive, possess a small yield, migration, good dielectric properties, but are less efficient, leached with water, impart PVC films with a smaller low-temperature resistance.
Phthalates are well matched with polyvinyl chloride and improve its processing; do
not migrate and are not extractable with oils. However, at low temperatures they worsen
the properties of films. Other polymers are also used for plastification. Thus, for polyethylene and polypropylene, it is polyisobutylene; for polyvinyl chloride, chlorinated polyethylene and copolymers of butadiene and acrylonitrile. The efficiency of their plasticizing
action is higher for restrictedly compatible copolymers.
Low-molecular-mass plasticizers increase elasticity and low-temperature resistance of
the film, but worsen its resistance in liquid media; decrease tensile strength, increase the
permeability of vapours and gases through plasticized film, which is indicative of the formation of a defect inhomogeneous structure.
Physiologically safe plasticizers (permitted to be used in polymer films of food
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purpose) are used in fabrication of packagings for food products. However, even in the case
of using nontoxic plasticizers it is necessary to take into account their volatility and the possibility of extraction by food media, which leads not only to the change of properties of the
film itself, but also to the emergence of foreign taste and smell in food products.
Inert high-molecular-mass compounds are used for packaging. A source of hazard in
them are low-molecular-mass components, such as the residual monomer, emulsifiers, stabilizing plasticizers, as well as substances formed as the result of decomposition in processing and operation of articles. Harmlessness of all ingredients introduced should be taken
into account in production of packagings. However, even in this case it is impossible to
guarantee the inertness of the material due to the difficulty of determining the interaction
of all its constituents between themselves and with the medium. With account for this, it is
necessary to carry out the sanitary-hygienic and toxicological assessment of the material.
The conclusion of the possibility of its use is made based on tests in individual media imitating the composition of the liquid phase for food products (bottled water, vegetable oil,
weak solutions of cooking salt, bicarbonate of soda, hydrochloric acid, 50% ethyl alcohol
etc.).
Determination of the extractability of particular components with model media is preceded by the organoleptic assessment of the material and the aqueous extract on the absence
of taste and smell, as well as by the establishment of the character and amount of substances
migrating into these media.
Introduction of low-molecular-mass substances into the composition, as a rule, affects
unfavourably the sanitary-hygienic characteristics of film materials. Plasticizers, by increasing the flexibility of chain macromolecules, improve the low-temperature resistance
of the film but can migrate and contribute to migration of other components in the liquid
medium, thus worsening its protective and mechanical properties, as well as the quality of
overprinting. The small thickness of films hinders the modification of their structure by fillers and powdered additives (pigments, modifiers etc.); the latter should be finely dispersed
and actively interact with the polymer.
9.5
Structure and properties of film materials
The peculiar feature of polymer films, including those used for packaging, is that they are
characterized by a structure, which is inhomogeneous along the thickness of the film. This
is typical in the formation of films from crystalline polymers on various supports. In production of films from the polyethylene melt, the adsorption interaction of polymer with the
surface of the support prevents the formation by crystallites of more complex lamellar-type
supramolecular structures, which are formed in layers bordering with the air. However, the
mobility of structural elements, which is required for complex supramolecular structures to
be formed should, apparently, be optimal. This is indicated by the data in the formation of
films from powdered compositions of low-density polyethylene, obtained by preliminary
holding over vapours of a solvent (xylol). Swelling of the surface layers in vapours of the
solvent contributes to the decomposition of their lamellar structure and its formation in layers bordering with the surface of solid bodies.
Optical studies of thin transverse sections (1520 mm) of films from powdered polytrifluorochloroethylene revealed an inhomogeneous supramolecular structure along the
cross section. Hardened films, in the zone of contact of polymer with the support, were
found to have fine supramolecular formations. Large-spherolite films formed at a melt cooling rate of 1 deg/min were found to have a 5070-m-thick layer of structural elements,
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occurring in spherolites, at the interface with the support. Studies of the structure of longitudinal cross sections in this zone found it to be homogeneous fine-spherolite one in the
polymer. The size of spherolites increases by an order of magnitude in passing to the layers
bordering the air. The support plays the role of a nucleating agent and contributes to a faster
and more complete ordering of the structure. The effect of structural inhomogeneity on the
melting and crystallization temperatures of polytrifluorochloroethylene along the cross section of the film was studied. It was found that polymer begins to melt in the surface layers
of the film. The layer at the interface with the support melts 1015 min later at a temperature 12C higher than the subsequent layer, and crystallizes 4060 min earlier than they
at a temperature 46C higher. Thus, the texturing influence of the support leads to the
two-stage process of crystallization of films and to the inhomogeneity of the structure along
the thickness.
An inhomogeneous structure (along the thickness) is formed in films from solutions
of polystyrene (PS). When they are produced from solutions of PS in carbon tetrachloride
in layers bordering with the air, a structure of the type of quasicrystals is formed, which
group into networks. However, X-ray patterns of tactic polystyrene indicate that the polymer is amorphous. Etching of films reveals a globular structure with a denser packing of
structural elements at the interface with the support. In the surface layers of the films, along
with the globular structure characteristic of polystyrene blocks, we observe secondary supramolecular structures. The character of the arrangement, the morphology and extent of
ordering of these structures depend on the nature of solvent. This is, evidently, due to different solubilities of polystyrene in solvent naphtha, xylol, carbon tetrachloride; different
rates of their evaporation in the formation of films; as well as to the effect of the values of
internal stresses and strength of interaction at the polymersupport interface on the orientation of structural elements. The largest secondary supramolecular structures of up to 45
m in size are observed in films formed from solutions of polystyrene in xylol, which is
distinguished by the highest boiling temperature. In films from solutions of polystyrene in
solvent naphtha, the size of the secondary needle-type structures decreases down to 34
m. The smallest size of the structural elements forming a network (0.20.3 m) is observed to occur in films obtained from solutions in carbon tetrachloride. The size of the predominant globular structure also depends on the nature of solvent.
The finest globules 3070 nm in diameter are found in films formed from solutions in
xylol. With the quality of solvent worsening, their size increases up to 50100 nm for films
obtained from solutions in solvent naphtha; up to 80400 nm, from solutions in carbon tetrachloride.
To elucidate the role of solvent in the formation of the properties of coatings, we investigated the influence of its nature on the drying process, the change of internal stresses,
the physicochemical characteristics. It was found that the drying of films from solutions of
PS in carbon tetrachloride is completed sooner than of those from solutions in o-xylol; herewith, the solvent elimination rate, irrespective of the nature of solvent, is much higher than
the rate of increment of internal stresses. Upon removal of 7080% solvent from the system, comparatively small internal stresses emerge in the films. They reach an ultimate value
at no more than 13% of the solvent. The thermal conductivity coefficient of films decreases with internal stresses increasing. Its value and kinetics also depend on the nature of solvent.
Structural transformations at different stages of solvent elimination were studied. The
size of globules found at the early stages of solvent elimination at 80C in 510 min was
found to be about 30 m and gradually increased owing to their aggregation. A sharp in-
292
crement of internal stresses was observed upon completion of this process owing to the formation of local bonds between these elements.
The high mechanical, adhesion and thermophysical parameters are observed for films
formed from in xylol; they feature a more homogeneous fine-globular structure with a small
content of secondary associates.
Tables 9.1 and 9.2 present the data on the nature of solvent on, respectively, the physicomechanical and thermophysical characteristics of polystyrene films and on the shearing
and tearing strengths of glue layers produced from solutions of PS.
Table 9.1
Solvent
Xylol
Solvent naphtha
Rupture
strength,
MPa
Internal
stress,
MPa
Adhesion,
MPa
Thermal
conductivity,
W/(mK)
Thermal
diffusivity,
108 m2/s
13.5
12.8
12.0
1.0
0.7
0.4
1.6
1.0
0.7
0.28
0.27
0.24
5.15
4.84
4.70
Table 9.2
Solvent
Xylol
Solvent naphtha
Type of failure
Shear
Tear
Shear
Tear
Shear
Tear
Strength of films (MPa) at testing temperatures, C

40
20
20
40
60
3.44
0.78
3.96
0.75
3.22
0.78
6.45
0.94
5.84
0.85
5.05
0.58
5.90
0.90
4.52
0.90
4.60
0.82
5.47
1.83
2.70
1.72
3.40
1.35
2.30
2.50
0.68
1.32
2.14
1.80
Specimens were prepared as follows. A solution of polystyrene was applied to the surface of aluminium plates, the coatings were dried at 20C for 25 h, then bonded under a
pressure of 1 MPa during 10 min at 100C. From the data of Table 9.2, it is seen that at a
testing temperature higher than 40C both in tearing and shearing tests the highest values
of adhesion strength are observed in most cases for glue layers of films produced from solutions of PS in xylol.
Internal stresses in polystyrene films significantly depend on the chemical composition and structure of the material on which it is formed. We investigated the kinetics of increment of internal stresses in the formation of films from solutions of PS in xylol, solvent
naphtha on steel and copper supports obtained by metallization in vacuum. Depending on
the nature of the support, the values of internal stresses and the rate of their increment
change significantly. Stresses increased with the quality of solvent and the strength of adhesion interaction improved. These data indicate that polymer coatings with optimal protective properties, internal stresses and adhesion strength can be produced by regulating
their structure by means of modifiers.
Methods of decreasing internal stresses and improving the performance properties of
combined polyvinyl chloride films were developed.
Particles of powdered PVC used for fabrication of films represent complex secondary
CHAPTER 9
293
supramolecular formations. They are not destroyed completely during the swelling in plasticizers and the heating of compositions in processing. To improve the performance properties of films, an efficient method is to modify compositions by structure formers, which
disperse particles in plastisols. Dispersions of polyvinyl chloride are modified using synthetic fatty acids (SFA); the effect of the molecular mass of their hydrocarbon radical and
of the valency of the cation of the salts on the character of structural transformations and
properties of films was studied. PVC plasticized by dioctyl phthalate was modified by magnesium salts of SFA with hydrocarbon radical of various molecular masses (C7 C9,
C10 C16, C17 C20), as well as by a sodium salt of SFA of the series C10 C16 and aluminium stearate. The composition was held at 90C for 1.5 h and processed into films on rolls
at 130135C for 10 min.
It was found that, with the molecular mass of the hydrocarbon radical increasing, the
contact angle of wetting PVC by glycerol does not practically change. Wettability depletes
in the series Na > Mg > Al. In accordance with this, the modifier, depending on the valency
of the cation, renders different effects on the character of structure formation in films.
The structure of films from PVC dispersions is inhomogeneous and consists of globules of various sizes. This indicates that particles of the dispersion are not totally broken
down into initial structural elements even at a significant content of plasticizer in the system
and the effect of high temperature. Introduction of the SFA sodium salt of the series
C10 C16 contributes to additional aggregation of structural elements, and modification of
the dispersion by the SFA magnesium salt promotes the dispersing of structural elements
and forming of a homogeneous structure; herewith, the size of the structural elements depends on the length of hydrocarbon radical and decreases as it is increased. At the introduction of modifiers, internal stresses decrease the greater, the longer the SFA hydrocarbon
radical is.
Introduction of SFA makes it possible to significantly improve the properties of filled
films by regulating the structure formation conditions. Most mineral fillers and pigments
usually introduced into PVC films are more hydrophilic than PVC. A mixture of chalk and
titanium dioxide have an effect on PVC films as inactive fillers. The increase of their concentration contributes to the decrease of the breaking strength of these films, their relative
elongation and internal stresses as the result of weak interaction of polymer with filler particles. Filled films are characterized by an inhomogeneous globular structure, owing to a
poor compatibility with the filler. The contact angle of wetting of polymer films is much
larger than that of the filler. The character of the supramolecular structure of modified polyvinyl chloride is preserved at the introduction of a larger amount of filler into the composition up to 150200 weight fractions.
Formation of a homogeneous fine-globular structure is observed at the introduction of
the magnesium salt of the series C17 C20 into the composition. Formation of films with
this structure increases elasticity from 40 up to 70%, reduces rigidity from 3.48 down to
3.11 g, increases the breaking stress from 3.2 up to 4.0 MPa, decreases internal stresses from
1.3 down to 0.6 MPa, as well as the yield temperature of the compositions, which enables
the processing of filled polyvinyl chloride compositions on the existing equipment.
9.6
Ways of protecting metallized packaging materials
One of the ways of protection is formation of a metal layer between film materials. The
properties of combined materials are determined by various physicochemical factors. They
include the nature of polymer and nonpolymer layers, molecular mass, molecular-mass
294
distribution, extent of polydispersity, composition and concentration of modifiers; interlayer adhesion strength; supramolecular structure of polymer layers, which also depends on
their production process; surface phenomena determined by their small thickness, large
specific surface and extent of orientation of the structural elements in the layer. Individual
layers of a combined material can perform reinforcing functions with respect to the material
as a whole. It is commonly recognized that at precritical loads two main conditions are observed: the additivity of partial forces and the simultaneous deformation of layers.
Using model systems as an example, the tensile forces of multilayer materials were
determined, for instance, of low-density polyethylene and polyethylene terephthalate wetted with water and joined. Their tensile forces proved to be strictly equal to the sum of partial tensile forces determined from the stressstrain curves for particular layers. At the same
time, the breaking stress proved to be higher than the calculated value as the result of a larger elongation of the system at the moment of rupture than that of the component, which determines the strength of all the specimen.
Of great importance is the order of the layers. The largest strengthening factor is
achieved using the sequence of elastic rigid elastic material. The elastic polymer layer
protects the rigid layer from the rapid formation of cracks in it. The rigid layer impedes the
deformation of elastic layers. More elastic layers, in turn, affect the deformation of rigid
layers. Two films from the same material, joined by an adhesion layer, have a higher relative breaking elongation than the single film of the same total thickness, and the
stressstrain curve does not depend on whether the layer functions independently or as part
of the composition. The cause of this phenomenon is associated with the features of structure formation at the interface of the layers. The layer of an adhesion-promoting agent has
an effect on the magnitude and concentration of internal stresses in the system and the properties of materials on the whole.
9.7
Effect of modification on the properties of protective coatings from

epoxy compositions
The anticorrosion properties of epoxy coatings and their chemical endurance in various aggressive media depend on the nature of hardener. To increase the protective properties of
epoxy coatings, use is made of acidic type hardeners, in particular, anhydrides of carboxylic
acids (aromatic, alicyclic and linear aliphatic), as well as complexes with catalysts based
on aromatic amines and hardeners of acidic type, derivatives of dicyandiamide
HN=C(NH2)NHCN and tertiary amines. The most widely used aromatic amines are m-phenylene diamine and 4,4-diamino diphenyl methane. Coatings produced from epoxy oligomers hardened by these hardeners are distinguished by an increased resistance to organic
acids, for instance, to acetic acid. However, a significant drawback of epoxy compositions
with these hardeners are the high temperature of hardening (150C and higher), as well as
significant internal stresses commensurable with the adhesion and cohesion strengths of
coatings. In this connection, of great practical importance is the development of methods
for increasing the durability of such coatings on the basis of a decrease of internal stresses
in them and an improvement of their adhesion properties by means of special additives. We
proposed A-2 as such an additive. Introduction of additives in the amount of 23 wt. % to
epoxy oligomer ED-20 makes it possible to improve significantly the properties of coatings
(Tables 9.3 and 9.4).
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CHAPTER 9
Table 9.3 Effect of structural additive on the properties of epoxy coatings with acid-type
hardeners.
Properties
Concentration of additive, wt. %
Bending strength, MPa:

after heat cycling from 60C up to +80C
initial
Adhesion strength, MPa:
initial
after heat cycling in 20 days
at high relative humidity
after heat ageing at 180C (1000 h)
Internal stresses, MPa
Preservation of initial adhesion strength, %:
after heat cycling
after fog room
after heat ageing
86
69
128
125
120
120
5.0
4.8
2.8
4.5
8.0
9.0
56
91
10.0
10.0
8.3
10.0
3.0
9.6
9.6
7.3
9.5
2.5
100
83
100
100
78
100
4
90
5.7
8.0
Table 9.4 Effect of structural additive on the properties of epoxy coatings with cyanamine-type
hardener.
Parameters
Bending strength, MPa:

initial
after heat cycling
Adhesion strength, MPa:
initial
after heat cycling
after heat ageing at 180C (1000 h)
Hardening time at 85C, h
Preservation of initial adhesion strength, %:
after heat cycling
after heat ageing
Concentration of additive
0
10
20
30
120
97
123
145
134
150
140
7.4
6.7
5.8
9.0
6
90
78
7.4
8.0
6
9.4
9.3
9.6
3.5
3
99
102
10.5
10.5
10.9
4.9
4
100
104
From the analysis of the results given in the tables, it follows that introduction of an
optimal amount of a structural additive to epoxy compositions with hardeners of different
nature makes it possible to significantly improve the physicomechanical and adhesion properties of coatings, especially under conditions of the performance at increased humidity.
Formation of a more homogeneous and ordered structure in epoxy compositions and
coatings on their basis by small additions enables a significant (23-fold) decrease of internal stresses and an increased resistance of coatings to ageing under various conditions.
The properties of modified coatings in various aggressive media depend on the concentration of A-2.
296
Equipment and shipping containers of meat and dairy industries are operated under
conditions characterized by the diversity of aggressive media. They include acids (lactic
etc.), water, steam, blood; besides, the equipment is subjected to regular washing by special
alkaline compositions.
Of great importance for protection of equipment from corrosion are polymer coatings.
The following requirements are imposed on protective coatings:
resistance to the impact of the manufactured product and to the operation of the
equipment;
high physicomechanical properties;
good decorative appearance;
harmlessness for the human organism and the environment;
possibility of using energy- and resource-saving processes in application and formation of coatings.
Container and packaging materials, equipment of meat-and-dairy industry have been
painted up to the present mainly by alkyd, pentaerythritol-modified phthalic coating compositions or nitrocellulose and other compositions, which do not provide for high-quality
coatings resistant to aggressive media. Therefore, the problem of developing long-lasting
protective coatings for meat-and-dairy industry is topical and of great practical significance.
Based on earlier studies of various classes of film formers for developing chemically
resistant anticorrosion coatings for protection and decorative finish of components and
equipment of meat-and-dairy industry and other branches of the agroindustrial complex, we
chose epoxy enamels. However, coatings from these enamels, formed at room temperature,
are also characterized by comparatively low properties.
The further increase of the durability of anticorrosion coatings was achieved by introduction of special modifying additives. The protective properties of the coatings developed
were investigated in interaction with various aggressive media characteristic of these industries.
Objects of studies were lacquer-and-paint coating based on commercially used enamel
EP and enamel EP modified by addition A-2 at a mass ratio of 100:2.
Compositions were applied to respective primers (EP-0010) by spraying. Coatings
were formed at a temperature of 1820C on steel plates.
Tests were carried out in model media characteristic of meat-and-dairy industry and
food industry: 3% solution of lactic acid and 1.5% solution of NaOH by immersing a specimen into solutions at a temperature of 202C. During the tests, we registered the changes
in the appearance of coatings, adhesion and impact strengths by the respective State Standards GOST 9.403-80 and GOST 9.407-84.
We obtained comparative data on the effect of the alkoxysilane additive on the physicomechanical and protective properties of epoxy enamel EP during the impact of aggressive media at a temperature of 20C.
As the result of studies, it was found that the coating based on enamel EP applied over
the primer EP-0010 does not change its protective properties at the impact of a 3% solution
of lactic acid for 14 days, points of corrosion appear in 20 days; at the impact of a 1.5%
solution of alkali, the coatings do not change their properties for 60 days, and points of corrosion appear in 150 days.
To increase the chemical resistance of coatings, the alkoxysilane additive A-2 was introduced into enamel EP before the application to plates.
Coatings based on enamel EP with a 2% modifying additive A-2 with primer EP-0180
thoroughly applied to the plates at the action of a 3% lactic acid solution do not change their
CHAPTER 9
297
properties for 300 days, and points of corrosion appear in 500 days in a medium of 1.5%
alkali liquor; the loss of decorative properties begins in 300 days, and points of corrosion
appear in 360 days.
The improvement of the physicomechanical and protective properties of coatings
based on enamel EP modified by the oligomer alkoxysilane additive A-2 is due to a
57-fold decrease of internal stresses of coatings; adhesion to metal supports increases two
times after the ageing in a 3% solution of lactic acid and 1.5% alkali liquor.
The studies showed that alkoxysilane additive A-2 in small amount plays the role of
an inhibitor of corrosion in coatings and is a modifier providing for the required set of performance properties of lacquer-and-paint coatings intended for protection of components
and equipment in meat-and-dairy industry and food industry, which have no immediate
contact with food products.
In accordance with the recommendations, the durability of coatings based on enamel
EP modified by alkoxysilane additive A-2 is 10 years.
The effect of alkoxysilane additive A-2 on the resistance of coatings from epoxy enamel EP at the impact of aggressive media of mineral fertilizers was studied by immersing
specimens, 15075 cm steel plates, with the coating into solutions and suspensions of mineral fertilizers at a temperature of 202C.
Coatings based on enamel EP with the 2% modifying additive of cold-drying additive
A-2 were tested as compared with specimens of coatings without the additive, hardened at
a temperature of 1202C.
As mineral fertilizers, we used 10% solutions of potassium chloride, ammonium nitrate; a suspension of ammonium sulfate. Tests were continued for 120 days.
During the tests, we registered the change of the appearance of coatings in accordance
with State Standard GOST 9,407-84.
It has been found that the change of the protective properties of EP coatings with addition of cold-hardened A-2 is similar to that of coatings and EP enamel of hot hardening
in all media studied at 1202C for 2 h.
For the second layer of enamel, the composition is prepared according to the same
principle as for the first layer. The thickness of the overall lacquer-and-paint coating should
be 100120 m.
The second layer is dried at room temperature for 24 h or at 1202C for 2 h.
The complex system of coatings should be held for no less than 7 days before its
operation.
Green enamel EP-525 can also be used in the complex system as the coating layer.
Enamel EP-525 is a suspension of pigments in solution of resin E-41. The enamel should
be applied in 23 layers over the primed surface at a working viscosity of 1215 s according to VZ-4.
Before the application, a hardener is added to enamel; the contents are thoroughly
mixed, held for 1530 min, then a corrosion inhibitor is added in terms of 2 g per 100 g
enamel. The contents are mixed again and brought to the working viscosity by solvent R-5.
The prepared enamel can be used for no more than 8 h.
The enamel is dried at 1202C for 2 h, in repair painting it could be dried at a temperature of 1023C for 24 h.
The process sheet of painting external surfaces of the equipment and metal structures
from ferrous metals was worked out based on recommended systems of complex anticorrosion lacquer-and-paint coatings for use in meat-and-dairy industry and other food industries.
298
The quality of painting works is controlled visually. The service life of lacquer-andpaint coatings and their appearance depend on the correct choice of the coating system, the
observance of the surface preparation process before painting, on the application and drying
of lacquer-and-paint coatings.
The quality of prepared and painted surface is controlled by a visual examination of
100% articles by naked eye.
The quality of surface preparation before painting is controlled in accordance with
GOST 9.402-80, Section 5.
The extent of drying of the coating is guaranteed by the observance of the drying
regimes, and if necessary is controlled on witness specimens according to GOST 19007-73.
9.8
Technology of producing protective coatings with improved

performance properties
The process of anticorrosion coatings production is traditional and consists of the successive execution of the following operations: preparation and control of lacquer-and-paint
materials, preparation of the surface, priming and drying, application of a required number
of layers of coating lacquer-and-paint materials with intermediate and final drying.
Preparation of the surface. The surface preparation process includes all or part of the
following technological operations: removal of old coatings, corrosion products and foreign
impurities, cleaning of hot-sealed seams and degreasing. The surface is treated using one
of the methods of abrasive preparation: shot-blasting, shot-throwing, hydroabrasive; or a
mechanical method using a hand tool.
The extent of purification of black-metal surfaces from corrosion products should be
no less than 2 according to GOST 9.402-80, i.e., examination by naked eye should find no
scale and rust.
Degreasing of metal surfaces is performed using brushes or cleaning cloth wetted with
white spirit. Brushes and cleaning cloth should leave no traces on the treated surface (particles of material, fluff etc.).
The extent of surface degreasing should correspond to grade 1 as per GOST 9.402-80.
The interval between the abrasive cleaning of the surface and the painting should not
exceed 7 hours; it is admissible to exceed this interval up to 24 h in the absence of visible
changes on the prepared surface.
Duration of the interval between the end of degreasing and priming should be no more
than 1 hour.
In the cases when the use of abrasive treatment of metal surfaces is impossible, it is
recommended to use primers rust modifiers EP-0199.
One of the ways to prepare the surface of articles is metallization with aluminium or
nickel. To determine the protective properties of coatings, specimens of plates with the metallized coating from Al and Zn, as well as specimens with the combined coating from enamel and EP and modified anticorrosion additive were immersed into distilled water, 3% and
30% NaCl solutions, 1.5% NaOH solution and 3% solution of lactic acid; the change of the
appearance in time was registered. The results of the tests showed (Table 9.5) that metallized coatings possess a low chemical endurance in food media; application of a combined
coating leads to an increase of the protective properties. Modification of EP enamel in an
optimal amount (2%) by additive A-2 makes it possible to increase the corrosion resistance
of metal several times, except the coating with a zinc sublayer in a 3% solution of lactic
acid.
299
CHAPTER 9
Preparation of the surface of equipment and metal structures prior to painting works
is of great importance for producing a lacquer-and-paint coating with high protective properties, which possesses a good adhesion to metal and provides for a highly efficient protection from corrosion.
Studies were carried out to reveal the effect of an aqueous solution of product A-2, as
well as aqueous extracts from coatings based on epoxy resins containing 2 wt. % of product
A-2, on the electrochemical characteristics of the system, the value of steady-state potential,
pH of the medium and current density. From Table 9.5, it follows that product A-2 provides
for the efficient inhibition of electrochemical processes, which cause corrosion of metal,
i.e., reduce the value of steady-state electrode potential by shifting it to the positive side, as
well as decrease the current density and increase pH of the medium (Table 9.6).
Table 9.5 Results of tests of metallized and combined coatings in media.
System
Time before bubbles appear, days

H2O
Metallization by aluminium
Metallization by EP
Metallization by EP + A-2
Metallization by zinc
Metallization by EP
Metallization by EP + A-2
15
60
380
1
30
60
3% solution 30% solution

1.5%
of NaCl
of NaCl
solution of
NaOH
30
380
380
15
60
90
10
380
380
90
90
380
1
60
380
1
60
90
3% solution of
lactic acid
60
230
380
1
1
60
Table 9.6 Effect of corrosion inhibitor on the steady-state electrochemical potential of steel,
current density and pH of the medium measured using an KhSO-1 chlorine-silver reference
electrode.
Test object
Testing
time
Steady-state
electrochemical
potential, mV
Current
density,
mA/cm2
pH
Water
Aqueous solution of A-2 product
Aqueous extract from an E-40-based coating
Aqueous extract from a coating based on E-40
+ 2% A-2
5 hours
5 hours
10 days
10 days
700
200
570
390
50.00
18.00
2.40
2.07
5.1
6.5
5.3
6.0
9.9
Ways of thixotropic decrease of internal stresses in the formation of

coatings from polymer dispersions for finishing of packaging materials
Polymer dispersions are widely used for production of coatings, glue layers, sealants,
industrial-rubber articles, nonwoven and laminated materials of various purposes. The development of the physicochemical bases of producing materials from such systems related
to the studies of the structure of dispersion particles, its effect on the specific features of
structural transformations and changes of the properties at various stages of the film formation process. When conducting such studies, which are aimed at establishing a relationship
10, MPa
300
20
2
3
10
96
192
288 , h
Figure 9.1 Kinetics of internal stresses in the formation of coatings from solutions of SKS-50 (1),
SKN-40 (2), SKD-1M (3).
between the structure of particles of dispersions and the kinetics of the change of properties
and structure at various stages of film formation, special attention was paid to studies of the
kinetics of increment and relaxation of internal stresses, which characterize the incompletion of the relaxation processes and cause a spontaneous curling, warping and breakdown
of materials both in the process of their formation and in operation.
This made it possible to develop the physicochemical ways of decreasing internal
stresses in the formation of various-purpose coatings and to obtain materials with a given
set of properties. The object of study were various types of dispersions latexes, emulsions
of polymers and oligomers, powdered compositions from oligomer and polymer systems.
A peculiarity of forming films from polymer dispersions is related to the complex and inhomogeneous structure of their particles. Using the method of electron-microscopy, particles of dispersions were shown to represent supramolecular formations consisting of
structural elements, which are characteristic of amorphous and crystalline polymers. For
most polymer dispersions, the structure of particles is globular. The size of globules, their
number and packing density depend on the molecular structure of polymer (its chemical
composition, nature of functional groups and character of their distribution in the chain, of
conformations and flexibility of macromolecules), as well as on the colloidal-chemical
properties of dispersions. Studies of the structure of particles of dispersions based on synthetic rubbers and elastomers showed that, given rigid aromatic fragments in the chain,
globules 510 nm in diameter are formed from individual folded macromolecules; the
structure of part of butadiene nitrile latex SKN-40 was presented. The particles are seen to
reveal a globular inhomogeneous structure with a more dense packing of structural elements in the boundary layers. The structure of various types of particles of dispersions was
given: of suspension polyvinyl chloride used for fabrication of plastisols, dispersions of
polyurethane based on polyester and diphenyl methane diisocyanate obtained by mechanical dispersion of granules in an aqueous medium in the presence of surfactants, fluoroplastic dispersions. It was revealed that globules in polyvinyl chloride particles 100150 nm in
size represent complex secondary structures. They are not broken down during the swelling
of dispersion particles in plasticizer. This results in the formation of an inhomogeneous defect structure in coatings; the structure does not match well with fillers. Particles of polyurethane and fluoroplastic dispersions consist of finer structural elements 5100 nm in diameter, which are commensurable with the size of individual macromolecules. For
dispersions from polar polymers containing a significant number of functional groups capable of participating in specific intermolecular interaction, particles of dispersions consist
CHAPTER 9
301
U, %
10, MPa
80 8
60
40
20
1
2
6
3
48
240 , h
Figure 9.2 Kinetics of internal stresses (13) and of moisture content changes (46) in the formation of coatings from dispersions of SKS-50 (1, 4), SKN-40 (2, 5), SKD-1M (3, 6).
of unfolded macromolecules. This takes place, for instance, for dispersions based on alkyl
acrylates with a large concentration of carboxyl groups. When obtaining dispersions from
oligomers with the regular alternation of active groups, for instance, from oligourethane
methacrylates with aromatic and aliphatic oligomer blocks, particles of dispersions are
characterized by a plate- or flake-like crystalline structure.
Inhomogeneity of the structure of dispersion particles, as well as the presence of special protective layers on their surface in some cases stipulates the incompleteness of the relaxation processes in the formation of films from such systems and the complex character
of the occurring structural transformations. This is especially pronounced in studies of the
kinetics of increment and relaxation of internal stresses in the process of film formation
from dispersions. Such investigations are rather important not only for studying the specific
formation of films from dispersions, but also for developing the physicochemical ways of
decreasing internal stresses. Figures 9.1 and 9.2 present the data on the kinetics of increment
and relaxation of internal stresses in the formation of coatings from dispersions and solutions of synthetic rubbers of various chemical compositions. These curves are typical in the
formation of coatings from dispersions of polymers of various chemical compositions. In
contrast with solutions of polymers, formation of films from dispersions is seen to be
multi-stage and not to be competed after the removal of the liquid phase. Formation of local
links between particles of dispersions as the consequence of the removal of the medium at
the initial stage of film formation is accompanied by a sharp increment of internal stresses.
The subsequent relaxation of internal stresses indicates the incompleteness of relaxation
processes, instability of the properties of coatings and occurrence of complex structural
transformations in the system. Depending on the structure of dispersion particles, the relaxation processes can proceed very slowly, more than 30 days. The structure of coatings from
latex SKS-50 was presented, which corresponds to the maximal and equilibrium value of
internal stresses in 30 days of formation at 20C. It is seen that after the liquid phase is removed, the structure of individual particles of dispersion and the interfaces between them
are clearly revealed. A homogeneous structure emerges after the regrouping of structural
elements and the completion of relaxation processes in the system. This character of
302
structural transformations is typical in the formation of coatings not only from latexes, but
also from dispersions of various types of polymers; the structure of coatings from a polyvinyl acetate emulsion at various stages of their formation was given; structure formation
in production of coatings from acrylic powders in their melting at 200C was presented. It
is seen that, irrespective of the type of dispersion and its chemical composition the structure
of dispersion particles and the interfaces between them are revealed. In subsequent formation, structural elements are regrouped and a homogeneous structure is formed.
It follows from these data that the breakup of dispersion particles into initial structural
elements and their regrouping in the process of film formation are typical of many polymer
dispersions obtained by different methods. However, each of them imposes its own specific
features on the rate of these processes and the character of the kinetic curves of the change
of internal stresses. In the formation of coatings from powdered materials, the kinetics of
the change of internal stresses is observed to have an induction period associated with the
inhomogeneity of the structure of particles and a broad molecular-mass distribution. This
leads to a weak intermolecular interaction at the initial stage of film formation due to the
melting of, apparently, the most low-molecular-mass fractions and the presence of a defect
structure with air bubbles. The subsequent warming-up of coatings at a temperature significantly exceeding the melting temperature of the oligomer is accompanied with the total destruction of particles and the emergence of local links between their constituent structural
elements. Regulation of the film formation process from such powdered systems is rather
complicated, as it proceeds at temperatures close to the decomposition of the polymer and
is accompanied with the formation of craters and other defects.
Thus, these data sugest that the complex structure of dispersion particles, the presence
of protective layers from more fine and densely packed structural elements and surfactants
on their surface significantly extend the period of film formation, determine the instability
of the properties of materials and the occurrence of significant internal stresses. The development of the physicochemical ways of forming coatings with stable and high performance properties can be done by introducing modifiers, which facilitate the breakup of dispersion particles into initial structural elements and provide for a stronger interaction
between them, as well as by synthesizing dispersions with a homogeneous structure of particles, increased concentration of polar groups on their surface and an optimal flexibility of
the chains.
It was shown that in the formation of coatings from latexes based on alkyl acrylates
with a large concentration of carboxyl groups on the surface of dispersion particles and their
homogeneous structure, the coating formation time decreases to several minutes instead of
tens of days; coatings are characterized by high and stable physicomechanical properties
and low internal stresses. In the formation of coatings from powdered materials with the
regular distribution of functional groups in the chain, the homogeneous structure emerges
very rapidly at the oligomer melting temperature of 6070C.
To decrease internal stresses and improve the properties of coatings from dispersions
with an inhomogeneous structure of particles, we used various modifications of methods
based on the creation of a thixotropic structure by preliminarilyy dispersing the particles
and crosslinking them by means of special additives. This enables a significant improvement of the adhesion and stress strain properties of coatings and an increased durability
of materials. The choice of modifiers depends on the type of dispersion, structure of particles, chemical composition of polymer. For dispersions based on butadiene and its derivatives, it is achieved by modification with water-soluble oligomers and polymers; for those
of polyurethanes, by introduction of various surfactants; for emulsions of epoxy resin-based
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303
oligomers, by a correct combination of dispersing and stabilizing surfactants in the system;

for dispersions based on alkyl acrylates, by introduction of bifunctional compounds and organosilicon oligomers contributing to the crosslinking of particles of dispersions.
Depending on the type of modifier introduced, the development of a thixotropic structure can be performed as the result of dispersing particles and increasing the intermolecular
interaction between their constituent structural elements contributing not only to the dispersing of particles but also to the orientation of the structural elements to form a sparse
three-dimensional network from ordered anisodiametric structures.
Modification of polymer dispersions is based on the formation of an ordered structure
with a certain distribution of the physical and chemical bonds in the systems by using various additives or by changing the colloidal chemical properties of the dispersions. Depending on the character of this structure, materials with a certain set of properties can be
created. A significant change of the properties of elastomers can be done by regulating their
colloidal chemical properties (pH of the medium, molecular mass of polymer, nature and
concentration of emulsifier). The action of these factors leads to the change of information
of macromolecules, size and morphology of supramolecular structures present in the particles of the dispersions. For butadiene styrene latexes and their derivatives, for dispersions
based on alkyl acrylates, an ordered supramolecular structure of structural elements of anisodiametric type was found to be formed at a certain optimal pH of the medium owing to
the unfolding of macromolecules; this structure is characterized by higher adhesion and
strength properties and low internal stresses, which makes it possible to eliminate coiling
and warping of backed materials in the production process. It was shown that the structure
of coatings from butadiene styrene latexes with pH 11.7 is globular. It is known that the
globular conformation of macromolecules does not make it possible to realize the properties
of polymers associated with peculiar structural features of the polymer chain. With pH decreasing to 8.7, a pronounced anisodiametric structure is formed in coatings under the same
conditions. The change of the ultimate shearing stress and viscosity of latexes depending
on pH of the medium is associated with the possibility of unfolding macromolecules of carboxylated latexes. The mechanism of this process is explained by the electrostatic repulsion
as the result of the neutralization of carboxyl groups in an alkaline medium and their conversion to COO ions. It is possible that the unfolding of macromolecules in this case is due
to the increased intermolecular interaction as the result of the hydrolysis of anion-active
emulsifiers of the type of soaps, which is enhanced at a decrease of pH. The further decrease
of pH leads to the emergence of an inhomogeneous globular structure, which consists of
densely packed latex particles 0.1 m in diameter and finer structural elements in between
them. Etching of specimens by active oxygen revealed that latex particles under these conditions consisted of larger globules than particles in the initial latex with pH 11.7. The cause
of this phenomenon is due to the fact that, as pH is decreased, the purely coagulating action
of hydrogen ion is of importance besides the shift of the hydrolytic equilibrium. This character of structure formation in dispersions of polymers depending on pH of the medium
leads to a nonmonotonic change of the thermophysical adhesion and mechanical parameters
of films and coatings. The best properties were found to exist at an optimal pH 8.7.
A significant improvement of the physicomechanical properties by regulating pH of
the medium was also done for coatings from acrylic dispersions. At an optimal pH of the
medium, a thixotropic structure from ordered structural elements is formed in acrylic dispersions; this structure contributes to the acceleration of the relaxation processes, a decrease
of internal stresses and a significant improvement of the stress strain properties of films
(Table 9.7).
304
Table 9.7 Effect of PAA on the properties of coatings from acrylic dispersions.
Amount of
PAA, %
Gloss
value, %
Agglutination,
MN/m2
Adhesion,
MN/m2
Relative
elongation, %
Breaking
strength, MN/m2
0
0.6
1.2
3.6
30 45
20 35
40 55
15 25
0.11 0.13
0.08 0.10
0.10 0.12
0.16 0.17
5.5
4.4
9.0
6.6
200
250
300
120
7.8
8.0
8.5
8.5
An especially efficient factor for the regulation of the properties of dispersions is their
modification by surfactants containing polar groups, which specifically interact with polymer to form hydrogen bonds. Surfactants of this type not only contribute to the dispersal of
the dispersion particles, but also cause the orientation of structural elements in the presence
of aromatic groups in the chain. Surfactants with polar groups are efficient for dispersions
based on polar polymers, for instance, polyurethanes based on polyesters, acrylic polymers
with a greater concentration of polar groups, polyester amidourethanes.
The use of surfactants of this type in dispersions of polymers makes it possible to reduce the size of structural elements, to create an ordered structure, to increase the intermolecular interaction during the formation of films. Along with a decrease of internal stresses,
this is accompanied by an improvement of the stress strain properties.
A significant improvement of the adhesion and physicomechanical properties of coatings from dispersions of polymers is observed in their modification by bifunctional compounds with various chain flexibilities, which crosslink the structural elements of the
dispersion and provide for a sufficient elasticity of the system. However, with the concentration of polar groups in polymers decreasing, these compounds act as plasticizers, which
contribute to an increase of the elasticity of coatings and a decrease of their strength.
For dispersions based on nonpolar polymers the development of a thixotropic ordered
structure can be done by introduction of sodium salts of some surfactants, which contribute
to the increase of the local bonds between the structural elements. This is explained by the
interaction of sodium ions with polar groups of surfactants adsorbed by dispersion particles.
This makes it possible to sharply decrease internal stresses in the formation of coatings, to
improve the strength properties of coatings based on butyl rubber dispersions.
However, in some cases the choice of modifiers is stipulated by the need to impart the
coatings with special properties. For instance, a rather important characteristic of coatings
and films based on butyl rubber dispersions, along with the above properties, is their high
tearing strength. In this connection, of great practical significance are methods of modifying
dispersions by oligomer systems polymerized in an aqueous medium to form the threedimensional network formed by chemical bonds, as well as the use of water-soluble polymers as modifiers. For these purposes, use is usually made of phenol-formaldehyde and resorcinol-formaldehyde resins and their initial components (resorcinol, urotropine etc.). The
improvement of the physicomechanical properties is observed at the direct introduction of
oligomer modifiers into the polymer dispersion. Introduction of water-soluble polymers can
have different effects on polymer dispersions depending on the chemical composition and
concentration of additives.
Small additions of polyvinyl alcohol, gelatin, sodium carboxymethyl cellulose in the
amount of 1 up to 5% accelerate the first stage of coagulation of diluted latexes. With the
concentration of polymer additives increasing, the duration of the first stage of coagulation
increases, and at concentrations higher than 20% additions of polymers have no effect on
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305
coagulation. Coagulation at the introduction of small additions of the given polymers is explained by the formation of bridge bonds between individual latex particles. With the concentration of polymer increasing, the saturation of the surface of latex particles and their
stability increase. The effect of polymer additions is manifested the stronger, the greater the
molecular mass of polymer is and the less saturated the surface of latex particles is.
Slightly different regularities are observed in studies of the effect of the same additives
on the coagulation of nondiluted latexes based on butadiene and its derivatives. It proved
that at a small concentration of polyvinyl alcohol (up to 5%) the stability of latexes to the
action of electrolytes increases. At a further increase of the concentration of polymer up to
10% the rate of coagulation increases. The stability of latexes to the action of small additions of polymers is explained by the structuring of the adsorption layer. The further increase of the concentration of polymer above 10% leads to the stabilization of the system
as the result of the total coating of the surface of latex particles by polymer.
Thus, at small concentrations of polymer additives the stability of dispersions can be
increased as the result of the formation of envelopes with high structural-mechanical properties around particles. With the increase of the concentration of polymer in the dispersion,
the intermolecular interaction between particles can increase to form a three-dimensional
network. This effect is observed not only in the modification of polymer dispersions by linear polymers with a high molecular mass, but also during the introduction of oligomer systems of the type of resol, phenol- and urea-formaldehyde resins capable of condensation in
an aqueous medium to form a three-dimensional network. Such additives are usually introduced to improve the strength properties of films, as well as to fix porous structures formed
under certain conditions. Of especially great practical significance is the introduction of
such additives in production of films from dispersions of polymers by the ionic deposition
method, when the action of electrolytes in some cases leads to a considerable decrease of
their strength.
9.10 Modification of finishing dispersions for paper and offprints by

polymer systems
Studies of the effect of resorcinol-formaldehyde resin on coagulation of diluted latexes
showed that in small amounts it reduces the time of the first stage of coagulation. With the
concentration increasing, its stabilizing effect is manifested, similar to the case of linear
polymers. Unlike linear polymers, small additions of this resin are not observed to lead to
the growth of aggregates. Resins condensed before being introduced into latex do not contribute to the improvement of the properties of materials. Introduction of partially condensed resins leads to an increase of the strength of films from dispersions of rubbers.
Introduction of these additives considerably improves the adhesion properties of films from
dispersions of butyl rubber.
The possibility of using phenol-polyamide-formaldehyde resin as a modifier of chloroprene latex L-7 was studied. Mixtures of the latex with the resin are distinguished by a
good stability. The greatest strength of films is achieved at a small content of the resin
(about 1%).
The effect of the character of interaction between butadiene styrene rubber and resorcinol-formaldehyde resin on the reinforcement of rubbers was studied. The latexresin system was coagulated by solutions of aluminium and potassium salts. Isolated rubber,
modified by the resin, was dried and treated on rolls at 70C. The absence of chemical bonds
between molecules of rubber and resin was shown. Formation of a network structure is ob-
306
served during the storage of the system, as the result of which the rigidity of the system increases and the mechanical and process properties become worse. In the presence of only
the physical interaction between the modifier and rubber the reinforcing effect from the introduction of the modifier and the stability of the process properties are preserved in
long-term storage of specimens.
Application of modifying additives and surfactants renders a significant effect on the
vulcanization of rubbers; the effect of several surfactants on the kinetics of sulfur vulcanization of films from an aqueous dispersion of polyisoprene synthetic rubber SKI-23 and
rubber mixtures on its basis was studied. Anion-active potassium resinate and cation-active
cetyl pyridinium chloride were used as emulsifiers of aqueous dispersions. It was shown
that the rate and extent of sulfur vulcanization of films from aqueous dispersions of rubbers
is considerably higher than using respective rubber mixtures containing no surfactants.
The possibility of using unsaturated urethane rubbers of alkyl-phenol-formaldehyde
resins as texturing agents was studied, as well as the use of phenol and n-tert-butyl phenol
disulfides as the curing agent of general-purpose rubbers. Resin vulcanizates are inferior
than sulfur vulcanizates with respect to a number of physicomechanical characteristics
(resistance to rupture and tearing strength, elasticity, wear resistance) and exceed them by
other properties (residual elongation, hardness, endurance). Resin rubber mixtures also
have much better process properties. When comparing the texturing activity of various
n-tert-butyl phenol sulfides, it was found that an increase of the number of sulfur atoms between phenol rings and an increase of the extent of condensation of alkyl pnenol sulfides
contributes to the increase of their curing capacity; what is more, with the increase of the
content of methyl groups in the resin the physicomechanical characteristics of vulcanizates
increase.
The distribution and texturing action of modifiers in rubber mixtures based on
polychloroprenenairine for creating a stable bond in the rubbertextile system were studied. For better compatibility and more uniform distribution of modifiers of the type of resorcinol and resotropin in the mixture, they were treated with surfactant Alkamon.
Introduction of such modifiers contributes to the structuring of the system.
Thus, introduction of modifiers from oligomer and polymer systems in an aqueous dispersion of polymers makes it possible to significantly improve the physicomechanical and
adhesion properties of films and coatings as the result of creating a more homogeneous and
ordered structure. However, the mechanism of action of these additives on the structural
transformations in dispersions of polymers and coatings on their basis has been little studied, the cause of reinforcement of rubbers by oligomer systems is associated with the condensation of resin as thin films on the surface of particles of dispersions to form a
continuous chain structure. Based on electron-microscopy studies of vulcanizates containing phenol-formaldehyde resin, a conclusion was made on the possibility of hardening of
phenol-formaldehyde resin particles in latexes. More fine particles of the resin are covered
in this case by a rubber envelope, which can be coupled with the surface of resin particles
by chemical or intermolecular bonds. Rubberresin particles have a uniform dense packing
with a specific chained distribution, which provides for higher strength parameters; herewith, the vulcanizate has a greater elasticity and lower hardness. In a number of cases, the
interaction of oligomers with latexes is explained by electrostatic forces, as well as by
crosslinking rubber macromolecules by a phenol-formaldehyde resin of the resol type as
the result of the interaction of methylol groups of the resin with -methylene hydrogen of
isopentene groupings of rubber. Formation of chemical bonds is assumed in many works.
Considering the strong dilution of the resin in latex, the possibility of its condensation in
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307
latex is excluded, and the increase of the strength of films is related to the effect of the resin
as a fine-dispersed filler.
A significant thing for elucidating the mechanism of action of such additives is to study
the kinetics of increment and relaxation of internal stresses in such systems; studies of the
formation of coatings from dispersions of butadiene rubbers showed that introduction of
phenol-formaldehyde resins renders an effect not only on the value of internal stresses but
also on the character of their change in the coating formation process. In latex coatings not
modified by oligomers, relaxation of internal stresses is observed after drying. In coatings
from modified latexes internal stresses remain constant after achieving an ultimate value
(see Figs. 9.1 and 9.2) and in prolonged storage of specimens under conditions of their formation. The value of internal stresses sharply changes depending on the time of preliminary
holding of the modified dispersion prior to its application to the support. If the dispersion
is applied to the support immediately after modification, comparatively small internal
stresses are observed. With the holding time of the mixture of the dispersion and resin increased up to 30 min, a sharp increment of internal stresses is observed; their values significantly exceed those of the stresses in coatings from the initial components and from the
freshly prepared mixture. At a further increase of the holding time of the mixture up to 60
min prior to its application to the support, internal stresses sharply decrease. At the same
time, the value of internal stresses depends significantly not only on the holding time of the
resinlatex mixture, but also on the maturation time of the resin itself prior to its introduction to latex. For coatings from a freshly prepared mixture the dependence of internal stresses on maturation time of the resin is nonmonotonic. At an increase of the maturation time
of the resin, internal stresses first go up and then sharply drop down. These data suggest
that the character of the change of internal stresses is determined by the extent of completion
of the polycondensation process in the resin itself. In the absence of latex, this process is
much faster, which is due to the strong dilution of the resin at its introduction into latex. A
sharp increment of internal stresses is observed only at a certain extent of condensation of
the resin. A significant condensation of the resin prior to its introduction to latex contributes
to a decrease of internal stresses down to the values smaller than internal stresses in coatings
from nonmodified latexes.
Conditions for the destruction of latex particles in the dispersion and for the formation
of a thixotropic structure were found; as well as the effect of structural transformations on
the physicomechanical properties of dispersions and coatings on their basis was studied
with the view of developing the physicochemical ways of reducing internal stresses. The
object of study was divinyl styrene latex SKS-50. The structure of dispersions and coatings
was regulated by introduction of polyacrylamide (PAA) of various molecular masses and
urea-formaldehyde resin (UFR). Modifying additives render a significant effect on the
rheological properties of dispersions.
The flow curves for the initial latex modified by UFR and polyacrylamide or their mixture were presented. It is seen that the initial latex is a semistructured system with a relatively low viscosity. Introduction of resin does not have a significant effect on the character
of the flow curve, and only in the presence of polyacrylamide or its mixture with the resin
a considerable structuring of the system is observed, which is accompanied with an increase
of the ultimate shearing stress and a 23-fold increment of viscosity. Introduction of additives also has an effect on the kinetics of increment of viscosity. The viscosity of the initial
latex does not change in long-term holding under room conditions, whereas in the presence
of texturing agents, especially of a mixture of polyacrylamide and UFR, an increment of
viscosity in time is observed.
308
Studies of the properties of coatings obtained from modified and nonmodified dispersions found that the rate of increment and relaxation of internal stresses in the formation of
coatings also depends on the nature of additives and time of preliminary structuring of a
modified dispersion prior to its application to the support. Coatings modified by resin are
characterized by an increase of internal stresses without any significant change of the character of the kinetic curves. In the presence of low-molecular-mass polyacrylamide with a
molecular mass of 0.25106, a sharp increment of internal stresses is observed. As the molecular mass of polyacrylamide increases, internal stresses go down at a simultaneous increase of the rate of their increment and relaxation.
Modification of latex by a mixture of UFR polyacrylamide contributes to a decrease
of internal stresses and an increase of the rate of the relaxation processes. Herewith, a significant decrease of internal stresses as compared with coatings from the initial latex is observed to occur at a preliminary holding of the mixture for 20 min up to 24 hours prior to
the application to the support. During the formation of coatings from structured dispersions,
the period of formation of coatings with more stable properties is considerably reduced.
Modifying additives render an effect on the value and kinetics of the change of the thermophysical parameters of latex coatings. During the formation of coatings, the thermophysical
characteristics change antibately to internal stresses. UFR has a lesser influence on the value
and rate of change of the thermophysical parameters of coatings as compared with other
modifying additives, whereas polyacrylamide sharply slows down the rate of the relaxation
processes and decreases the thermophysical parameters. Modification of latex by a mixture
of polyacrylamide and UFR is observed to lead to an increase of the thermophysical characteristics up to the values observed for coatings from initial latex, and the increase of the
rate of the relaxation processes.
Introduction of modifying additives in latex has an effect on the adhesion and strength
properties of coatings (Table 9.8). In the presence of polyacrylamide and its mixture with
UFR, the strength of films sharply increases, along with good deformation properties and
elasticity. From comparison of the structural-mechanical properties of dispersions modified
by texturing agents, and coatings obtained on their basis, it follows that the high strength in
Table 9.8 Effect of the nature and molecular mass of modifying additives on the properties of
laminated materials.
Composition Molecular mass
of PAA,
106
SKS-50
MFS
PAA
PAA + MFS
0.25
0.55
0.75
1.45
1.75
0.25
0.55
0.75
1.45
1.75
Breaking
strength,
MN/m2
Elasticity
modulus,
GPa
0.8
2.7
0.6
1.3
1.8
2.3
1.8
2.3
2.5
4.2
8.5
6.0
5.0
9.0
9.0
8.0
7.8
8.8
Resistance to Rigidity,
delamination,
G
MN/cm
0.39
0.83
0.52
0.11
0.14
0.28
0.73
0.75
0.87
0.83
0.70
1.10
40
92
52
47
42
44
38
55
51
39
54
65
Vapour
proofness,
mg/(cm2 h)
3.00
4.97
5.60
4.62
5.10
4.49
4.70
5.30
5.50
5.35
5.30
5.50
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309
combination with elasticity and high rate of relaxation processes is observed only for coatings produced from thixotropic dispersions characterized by an ordered structure.
To elucidate the role of introduced additives in the formation of the structure of latex
coatings, we studied their supramolecular structure at various stages of structure formation
by means of an electron microscope, using the method of oxygen etching of specimens,
which makes it possible to reveal the structure of latex particles. We obtained replicas from
the surface of coatings from initial latex SKS-50 and modified PAA, as well as UFR. It was
shown that at the introduction of PAA the initial structure of dispersion particles breaks
down into finer structural elements observed for coatings obtained from solutions of the
same polymers. Simultaneously with the destruction of the structure of latex particles we
observed aggregation of newly formed structural elements. The rates of destruction and
subsequent aggregation depend on the molecular mass of PAA. With the molecular mass
of PAA decreasing, structural transformations proceed slower, which is indicated by the
data on the kinetics of increment and relaxation of internal stresses, as well as the data on
the change of the thermophysical parameters of coatings.
In the presence of modifying additives, structural transformations are much faster in
the dispersion itself before the film formation process as the result of a preliminary holding
of the mixture of latex with additives prior to the application to the support.
In coatings obtained from latex modified by PAA prestructured for 30 min, a globular
structure is observed, similar to the structure of coatings from nonmodified latex and having
a higher strength and elasticity due to the binding of individual structural elements by PAA
molecules. Destruction of dispersion particles and crosslinking of structural elements of latex particles occur the fastest during the formation of coatings from latexes modified by
UFR. However, in the presence of only UFR the destruction process is, apparently, not totally completed, as the result of which an inhomogeneous structure is observed in coatings,
which consists of various-size particles bound by molecules of the resin. Along with this,
such coatings are found to have structural elements not observed earlier in latex coatings
and formed as the result of polymerization of the resin in the latex medium. Coatings with
this structure, despite a high strength, are distinguished by an increased rigidity (see Table
9.8). Coatings obtained from latexes modified by a mixture of UFR and low molecular mass
PAA are characterized by optimal properties. Along with high strength and adhesion, they
are distinguished by a small value of internal stresses as the result of relaxation processes
at two different levels: in the formation of a thixotropic structure in the liquid phase and in
the formation of coatings. In coatings with optimal properties, a band- and network-type
structure is observed.
Phenol-formaldehyde resins were also used for modifying dispersions of butyl rubber.
The physicomechanical properties of coatings depend on the modification method. In experiment I, resorcinol-formaldehyde resin (RFR) precondensed for 18 hours under room
conditions was added to the dispersion; in experiment II, the resin was added to the dispersion after a condensation for 1 hour ((Table 9.9). Films were formed by the method of ionic
deposition. It is seen from the table that modification of a butyl rubber dispersion by 10%
RFR under optimal conditions according to method I makes it possible to increase the
breaking strength of films more than twofold and the tearing strength more than threefold
with the elasticity of films preserved. To elucidate the mechanism of strengthening butyl
rubber by resin, we investigated the effect of additives on the properties of films obtained
from dispersions unfilled and filled with carbon black. Films were hardened under the same
conditions (Table 9.10). From the data of the table it follows that for films from unfilled
dispersions of butyl rubber the breaking strength and tearing strength are increased by more
310
than an order of magnitude in the presence of modifying additives. From the comparison
of the data of Tables 9.9 and 9.10, it follows that at an optimal concentration of the modifying additive the tearing strength of films from carbon black-filled and unfilled butyl rubber dispersions is the same. This indicates that the tearing strength of films from butyl
rubber dispersions modified by resin is determined by the density of the three-dimensional
network formed by the resin in the dispersion.
Table 9.9 Physicomechanical properties of films from compositions based on RFR-modified butyl
rubber dispersions.
Test
Content of
RFR, %
Breaking
strength,
MN/m2
Tearing
strength,
MN/m2
Elasticity
modulus,
GPa
Shrinkage,
%
Relative
elongation,
%
0
5
10
30
5
10
30
11.0
18.9
24.5
17.1
9.0
18.2
22.0
1.8
5.5
6.3
3.7
4.6
5.4
5.7
5.0
7.4
1.0
3.2
16
6
8
6
12
11
6
520
750
500
620
800
650
500
II
Table 9.10 Physicomechanical properties of films from RFR-modified butyl rubber dispersions.
Content of RFR, %
Breaking strength,
MN/m2
Tearing strength,
MN/m2
Elasticity modulus,
GPa
Shrinkage,
%
0
5
10
30
0.7
10.5
13.3
16.2
0.10
2.00
6.44
7.50
12.5
11.2
18.5
12.6
0
8
5
5
The concentration of an additive has a significant effect on the value of internal stresses in the formation of coatings (Table 9.11). At an optimal concentration of a modifying
additive, internal stresses are sharply reduced. Thus, it has been shown that modification of
polymer dispersions by oligomer and polymer systems soluble in the liquid phase makes it
possible under certain conditions to create a thixotropic structure in the initial film former
and in coatings on their basis. This was achieved by introduction of modifiers with an optimal flexibility and extent of branching of the chain into the dispersion; the modifiers had
a reduced solubility in the liquid phase and formed a three-dimensional network in cells of
which dispersion particles or the supramolecular structure of the main polymer are located.
In dispersions with a broad distribution of polymer particles by size, the skeleton of
the network structure is formed from finer particles, whose surface is not completely exposed to surfactants owing to dissimilar adsorption of emulsifier by particles of different
size. The use of surfactants of a polymer type with active polar groups for producing such
dispersions enables a stronger bond of larger dispersion particles with the network structure.
Regulating the nature of polymer or oligomer, which forms the network structure, by
introduction of various types of modifiers, it became possible to increase significantly the
adhesion strength of coatings, to change within broad limits their stress strain characteristics. Creation of a thixotropic structure enables a sharp reduction of internal stresses in the
CHAPTER 9
311
formation of coatings and an increase of the rate of relaxation processes, which made it possible to produce coatings with stable physicomechanical properties and sharply reduce their
formation time.
Table 9.11 Effect of the concentration of RFR on internal stresses in coatings from
butyl rubber dispersions.
Concentration of RFR, %
Internal stresses, MN/m2
0
5
10
30
0.6
0.6
0.3
0.6
Formation of the thixotropic structure was performed also without destruction of dispersion particles. The object of study were latexes of acrylic copolymers based on butyl
acrylate and butyl methacrylate taken at a ratio of 30:70 with monomers containing polar
groups of different nature (methacrylic acid, nitrile of acrylic acid). Polyacrylamide of the
molecular mass 0.25106 (PAA) and low-molecular-mass bifunctional compounds (ethylene glycol, propylene glycol) were used as modifiers changing the structure and properties
of the three-dimensional network. This problem was solved by comparing the structure of
the network using the method of electron microscopy and by studying the rheological properties and comparing them with the stress strain, relaxation and adhesion properties of
coatings. Films and coatings were formed on glass supports, papers, fibrous bases at 20 and
70C. The structure was studied by taking carbonplatinum replicas from the surface of
coatings. The stress strain characteristics were studied at a deformation rate of 10
mm/min. The kinetics of increment and relaxation of internal stresses and adhesion of coatings to the glass support was studied by the photoelastic method; adhesion to fibrous supports, by the delamination method.
Studies of structure formation in films from latexes of acrylic copolymers showed that
the network from latex particles is formed at a large concentration of polar groups in the
system and on their surface, which takes place at the introduction of more than 12% monomers with functional groups into acrylic latexes in the process of their emulsion polymerization. Data on the structure of films from acrylic copolymer with 12% methacrylic acid
(BMM) and 12% nitrilacrylic acid (BMN), obtained under the same conditions were presented. It was shown that coatings from BMM have a structure consisting of latex particles,
which have no dense packing; in gaps between particles, this structure is not revealed. The
fine structure of latex particles is not revealed by oxygen etching of specimens, either. This
is, probably, due to the fact that at a large concentration of carboxyl groups in the macromolecule system the polymer is characterized by an unfolded conformation of macromolecules, and the connection between individual latex particles is performed as the result of
the formation of a network from a finer structural elements 1020 nm in diameter, found
in studies of the initial latex structure. This network structure is strong and is preserved at
a prolonged heating of films at 70C. Formation of a network from such structures is, probably, due to the fact that their surface is not coated with an emulsifier, unlike latex particles.
Similar regularities in the formation of the network from latex particles are observed at a
large concentration of nitrile groups. Owing to a greater flexibility of macromolecules and
a smaller intermolecular interaction, the skeleton of the three-dimensional network in films
from copolymer BMN consists of globular structures similar by their size to the globules
312
that form latex particles. In cells of such a network, latex particles are characterized by a
hexagonal packing.
The specific features of the formation of the three-dimensional network in copolymers
distinguished by the nature of functional groups have a great influence on their physicomechanical properties. From the analysis of the stress strain properties of films from latexes
BMM and BMN, it is seen that films from BMM have a high modulus, breaking strength
and comparatively low relative elongation in contrast with films from BMN, which are
characterized by a larger strain, low elasticity modulus and strength. Studies of the kinetics
of increment and relaxation of internal stresses in the formation of coatings from these systems showed that the relaxation processes in coatings from BMM are slower. At the initial
stage of formation, comparatively high internal stresses emerge in them; these stresses can
cause a spontaneous disruption of materials in operation.
To accelerate the relaxation processes, latex BMM was modified by polyacrylamide.
Introduction of polyacrylamide does not change the size and shape of latex particles and
leads to an increase of the distance between them. Probably, polyacrylamide interacts with
finer structural elements located in between latex particles, and contributes to an increase
of strength and elasticity of the network, as well as adhesion of coatings. This is accompanied with a decrease of internal stresses in the system and an increase of the rate of the relaxation processes. We obtained data on the kinetics of increment and relaxation of internal
stresses in the formation of coatings from BMM, modified by an optimal amount of polyacrylamide at 20C. Introduction of a thixotropic additive significantly decreases internal
stresses and reduces the formation period of coatings on different-type papers and offprints.
This regularity is manifested under different conditions of formation of coatings, both at
20C and at 70C; the rheological properties of latex modified by polyacrylamide were presented. Introduction of modifier was shown to contribute to an additional structuring of the
system.
Data on the effect of polyacrylamide on the properties of latex coating were obtained.
It was shown that introduction of an optimal amount of PAA improves the decorative and
physicomechanical properties of coatings.
A different character of structure formation is observed in modification of latexes by
low-molecular-mass additives.
In the presence of these additives, the size of latex particles does not change, and the
coupling between them is performed by means of the network formed by fine globular
structures. At the introduction of propylene glycol, hexagonal packing of the structural elements of the network are observed. In the formation of coatings at 70C, the ordering of
the structure of the network skeleton is disturbed; herewith, fine globular structures are distributed unevenly in the gaps in between latex particles; the data on the dependence of the
physicomechanical properties of films on the concentration of modifier involved in the formation of the network structure were presented. It is seen that introduction of an optimal
amount of modifiers significantly increases adhesion of coatings to the tissue, increases the
strength and relative breaking elongation, decreases internal stresses in the system.
From these data, it is seen that formation of the network in disperse systems without
disrupting latex particles from finer structural elements and regulation of its structure using
various modifiers makes it possible to significantly increase the rate of coatings formation
and improve their physicomechanical properties.
CHAPTER 9
313
9.11 Combined packaging materials with increased protective properties

The use of polymer packaging materials is of great importance for the economy, as it makes
it possible to intensify foodstuff production processes, reduce the losses of foods, improve
quality, extend service life, decrease transportation expenses and in some cases to refrain
from the use of deficit tinplate containers.
A process for producing a number of novel combined materials was developed; the
materials are intended for packaging various foodstuffs: those subjected to heat treatment;
of a high degree of preparedness, including freeze-dried; second-course meals warmed before use; various conserves and preserves (fish, fruit-and-vegetable, milk etc.), granular
products.
Developed materials make it possible to perform sterilization of packages at a temperature of 120C for 1 hour in an aqueous medium, to perform packaging and long-term storage in an inert gas medium and under vacuum. They can be successfully processed on
high-speed packaging equipment, have an attractive appearance owing to the possibility of
multicolour printing. Their production technology makes it possible to apply colour images
both on the external layer and in between layers.
Combined sterilized materials are obtained by modification of batch-produced polyurethane glues. This provided for the stability of the performance characteristics of films at
the autoclave sterilization and chemical endurance in media modelling food products.
Works on the modification of glues were carried out with the aim to accelerate their
hardening. Preliminary results assume the development of a new process for production of
sterilized films using glues without solvents.
The characteristics of materials are given in Table 9.12.
Materials developed were thoroughly tested under performance conditions in contact
with media, which model food products: water, solutions of organic acids (acetic, lactic,
tartaric), solutions of cooking salt, crude vegetable oil.
Tests of pilot batches of materials for packaging and storage of various fruit-and-vegetable were carried out. Based on the data obtained, materials are recommended for packaging and storage of the following types of products: second-course meals (storage time,
1230 months); meat and vegetable conserves (storage time, 2430 months); vegetable
conserves (storage time, 1218 months); juices and beverages (storage time, 9 months); tomato hot-spices (storage time, 6 months).
Within the specified storage times, the quality of conserves corresponds to the requirements of normative and technical documentation for these products.
By the results of studies of containers and ready-prepared products, changes were introduced into the acting normative and technical documentation relative to packaging of
products into bags from polymer combined materials based on aluminium foil.
Tests of combined film materials PET + F + PEcm, PET + F + PP for packaging and
storage of bacterial preparations for cheese-making were conducted. The preparations were
packaged into investigated materials under vacuum, in a nitrogen and carbon dioxide medium. Six batches of biopreparations were tested. Preparations in these packagings were
tested in the process of storage in a combined regime, which reflected the regime of transporting the preparation to plants and its storage before use for the first 10 days at non-regulated (room) temperature, and then for up to 4 months at a subzero temperature (in the
freezing chamber of a refrigerator). The content of microflora (total amount) and aroma-forming compounds were determined, as well as the acid-forming activity, the mass
fraction of moisture, and the amount of inoculum prepared from the bacterial preparation
314
in the initial medium without replanting, in 10 days and at the end of storage. The control
was the preparation packaged into sealed glass vials.
Table 9.12 Characteristics of materials.
Parameter
PETP
+
PEcm
PETP
PA
+
+
PP
PEcm
Resistance to
delamination,
N/m
Breaking
strength, MPa
Ultimate
elongation, %
Puncture
resistance,
MPa
Weld seam
strength, N/m
Resistance to
delamination
after sterilization in aqueous
medium, N/m
Weld seam
strength after
sterilization in
aqueous
medium, N/m
290
290
PA
+
PP
290
OPP PETP PA+Al PETP

PA
OPP
+
+
+
+
+
+
PEcm Al+PP PEcm A1+PE Al+PP Al+PE
290
196
290
290
290
290
196
39.0 39.0 49.0 49.0 34.0 39.0 49.0 39.0 49.0 34.0
30
30
30
30
30
10
10
10
9.8
14.7 9.8
9.8
9.8
14.7 9.8
10
10
14.7 9.8
9.8
1200 1500 1200 1500 1200 1500 1200 1200 1500 1200
118
147
118
840
1050 840
147
118
1050 840
147
147
147
147
147
1050 840
840
1050 840
Note: 1. PETP, polyethylene terephthalate; PEcm, polyethylene; PP, polypropylene; PA, polyamide;
OPP, oriented polypropylene; A1, aluminium foil. 2. The width and admissible deviations for the
width are (60 750) 1 mm.
Table 9.13 Results of studies of preparations.
Parameter
Bacterial numbers,
billion cfu/g
initial total
initial aroma-forming
in four months
total
aroma-forming
Acid-forming activity
Vials
without
vacuum
Packets from film 1
Packets from film 2
under
vacuum
in N2
atmosphere
in CO2
atmosphere
under
vacuum
in N2
atmosphere
in CO2
atmosphere
380
360
330
230
370
240
340
260
360
250
330
270
280
240
350
230
315
CHAPTER 9
Table 9.13
Results
of studies of preparations.
(continued)
Parameter
initial
in 10 days
in 4 months
Mass fraction of
moisture, %
initial
in 10 days
in 4 months
Vials
without
vacuum
Packets from film 1
Packets from film 2
under
vacuum
in N2
atmosphere
in CO2
atmosphere
under
vacuum
in N2
atmosphere
in CO2
atmosphere
39
35
32
35
31
36
32
36
31
35
31
36
32
34
32
4.50
4.35
5.37
5.0
5.0
4.50
5.25
4.75
5.12
5.25
4.87
5.00
5.50
5.12
As the result, the materials (PET + F +PEcm and PET + F + PP, Table 9.13) were found
to be suitable for packaging and storage of dry bacterial preparations. These materials provide for a sufficiently good preservation of the preparation within the investigated period
of time. Storage of the preparation in packages under a vacuum, in a nitrogen or carbon dioxide atmosphere at a temperature regime required for the preparations showed (as compared with the control) a tendency to an increased survivability of microflora. In packaging
into packages without vacuum, the parameters after storage were identical to those of the
control specimen.
Thus, a series of promising combined materials with high protective properties and improved hygienic parameters were developed.
9.12 Effect of pH of the medium on the specific features of structure

formation and the properties of coatings from polymer dispersions
Studies of film formation from latexes of polyalkyl acrylates found that at a certain chemical composition they form coatings with a homogeneous ordered structure on fibrous bases
and on paper with good decorative properties, high physicomechanical and adhesion characteristics. However, at a low pH value of acrylic latexes they can cause the yellowing of
the fibrous bases and paper, the corrosion of process equipment.
The properties of dispersions and the process of film formation from these systems depend on the structure and composition of dispersion particles and interphase layers, the
composition of the dispersion medium. A significant effect on the properties of the dispersion and coatings from polyalkyl acrylates is rendered by pH of the medium. During the
titration of carboxyl groups of copolymers in the latex by alkali, the system exhibits the
properties of a weak acid with dissociation constants of 10 8 10 10 depending on the hydrophilicity of the dispersed phase, the glass-transition temperature, length and extent of
crosslinking of copolymer chains in particles and other factors, determining the accessibility of carboxyl groups in the titration by alkali. These effects are associated with the change
of entropy of neutralized latexes as the result of conformation changes of macromolecules
and the release of particles of hydrophilic groups to the surface.
The conductometric curves for acrylic copolymers, besides the main points of equivalency, corresponding to the complete neutralization of all carboxyl groups, were found to
316
have intermediate points of inflection corresponding to the neutralization of carboxyl

groups located near the interphase surface. The pH value of the medium has a significant
effect on the structure of the surface protective layers of dispersion particles. Salt groups
formed in the neutralization of acidic links of the polymer are concentrated on the surface
of the particles, which is accompanied by an increase of the saturation of interphase layers
and a redistribution of emulsifier, i.e., a decrease of the surface tension of the system. The
surface tension was found to be the lower, the larger the amount of bound methacrylic acid
(MAA) in the copolymer was; what is more, its dependence on pH passes through a minimum. The increase of the surface tension at large pH is explained by the increase of the interphase surface as the result of the swelling of dispersion particles in the neutralization of
inner carboxyl groups, which do not get to the surface of particles even in hydrated state
owing to steric hindrances. The ability of latexes of acrylic copolymers to become denser
under the action of alkali is associated with these phenomena. By the character of viscosity
change depending on pH, latexes of various copolymers are divided into three groups. For
systems of the first group, the viscosity of latexes does not change or changes slightly depending on pH; for systems of the second group, it increases significantly at the introduction
of alkali and then slightly decreases at high values of pH; for systems of the third group,
viscosity changes nonmonotonically and exhibits a maximum. It is assumed that the small
effect of pH on the viscosity of dispersions is characteristic of latexes from nonpolar copolymers, for polymer chains with a high glass-transition temperature, which do not in practice
swell in water alkali.
An increase of viscosity with the pH rise of second-group latexes is explained by the
total or partial dissolution of carboxylated copolymer owing to the fact that the energy of
hydration of salt groups formed in neutralization is higher than the energy of intermolecular
interaction, for instance, for styrene-carboxylated latexes with 20% MAA. However, even
at a MAA content of 2025%, the viscosity may not change depending on pH. An increment of viscosity with pH increasing was also found for hydrophilic carboxylated latexes
with a certain amount of crosslinking agents, which strongly swell in alkaline water but are
incapable of forming molecular solutions.
The nonmonotonic change of viscosity on pH was only found for copolymers of acrylic ethers. A sharp increment of viscosity at a certain pH and its subsequent decrease are explained by the successive processes (occurring with the neutralization developing) of
swelling and subsequent dissolution of swollen particles. It is believed that the thickening
of latexes occurs at the stage of true solutions as the result of the formation of intermolecular
hydrogen bonds between carboxyl and ester groups. Studies were carried out for strongly
diluted latexes to rule out the effect of protective interphase layers on the process of local
thickening and dissolution of particles. By the example of latex of the copolymer of ethylacrylate with methyl methacrylate and acrylic acid with the dry substance content of 50%,
it was shown that the extent of alkaline thickening can change from 1 up to 29 units at other
conditions equal, depending on the ratio of ionic and nonionogenic emulsifiers. The data
on the effect of colloidal chemical factors are rather contradictory, which indicates that
the mechanism of structural transformations and properties of dispersions at a change of pH
of the medium has not been studied sufficiently.
The effect of pH on the properties of dispersions and coatings from acrylic latexes
based on butyl acrylate, methyl methacrylate and methacrylic acid at a constant ratio of the
first two components and various contents of MAA, as well as at a constant content of MAA
and various contents of the first two components was studied. Latexes were obtained under
the same conditions using sulfanol S-10 as emulsifier and ammonium persulfate as initiator.
CHAPTER 9
317
The content of dry residue was 50%; size of particles, 0.09 m; the content of residual
monomer, 0.05%, pH 2.5; surface tension, 38 mN/m. For comparison, butadiene nitrile latex SKN-40 1GP was studied. The size of particles was determined by the method of sedimentation analysis in a centrifugal force field. Structural transformations in dispersions
were studied using the method of electron microscopy, potentiometric and conductometric
titration, rheological methods.
To study the conformational transitions of macromolecules depending on various
physicochemical factors, use was made of the concentration dependence of the reduced viscosity of the solutions of copolymers of latexes, as well as the curves of their turbimetric
titration. The process of film formation was studied by the kinetics of change of internal
stresses at various formation stages, stipulated by the incompletion of the relaxation processes. The physicochemical properties of films were studied by standard methods by establishing their thermomechanical curves, kinetics of swelling in organic solvents,
determination of tensile strength and relative elongation.
Studies of the properties of latex SKN-40 depending on colloidal chemical parameters of dispersions found that its viscosity does not practically depend on pH within a broad
range of values, from 3 up to 11. Similar regularities in the change of rheological properties
depending on pH were found for latexes of copolymer of styrene with a minor amount of
MAA. This effect is associated with the high glass-transition temperature of copolymers
and with the predominance of hydrophobic links in macromolecules, as the result of which
particles of dispersions do not in practice swell in water alkali. However, the investigated
butadiene nitrile latex is not hydrophobic, its particles swell in a dispersion medium and
change their sizes in the process of film formation. The change of pH in this case, too, has
a comparatively small effect not only on the rheological properties of dispersions, but also
on the physicomechanical characteristics of films, increasing them within the range of 15
to 30%. Studies of the structure of dispersion particles by the method of electron-microscopy found them to consist of more fine globular-type structural elements of up to 2025
nm in diameter, formed as the result of folding of individual macromolecules.
From the data on the kinetics of formation of coatings from these dispersions, it follows that, irrespective of pH, a sharp increment of internal stresses is observed after the removal of the liquid base; the increment indicates the emergence of local bonds between
dispersion particles, which clearly preserve their interfaces after the removal of moisture.
At a subsequent formation of coatings under the same conditions, one observes a regrouping
of structural elements present in the dispersion particles; the regrouping is completed in 15
days at 20C to form a homogeneous globular structure. At this stage of formation, one observes a decrease of internal stresses owing to the relaxation processes.
Other regularities are observed in the change of properties of dispersions and coatings
for latexes of acrylic copolymers. Studies of the dependence of the relative viscosity on pH
of acrylic latexes found that at a content of MAA up to 3% the change of pH has no influence on the value of relative viscosity.
At a MAA content of more than 3% in the copolymer, the curves for the dependence
of relative viscosity on pH are found to have two characteristic regions. Up to pH 8.5, the
viscosity is practically constant, and then a maximum is observed at pH 1011. Similar regularities are observed in the change of colloidal chemical properties of dispersions depending on pH. As is seen in Table 9.14, within the pH range of 3.4 up to 8.2, the size of
particles, optical density, structural viscosity remain constant.
At a further increase of pH, they change nonmonotonously, exhibiting a maximum, the
same way as the relative viscosity.
318
At a constant chemical composition of copolymers and the invariability of the other

colloidal chemical properties, within the pH range of 3 up to 8.5, it could have been expected that the change of pH in this region would not have rendered a significant effect on
the process of film formation and the properties of coatings. However, the character of the
change of the physicomechanical characteristics films depending on pH does not correlate
with the regularities in the change of the colloidal chemical properties of latex up to
Table 9.14 Colloidalchemical properties of latex of acrylic copolymers at different pH.
pH of latex
Most probable radius

of particles, nm
Optical density
3.4
5.4
6.7
7.5
8.2
9.2
10.2
10.5
12.5
45
45
45
45
166
204
290
100
140
2.42
2.42
2.43
2.62
2.84
2.70
2.20
1.38
1.24
Structural viscosity at
shear stress of 103 N/m2, Pas
3.1
3.1
3.2
3.3
10.5
12.4
127.2
99.7
90.3
pH 8.5. While the colloidal chemical properties of dispersions in this pH range do not
practically change, the tensile strength of films increases, and relative elongation drops
down. At a further increase of pH, the character of the change of the physicomechanical
characteristics of films and the colloidal chemical properties of latexes correlate. The effect of pH on the film formation processes is manifested differently depending on the range
of its change. At pH smaller than 8.5, internal stresses change nonmonotonously in the process of film formation: first they increase and then relax. This character of their change, as
is shown by the method of electron microscopy, is related to the features of structure formation at various stages of film formation. Internal stresses reach a maximum after the removal of the liquid phase and the emergence of local bonds between dispersion particles.
Then internal stresses relax to a constant value, which is due to the regrouping of structural
elements in the latex particles.
The extent of incompletion of the relaxation processes, which determines the value of
internal stresses and the character of their change in the process of film formation for latexes
from acrylic copolymers depends on pH. With pH increasing from 8.5 up to 1011, internal
stresses decrease 34 times and are observed to increase monotonically in the process of
film formation up to an ultimate maximum value, which remains constant at a subsequent
storage of specimens under the same conditions. It was found by the method of electron microscopy that the loosening of the structure of latex particles and their decomposition into
initial structural elements occurs in the dispersion at pH greater than 8.5. These regularities
are well consistent with the data of the rheological studies of copolymer solutions at various
pH values and with the results of their turbidimetric titration. It was shown that with pH
increasing the Huggins constant increases and the quality of the solvent worsens.
The solubility of copolymer with the change of pH depends on the content of MAA in
the chain. Copolymers with the content of MAA greater than 3% did not dissolve in dioxane
at pH 1012, and at pH 88.5 swelled within several days to dissolution. The change of
CHAPTER 9
319
the quality of the solvent with respect to copolymer from latexes with different pH affects
the dependence of the optical density of solutions on the share of the precipitation agent.
It is seen from the turbidimetric titration curves that, at pH greater than 2, inflections
or additional peaks are observed, which are determined by the formation of associates from
different-composition components. The result of this is that additional transitions are also
observed in the thermomechanical curves for films from dispersions with high pH. The decomposition mechanism of dispersions in pH range from 8.5 up to 12 was studied, as well
as the causes for the absence of correlation in the change of colloidal chemical properties
of dispersions and films in the pH range from 3 up to 8.5. The properties of coatings depend
on the size and structure of associates entering into the composition of latex particles.
To study the conformational transitions of macromolecules in associates depending on
pH, use was made of various physicochemical methods. Irrespective of the method of producing latex (the order of introducing components, time, dosage, other factors), an increase
of pH contributes to a monotonic increment of the surface tension from 4748 up to 5256
MN/m. This indicates that alkali as a surface-inactive substance diffuses depthward into the
latex particles. To study the mechanism of the processes occurring in the introduction of
alkali, the potentiometric titration curves of polymethacrylic acid (PMAA), synthesized under the same conditions in the presence of an emulsifier and initiator used in the synthesis
of latexes from copolymers, were recorded. From the analysis of these results, it follows
that the potentiometric titration curve of PMAA is typical of polyelectrolytes containing
secondary associated structures. The initial increment of pH is due to the ionization of the
functional groups of macromolecules. In transition from a weakly dissociated acidic form
to a strongly dissociated salt form in the associated state, an inflection on the curve and a
sharp slowdown of the rate of pH rise are observed. This part of the curve corresponds to a
conformational transition of macromolecules from a compact ball into a more unfolded
shape. The transition is accompanied by the mutual repulsion of macromolecules as the result of the accumulation of like-charged groups, which can lead to the loosening or destruction of associates. A weak change of pH in this region is stipulated by a possible
compensation of its increment with the chain charge increase, by unfolding of macromolecules and by the decrease of the linear density of the charge. Then an increase of pH in the
nonstructured system is observed. For latex of the copolymer, a significant increment of pH
is observed at the initial stage as compared with PMAA, which is, probably, due to a weaker
intermolecular interaction of associated macromolecules owing to a smaller number of polar groups in the copolymer. Further on, a point of inflection and a sharp slowdown of the
dissociation process are observed, which can be due to the loosening of associates owing
to the weakening of intermolecular interaction. The absence of a region of the subsequent
significant increment of dissociation indicates that, unlike PMAA, in the case of copolymer
the conformation changes of macromolecules are not completed by the destruction of associates. The higher the concentration of PMAA in the copolymer, the nearer the character of
potentiometric curves of copolymers approaches the similar curves for PMAA. The commonality of conformation changes in macromolecules of PMAA and PMAA-containing copolymers is confirmed by the results of studies of the dependence of reduced viscosity on
concentration. It is known that for solutions of uncharged polymers the dependence of reduced viscosity on concentration obeys the Huggins equation, according to which the viscosity increases by a linear law as the concentration is increased. In the case of polyelectrolytes, an anomalous dependence of viscosity on concentration of the solution is observed.
This is related to the increase of the linear sizes of macromolecular balls due to the electrostatic repulsion of like-charged links of the chain owing to the swelling of macromolecules
320
at a decrease of the ionic strength of the solution with its concentration decreased. The conformational transitions determining the character of the dependence of reduced viscosity on
concentration for PMAA and for copolymers are the same. The dependence of reduced viscosity on pH for diluted dispersions of copolymers is similar to the regularities in the change
of relative viscosity on pH for dispersions of the same composition. This is, probably, due
to the fact that conformational transitions in associated macromolecules are responsible for
structural transformations during the change of pH for solutions and dispersions of copolymers.
From the presented data, it follows that a significant effect on the film formation mechanism and properties of latex coatings is rendered by the structure of latex particles and associates that form them. A change of pH from 3 up to 8.5 has no influence on the
colloidal chemical properties of dispersions, but does significantly affect the film formation process and properties of films as the result of conformational transitions of macromolecules in associates and of the change of intermolecular interaction of the system. At a
further increase of pH, the conformational transitions in associated macromolecules lead to
the breakdown of particles of dispersions into initial structural elements. This is accompanied by an acceleration of the relaxation processes in the system, a sharp decrease of internal
stresses and an increment of the strength parameters owing to an increase of the intermolecular interaction.
The effect of pH of the medium on the formation and properties of properties of coatings from latex BM-12 based on acrylic monomers of methacrylic acid was studied with
the view of developing compositions with optimal process properties. Dispersions with pH
from 2.5 up to 8.4 were obtained by the method of hot neutralization by introducing various
amounts of ammonia into the latex. The kinetics of increment and relaxation of internal
stresses in the formation of coatings at 20C was studied. The character of the kinetic curves
and value of internal stresses were shown to depend on pH of the medium. At pH from 2.5
up to 5, coatings are formed very quickly, in 1530 min. At a subsequent prolonged holding
of coatings under formation conditions for 810 days, internal stresses do not change in
practice. With pH increasing above 5, internal stresses in the formation of latex coatings
were observed to change nonmonotonically. First internal stresses rise up to a maximal ultimate value, and then relax. The coating formation period up to the extreme and equilibrium values of internal stresses increases with pH of the medium increasing. The formation
process is the most quick for coatings from dispersions with pH of the medium from 2.5 up
to 5. However, internal stresses in this case are significant, from 0.4 up to 1.0 MPa. With
pH increased up to 7.7, the coatings formation time increases up to 34 hours at a significantly lower value of internal stresses about 0.2 MPa. At a further increase of pH up to
8.28.4 the equilibrium values of internal stresses are achieved in 5070 hours at a simultaneous increment of their magnitude.
The effect of pH on the rheological properties of latex was studied to elucidate the
causes of the different character of the change of internal stresses in the formation of coatings from latexes differing by pH of the medium.
From the results of the study of the dependence of viscosity on shearing stress for latexes BM-12 at different pH values, it follows that dispersions are structured systems. With
pH increasing from 2.5 up to 7.7, the ultimate shearing stress and viscosity of the disrupted
structure increases. At a subsequent increase of pH, the ultimate shearing stress decreases
and the character of the rheological curves changes. At pH 8.2, a sharp difference between
the upper and lower levels of viscosity is observed, which is indicative of the occurrence of
a small number of contacts between structural elements, weak intermolecular interaction
321
CHAPTER 9
between them. Latex with pH 7.7 is the most structured dispersion. Coatings produced from
this dispersion exhibit the lowest internal stresses (Table 9.15).
Table 9.15 Effect of pH on the properties of coatings from latex BM-12.
pH
Gloss, %
Adhesiveness,
MPa
a, MPa
b, MPa
p, MPa
, %
3.0
5.3
7.7
7.9
8.2
35 40
35 40
40 45
25 30
23 228
0.10
0.15
0.07
0.15
0.10
4.0
7.8
14.5
12.0
11.0
0.8
0.5
0.3
0.5
0.7
6.8
9.0
9.3
7.0
6.7
210
250
310
250
200
The data on the rheological properties were compared with the size of latex particles
determined by electron microscopy. The size of latex particles was shown to change nonmonotonically with respect to pH. With pH increasing from 3 up to 7.7, it decreases from
0.15 to 0.06 m, and then at the subsequent increase of pH up to 8.4, increases up to 0.2
m. The peculiar feature of these dispersions is that, starting from pH 7.7, the polydispersity
of latex significantly increases, and, along with large particles of up to 0.060.2 m, globules of 1520 nm in diameter are found, which correspond to the size of separate folded
macromolecules. This character of structure formation at higher pH values indicates the interaction of ammonium ions with carboxyl groups of macromolecules in the polymer, a decrease of intermolecular interaction and dispersal of latex particles at an optimal pH. At the
subsequent increase of pH, ammonia acts as an astabilizing agent contributing to the agglomeration of latex particles.
The structure of coatings, corresponding to the equilibrium value of internal stresses,
was studied using the method of oxygen etching to elucidate the peculiar features of structure formation in dispersions depending on pH of the medium. It was shown that at pH from
2.5 up to 7 latex particles are characterized by a very fine structure formed by unfolded
densely packed macromolecules. With pH decreasing, the ability of latex particles to coalesce worsens. At pH 7.7, a network structure from anisodiametric structural elements is
observed. At a subsequent increase of pH, an inhomogeneous globular structure from aggregated structural elements is formed.
Formation of a set of supramolecular structures of various sizes in dispersions with an
alkaline medium extends the formation time of coatings as the consequence of incomplete
relaxation processes and contributes to the nonmonotonic change of internal stresses in the
coating formation process. Formation of coatings from a dispersion with pH 7.7 makes it
possible to produce materials with optimal properties: low internal stresses, good physicomechanical characteristics and adhesion strength, high gloss and the absence of tack. Similar regularities in the change of the properties of coatings on the value of pH are observed
in their formation at higher temperatures, for instance, at 60C.
9.13 Polyurethane chemically resistant coatings for protection of container

and packaging materials
The main requirements imposed on modern polymer materials are economic feasibility,
ecological safety and high quality. It is not easy to provide for the combination of all these
properties in one product. As a rule, each of them has both advantages and drawbacks. Poly-
322
urethane polymers satisfy these requirements the most. They are widely used for protection
of airplanes, automobiles, bridges, chemical equipment, furniture, household electrical appliances, etc.
Over the past thirty years, the range of polyurethane materials has been significantly
expanded, and to date there are a larger number of formulations, beginning with traditional
lacquers and enamels and ending with modern ecologically favourable systems. By the volumes of production and consumption, they give way to other types of products. In Western
Europe, for instance, the share of polyurethane film formers on the market of resins is 15%,
whereas for alkides this parameter reaches 40%. However, by the consumption increment
rates polyurethanes are almost two times ahead of all other types of polymer materials. According to predictions by specialists, in the near future, demand for them would grow 46%
a year on average. At present, polyurethanes are produced by a large number of big and medium-size firms all over the world. Among the most known are ICP (England), Bayer (Germany), Akzo Nobel (Holland), Monsanto (USA), King Ind (USA), Reichhold (Germany),
BASF (Germany), Kemira (Finland), Cray Valley (England), DSM (Holland), Rhone-Poulenc (France) etc.
The rise of popularity of polyurethanes is explained by that coatings on their basis are
distinguished by a high quality. They dry fast, are resistant to the action of the atmosphere,
water, abrasion, low temperature and heat. Polyurethanes possess a high adhesion to various
supports, including metal, wood, plastic, concrete, as well as have good decorative properties.
Along with the unique performance properties, it is not difficult to fabricate ecologically friendly materials on their basis, which would totally satisfy the current sanitary
norms. They find ever increasing use in production of materials with a decreased content
of solvents, aqueous dispersions, ink powders and systems of traditional drying. As for the
economic feasibility of polyurethane materials, there is no common opinion in this issue.
This parameter is determined by the cost of initial raw materials: hydroxyl-containing oligomer and isocyanates. Polyols and hydroxylated acrylates, polyesters, epoxides, alkides,
vinyl compounds etc. are used as the former. For crosslinking of these oligomers, use is
made of aliphatic, aromatic, cycloaliphatic and other kinds of diisocyanates and polyisocyanates. The most widespread are 2,4- and 2,6-toluylene diisocyanates, 1,6-hexamethylene
diisocyanate, polyisocyanate biuret, isophorone diisocyanate and adducts based on the listed compounds.
Polyurethanes are more expensive than most known polymer materials. However, with
account for the durability of coatings and their performance properties they can be considered competitive.
Polyurethanes can be one- and two-pot systems. According to the international classification, they can be divided into several groups. The first are two-pot systems hardened at
usual or elevated temperature. The second group unites materials, which harden at usual
temperature by the air moisture. The third group are polyurethane materials of hot drying,
which form coatings at high temperature (up to 150C). The fourth group are polyurethanes,
which harden under room conditions, in particular, aqueous dispersions. The last group also
includes lacquer-and-paint materials based on modified polyurethanes uralkides of oxidative drying.
Polyurethane coatings of organic solvent-base type, as well as ecologically friendly
materials on an aqueous base, with a high dry residue, powdered and of radiation drying
have specific spheres of application; some of them are only suitable to be used in rather
narrow areas, whereas others are universal.
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Among organic solvent-base polyurethanes, the most popular are two-pot lacquers and
enamels, one of whose components is a solution of polyol with pigments and additives, and
the other is a solution of isocyanate hardener. Components are mixed directly before use,
because their spreadable time is restricted by an interval of 6 up to 72 hours. Many polyurethanes of this class harden at usual temperature, others require heating or introduction
of additional catalysts. However, in all cases they form coatings of high quality, which are
distinguished by abrasion, chemical, low-temperature and water resistance properties, have
good decorative properties.
Owing to their high corrosion resistance, two-pot polyurethanes are successfully used
as a component of multilayer coatings of various metal engineering structures operated under atmospheric conditions. As a rule, they serve as a material for the upper layers of coatings and to a large extent provide for their durability. In combination with epoxides or other
anticorrosion primers, polyurethane lacquers and enamels are used for protection of bridges, reservoirs, pipelines, airplanes, excavators, railway cars, combines.
In recent years, two-pot materials started to be actively used in automobile industry
for formation of priming, intermediate and top coatings. For instance, five production lines
for painting of automotive bodies operate at present in the USA. As the drying temperature
of such materials is not higher than 80C, it is very convenient to use them for the joint
painting of plastic and metal components of the body. To produce colourless finishing coatings of the bodies, use is made of acryl urethane lacquers based on aliphatic isocyanates.
Coatings from such lacquers do not exhibit the aptitude for gradual yellowing, as it happens
with lacquers containing aromatic isocyanates. Despite the fact that two-pot polyurethanes
quite satisfy the requirements imposed on their performance properties, they have a number
of drawbacks, which include the inconformity with modern ecological norms. One of the
possible ways to overcome this drawback is to reduce the content of volatile organic compounds by increasing the amount of the dry residue. This approach assumes the use of reactive thinners instead of volatile solvents.
When preparing formulations of two-pot polyurethanes with high dry residue, it is necessary to thoroughly choose the components in order to provide for the required balance of
the spreadable life, viscosity and drying rate of materials. The observance of these parameters makes it possible to produce compositions with the content of volatile solvents not
higher than 280 g/l. Polyurethanes with a high dry residue are used in the same fields as
traditional lacquers and enamels.
Of great interest are two-pot polyurethanes with 100% dry residue, which are widely
used for anticorrosion coatings. They are fabricated using low-viscous isocyanates and special polyols. Owing to high heat resistance, low-temperature resistance, wear resistance and
shock resistance, polyurethanes containing no solvents are used for protection of petroleum
and gas pipelines, metal constructions, sewage collectors and other facilities operated under
conditions of cold or hot climate. Polyurethanes of this class are also suitable coatings on
flexible supports (canvas, tents, rainwear).
Two-pot polyurethane materials are used, which are based on urethane prepolymers
hardened by air moisture. In this case, the composition consists of solutions of prepolymer
with free isocyanate groups and hardening catalyst, which are mixed before use. Moisture-hardened polyurethanes are also manufactured as one-pot systems, which are more
convenient to use. They preserve their resistance in storage, and rapidly harden in the presence of moisture to form water- and abrasion-resistant coatings. A promising application
of moisture-hardened polyurethanes is protection of metal, concrete and reinforced-concrete constructions operated under atmospheric conditions. These materials provide for
324
high-quality coatings with service life of 1520 years, resistant to the action of UV radiation and exceeding epoxy coatings by elasticity. A promising approach is to use moisture-hardened polyurethanes for thick-walled coatings of floors over the concrete base in
industrial, municipal and sports buildings. Such coatings impart the surface with vibration
resistance, elasticity, sound-absorbing properties and wear resistance.
Among one-pot polyurethanes, special mention should be made of hot-hardening systems, which are solutions of hydroxyl-containing oligomers and blocked isocyanates. They
are stable at usual temperature and, when heated above 100C, split to release free isocyanates, which play the role of hardeners proper. Owing to the achievements of polymer
physics and chemistry in the use of catalysts and the modification of film formers, thermosetting polyurethanes with a reduced drying temperature of up to 100C were developed,
which form high-quality long-lasting coatings.
The largest developer of two-pot aqueous dispersions of polyurethanes is the company
Bayer. They are distinguished by ecological safety, good spreadable life, the possibility
of producing thick-layer coatings up to 80 m, as well as strength, water resistance, chemical resistance and weatherability.
Despite the high quality, unique durability and ecological merits, water-base two-pot
polyurethanes have significant drawbacks, associated with restricted pot life and relative
toxicity of the isocyanate component. One-pot analogs based on prepolymers of physical
drying or self-crosslinking film formers are much more processible and safe. Polyurethane
dispersions find use for painting wood, concrete, plastics, leather and are manufactured by
the largest Western companies. A promising field of application is protection of metal
items: rolled metal, aerotechnics, nuclear facilities, finish hardware, as well as metal constructions operated in very contaminated atmosphere. Production of water-borne polyurethanes for coatings of wood parquet flooring expands at a high rate. In the last five years,
production of aqueous polyurethanes for these purposes increased 2.5-fold in the industrial
sector and 10-fold in retail sales. They are also used for finishing offices, furniture, interior
design. The systems most widely used for wood finishing are polyurethane dispersions in
a mixture with acrylic latexes, acryl urethane dispersions and compositions on their base
with particles of the nucleusshell type. They are intended for finishing not only wood but
also metal and concrete.
The most important sphere of use of polyurethanes is production of powdered compositions. These materials are most popular in the USA and Japan, where their share is up to
35% of the total marker of powders consumption. In Western Europe, this parameter is only
4%. Powdered compositions are widely used for protection of household appliances due to
their high hardness and shock resistance, resistance to yellowing in the process of hot drying. Acryl- and polyester-urethane powders are widely used for high-quality finishing of
electrical appliances.
Powdered polyurethanes are produced using polyester polyols as well as epoxy and
acrylate polyols.
Powdered compositions are characterized by a rather high hardening temperature,
which leads to a significant consumption of energy. To reduce the drying temperature, use
is made of tin-containing catalysts; in this case, the drying temperature decreases down to
140160C, which makes possible a 25% reduction of energy consumed for hardening. To
produce polyurethanes with a reduced drying temperature, use is made of powders based
on polyester polyols crosslinked using the toluylene diisocyanate trimer. These compositions occupy the third place by the volume of production in Western Europe after epoxy
and epoxy-polyester materials. Coatings based on powdered compositions are character-
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325
ized by a low water absorbance, good thermal resistance and light permanence. They are
widely used for protection of garden metal furniture, window frames, doors, electrical
household appliances and metal constructions operated under atmospheric conditions. On
their base, powders with decreased hardening temperature were developed; this factor is especially important for painting of metal profiles with plastic elements.
Polyester urethane materials based on isocyanate-modified alkyd resins harden due to
oxidative polymerization by the double bonds. They are used for packaging compositions
of solvent- or water-soluble types, are cheap and accessible among various polyurethane
materials. Coatings from them rapidly harden in the air and are distinguished with good protective properties. By the atmospheric and wear resistance, they exceed considerably coatings from alkyd materials, are resistant to air moisture due to the absence of free isocyanate
groups, which makes unnecessary introduction of additives for absorbing moisture from
raw-material components. The great diversity of polyurethanes makes it possible to produce
highly competitive long-lasting and high-quality coatings for various purposes. Among the
reasons impeding the introduction of polyurethanes into practice are complexity of work
with two-pot systems, toxicity of isocyanates, relatively high cost of raw materials and final
product. These reasons and the deficit of raw materials explain the unsatisfactory condition
of the market of polyurethane materials. The volume of domestic production can not satisfy
the requirements of their use. Unfortunately, production of Russian-made environmentally
benign polyurethane materials (aqueous and powdered) is insignificant.
When developing polyurethane materials, it is necessary to take into account the effect
of the structure of polyurethane blocks on internal stresses in coatings, causing a spontaneous delamination and destruction of coatings in operation, and being a criterion of their durability.
The developed polyurethane compositions are of great interest for protection of container and packaging materials.
9.14 Protective polyurethane coatings and adhesive compounds

Coatings based on polyurethanes are characterized by a valuable set of properties: high
chemical endurance, adhesion strength, good decorative and protective properties.
A great number of formulations have been developed, including traditional lacquers
and enamels, which are distinguished by modern ecologically friendly properties. However,
by the volumes of production and consumption polyurethane compositions give way to other kinds of polymer products. In spite of the comparatively small volume of their production
as compared with other film formers, the rates of consumption growth of polyurethane materials are two times higher than those of all the other film formers.
A valuable set of the performance properties of polyurethanes is determined by their
mesomorphic ordered structure, associated with the regular alteration of flexible and rigid
blocks in their structure.
The aim of our work is to compare the formation process and properties of polyurethane coatings of two different classes, distinguished by the chemical composition and coating-formation method.
Polyurethane (No 1) developed in Germany (grade Morefree 402A + C79) was obtained based on diphenyl methane diisocyanate and polyester, taken at a ratio of 2:1. The
composition contains no solvents. Formation of coatings is performed as the result of fusion
of particles of the powdered system. Hardening of films and coatings is performed by the
stepwise regime: at 60C, 20 min; at 165C, from 1 up to 5 min.
Dynamic viscosity, Pa s
326
60 C
90 C
200
150
100
50
200
15
150
90 C
20 Time, h
20 C
60 C
100
50
10
Figure 9.4
10
Dependence of viscosity on structuring time at various temperatures of composition 1.
Dynamic viscosity, Pa s
Figure 9.3
20 C
20
30
40 Time, h
Dependence of viscosity on structuring time at various temperatures of composition 2.
Coatings from composition No 2 of domestic production were held preliminarily for

24 hours at 20C to remove the solvent, then were hardened according to a regime similar
for films from composition No 1.
Viscosity of film formers was determined by the falling-ball method. The adhesion
strength was assessed by the effort of delaminating the splicings held in touch with the adhesion-promoting agent for 10 min under a load of 200 g. The physicomechanical characteristics were studied at a loading rate of 50 mm/min. Internal stresses were determined by
the photoelastic method on an instrument with the automatic registration of path differeence.
Figure 9.3 presents the dependence of viscosity of composition No 1 on time at various
temperatures. Preliminarily, the viscosity enabling quality films of materials with a homogeneous structure was determined. It is seen in the figure that, as temperature increases, viscosity rises, apparently, owing to the interaction of the systems components. At 20C, a
significant increment is observed in 5 h. The structurizing of the film former, associated
with the loss of yield at 20C, begins in 18 hours.
Figure 9.4 presents a dependence of viscosity on time at various temperatures for composition No 2. It is seen that, as compared with composition No 1, the same value of viscosity can be obtained at a temperature increase for a smaller time of the significant
increment of viscosity at 20C and is observed after 8 hours. The loss of yield by composition No 2 at 20C is observed in 3540 h.
Resistance to lamination, N/m
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327
3500
3000
2500
2000
1500
1000
500
0
0
50 100 150 200 250 300 350 400 450

Hardening time, h
Figure 9.5 Dependence of delamination resistance on hardening time of bonded joints from composition 1 (1) and composition 2 (2).
Optimal regimes were assessed by the delamination strength of compositions from

polypropylene with polyethylene bonded by bonding adhesives No 1 and No 2 (Fig. 9.5).
It is seen in the figure that the dependence of the delamination force on hardening time is
of a nonmonotonic character. For bonding adhesive No 1, the optimal hardening time is
from 50 up to 130 hours and is characterized by the maximal delamination load. For film
former No 2, this parameter is from 5 up to 50 h.
Due to the presence of a solvent in the film former, its hardening and an increment of
the resistance to peeling occur faster than in bonding adhesive No 1 to make 2700 N/m instead of 3200 N/m for system No 1.
Figure 9.6 presents the physicomechanical properties of films from systems No 1 and
No 2. It is seen that the character of the curves for films from system No 2 is typical of amorphous materials. They are also distinguished by a greater elasticity. The breaking stress for
them is 2.1 MPa, and strain is 460%. For films from composition No 1, these parameters
are, respectively, 6 MPa and 268%.
Studies of the kinetics of increment and relaxation of internal stresses found that (Fig.
9.7) they change nonmonotonically for coatings from composition No 1. Such regularities
in the change of internal stresses are characteristic of coatings adsorbing the moisture from
the air owing to their high porosity and imperfection of the structure.
Internal stresses in the formation of coatings from composition No 2 in similar conditions reach an ultimate constant value in 3 hours of hardening at 20C and remain stable
even after a heating of coatings at 165C.
From the analysis of the results of the studies, it follows that materials from polyurethane of domestic manufacture are characterized by stable and high performance properties.
They are used as glue compositions in production of packaging combined materials.
The CJSC Scientific-and-Technical Company Korona-Lak developed and organized commercial production of polyurethane lacquer-and-paint materials and the system
of coatings on their basis.
The main distinctive feature of polyurethane coatings is the high level of protective
properties due to the reactivity of the isocyanate group (N=C=O), the heterogeneous nature of its double bonds. This makes it possible to produce most diverse polyurethane lacquer-and-paint materials based on polyester, alkyd, acryl and epoxy resins containing active
hydrogen, which provides for the formation of urethane bonds.
328
Stress, MPa
4
3
2
1
0
0 10
50
90
130
170
210 250 268

Deformation, %
2.5
b
Stress, MPa
2.0
1.5
1.0
0.5
0
0 20 60 100 140 180 220 260 300 340 380 420 460
Deformation, %
Figure 9.6
Dependence of stress on strain for system 1 (a) and system 2 (b).
Polyurethane coatings are distinguished by light permanence and stability of the decorative properties in long-term operation of articles from ferrous and nonferrous metals,
plastics, wood and other materials in various climatic conditions. Coatings are stable to the
action of subzero temperatures, mineral and organic oils; possess water, petrol and abrasion
resistance.
Reliability and durability of polyurethane coatings depend on:
the properties of initial raw material components, chosen based on the technical requirements for the operation of coatings;
the system of a coating; conditions and regimes of its formation;
ways of preliminary preparation of the surface to be painted.
Due to the relatively high cost, polyurethane lacquer-and-paint materials should be
used in cases when expenses for their use are paid off by either durability (no less than 10
years), or by the necessity to restrict the volume of use of traditional lacquer-and-paint materials.
The feasibility calculations showed that in painting one railway car the replacement of
enamel PF-115 by polyurethane lacquer-and-paint materials leads to a 3-fold increase of
the service life, as the result of which not only the consumption of lacquer-and-paint materials decreases from 100 down to 30 kg and painting expenses by 25%, but, respectively,
the ecological load in painting works is reduced.
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329
Internal stress, MPa
1.2
a
1.0
0.8
0.6
0.4
0.2
0
Internal stress, MPa
0
0.50
0.45
0.40
0.35
0.30
3
4
Time, h
3
5
Time, min
0.25
0.20
0.15
0.10
0.05
0
0
Time, days
Time, min at 165 C
Figure 9.7 Kinetics of internal stresses for system 1 (a) and system 2 (b).
The world production of polyurethane lacquer-and-paint materials is approximately

700 tons/year. In Russia, polyurethanes are only 5% of the total range of produced lacquerand-paint materials. In the USSR, the development of polyurethane lacquer-and-paint materials was hindered by the insufficient means for importing raw materials, but the modern
economic situation significantly simplifies the solution of this problem. Starting from 1998,
in connection with the increasing demand for new domestic types of lacquer-and-paint materials, such enterprises as Yaroslavl Lacquer-and-Paint Plant Pobeda Rabochikh, Joint
Stock Company Ekolpol, Close Joint Stock Company Korona-Lak, conduct research
into development of polyurethane lacquer-and-paint materials. The company KoronaLak in a comparatively small period of time developed and phased in a number of new
polyurethane materials for painting airplanes, gliders, hydroplanes, petrol trucks, railway
cars, plastics and art objects (Table 9.16).
Introduction and phasing-in of new lacquer-and-paint materials is accompanied with
consumer technical service. Together with the Testing Center Kortest, accelerated climate tests, stardardization and certification of lacquer-and-paint materials are carried out.
Among the developed materials, of interest is primarily the polyester acryl urethane enamel
KPU-1, which by the properties of coatings is not inferior than aviation-grade enamels of
the company Akzo Nobel, and costs 1015% less.
Gliders painted with the systems of coatings based on epoxyurethane primer KPU-02
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and urethane enamel KPU-14 are exported to Great Britain and the USA.
There is already a three-year-long positive experience of painting gas tank trucks with
the coating based on red-orange enamel KPU-12.
Table 9.16
Application
Painting of passenger
aircraft
Lacquers / paints / system

of coatings
Primer EP-0215 (lightyellow)

Lacquer AK-113
Primer EP-028 (lightyellow)
Enamel KPU-1 (various
colours)
Painting of gliders and Primer KPU-02 (white)
water aircraft
Enamel KPU-14 (white)
Film former
Epoxy resin hardened with amino siloxane resin
Acrylic resin
Epoxy resin hardened with polyisocyanate
biuret
Epoxy resin hardened with polyisocyanate

biuret
Epoxy urethane resin hardened with polyisocyanate biuret
Painting of fuel tank Phosphating primer VL-02 Polyvinyl butyral resin with addition of acid
trucks
catalyst
Primer KPF-01 (russet)
Quick-drying alkyd resin
Enamel KPU-12 (orange- Alkyd urethane resin hardened with polyisored)
cyanate biuret
Painting of passenger Primer KPU-02 (yellow) Epoxy resin hardened with polyisocyanate
rolling equipment
biuret
Enamel KPU-14 (various Ditto
colours)
Painting of elastomeric Mat lacquer KPU-25
Oligourethane elastomer hardened with
plastics
isocyanate-containing adduct
Painting of wooden con- Lacquer KAU-1
Alkyd urethane resin
structions and artwork
Painting of metallized Lacquer KPU-15
Biuret-hardened epoxy urethane resin
plastics
The results of accelerated climatic tests of the coating system primer KPU-02 and
epoxyurethane enamel KPU-14 made it possible to recommend this system for painting
railway cars. These coatings provide operation for 10 years under conditions of cold and
moderate climate.
The most interesting developments include matte elastomer lacquer KPU-25 for decorative finish of rubberlike polyurethane films.
A 15-m-thick coating hardened at 80C has a matte silky surface and withstands the
tensile elongation up to the complete rupture of the support.
In the nearest future, it is planned to develop a broad range of two-pot epoxyurethane
lacquer-and-paint materials, coatings based on which have a high rate of hardening,
chemical endurance and resistance to scratches. Application of additives of the company
Byk Chemie made it possible to develop thixotropic lacquer-and-paint materials for painting furniture fittings, lacquers for finishing metallized plastics and articles from ebony with
a highly sliding surface, which excludes scratches. Operational tests of red transparent
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331
epoxyurethane lacquer are being carried at present; the lacquer is intended for painting
retroreflective road signs of the type of cats eye.
332
10
Methods of Developing
Polymer Gas-selective
Systems for Storage of
Fruits and Vegetables
10.1 Problems of storage of agricultural raw materials and foodstuffs

In the processing chain of foodstuff production from the field to the consumer, an important
place is occupied by the storage of raw materials and end products. The use of cold in transportation, storage and processing of products in the agroindustrual complex makes it possible to avoid considerable losses. By estimates of specialists, the energy expenses for
refrigeration and storage of a unit product is nine times lower than for its production.
At the same time, cold-storage facilities available in the country provide for one-time
storage of less than 12% of perishable products of agriculture and food industry. This makes
necessary the development of storage infrastructure. Special attention is paid to the development of storage parameters for various types of products, such as temperature, relative
humidity, composition of the gas medium, special protective properties of coatings. Industries manufacture insufficient amounts of modern equipment and instruments for the control and regulation of a microclimate in storage chambers, as well as mechanical appliances
for handling operations. Specially acute is the issue of the development of modern facilities
for storing fruit-and-vegetable products and potatoes in the country. Russia is the largest
producer of these products. At the same time, supply of domestic vegetables and potatoes
to the population in the course of the year does not exceed 5060%; and fruits, 25%. At all
stages of promotion of these products, the losses are up to 4050%; and the quality is sharply reduced.
Application of technologies using artificial cold and regulated gas medium (RGM)
makes it possible to decrease 57-fold the losses of fruit-and-vegetable products; 23-fold,
of animal-origin products. R&D on the development of technologies for production of
quick-frozen vegetables, berries and fruits is promising. The high level of the preservation
of vitamins and other nutritive substances, prolonged storage life, exclusion of the use of
aseptic means and sugar make these products indispensable infants food, dietary food,
health food and prophylactic food. Consumption of quick-frozen products per capita is in
Russia 0.5 kg per year; in Western countries, up to 50 kg per year.
334
10.2 Selectively permeable polymer materials

One of the most efficient inexpensive and simple methods of storage is the use of cooling
under conditions of a modified gas medium (MGM). Containers from polymer materials
with gas selective membranes are the least material- and energy-intensive devices for storing fruits and vegetables in MGM.
Storage of fruits and vegetables under these conditions is based on creating the atmosphere with an increased content of carbon dioxide and a decreased content of oxygen inside
a container. Such an atmosphere is established as the result of interaction of two processes
respiration of fruits and diffusion of gases through membranes. An increased content of
carbon dioxide and a decreased oxygen content inhibit respiration of fruits and contribute
to their larger storage life.
To create a modified gas medium, two methods are used the most the method of
forming the required gas medium (active method), given the name of the regulated gas medium (RGM), and the creation of a modified gas medium due to the vital activities of
fruit-and-vegetable products in a closed volume (passive method) given the name of the
modified gas medium (MGM).
During the storage in RGM, special gas generators and absorbents remove excess gases and maintain their preset concentration. This method is rather efficient; however, it has
not found wide use for all its positive merits due to the complexity and high cost of equipment.
The method of storing fruit-and-vegetable products in MGM is the least materialintensive, does not require special devices and installations. It assumes the use of various
membranes possessing a selective ability to pass gases, which contributes to the creation of
a medium with a decreased content of oxygen and an increased content of carbon dioxide
in closed tanks. To enable a required storage regime, it is necessary to know, besides the
parameters of the membrane, the characteristics of stored products and, first and foremost,
the respiration intensity. If this parameter is known, the calculation of the gas regime can
be done by, for instance, setting the concentration of oxygen. Then the concentration of carbon dioxide will be the function of this parameter.
The consumer properties were studied and containers for storing fruits and vegetables
were developed. For solving this problem:
processes occurring in storage were analyzed to develop an optimal gas regime,
the effect of various factors on the kinetics of attainment of the steady state regime
with consideration of the parameters of products was studied, as well as the method of packaging, selectivity and vapour permeability of the membranes for monitoring the gas composition,
the inhomogeneity of membranes with respect to their permeability and selectivity
was determined, as well as the admissible boundaries of scatter,
the method of calculating the parameters of containers with two different-type membranes was developed with the view of attaining an optimal regime of storage,
the method of and device for removing excess moisture from containers was developed, using capillary porous textile materials, for instance, nonwoven materials from synthetic fibres.
Broad industrial introduction of the MGM method throughout the country is impeded
by the labour intensity of assembling and operating gas selective devices, insufficient availability of tissue-base membranes. The absence of a systematic analysis of gas selective materials and systems from the point of view of a unified methodological approach prevents
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335
prediction of the composition of the gas medium as a function of the performance characteristics of these systems.
Quantitative dependences were established, which make it possible to regulate the gas
composition in containers and packagings from polymer materials by combining the performance characteristics of gas-selective polymer materials and developing novel gas selective systems. A relationship was found to exist between the contents of oxygen and
carbon dioxide in polymer gas selective systems and their diffusion and geometric characteristics. This enabled the development of optimal conditions for prolonged storage for each
concrete type of fruit-and-vegetable products.
For this purpose, gas-selective paper-polymer material was developed, which is a combination of two layers of paper or paperboard with reduced adsorbability and a polyethylene
layer in between them, 2060 m in thickness, as well as membrane material consisting of
the paper support with a hydrophobic layer and a layer of an organosilicon substance applied to it. The use of these materials made it possible to reduce natural losses of apples
after 6.5 months of storage 58-fold and to increase the yield of standard products by 30%.
10.3 Effect of diffusion characteristics of polymer materials on the formation

of a gas medium
Experimental works conducted in various climatic zones of the country dealt with the determination of optimal gas compositions for various types of fruits and vegetables, temperature regimes of storage, trade analysis of the results of long-term storage, experimental
selection of the area of membranes and development of various container/packaging designs using selectively permeable membranes. For industrial storage of fruits in MGM, use
is made of containers with polyethylene inserts 150200 m in thickness in combination
with gas selective membranes, which can be fixed directly in the wall of the polyethylene
insert or be mounted into the internal cavity of the gas selective device from shock-proof
polystyrene. Perforated walls of the body do not prevent the gas exchange through the membrane and protect it from the mechanical impact of the surrounding fruits.
As the sizes of containers are constant, approaches to the choice of diffusion characteristics of polymer materials for gas-selective containers were developed for creating
optimal regimes of storing fruit-and-vegetable products in gas media. According to the
modern views, the limiting stage of gas transfer through polymer material is diffusion, and
the main characteristic of polymer materials for these purposes are their diffusion coefficient for oxygen and carbon dioxide. The effect of diffusion characteristics of a wide range
of domestic materials on the composition of the modified gas medium in storage of apples
was studied. For this, packagings from gas-impermeable material cellophanefoilpolyethylene and packagings from the same material with inserted membranes from various
polymer materials were fabricated.
Coefficients of diffusion and permeability of materials with respect to oxygen or carbon dioxide at apple storage temperature were determined with consideration of the area of
the polymer membrane, diffusion coefficients of oxygen and carbon dioxide, difference of
their concentrations on both sides of the membrane, respiration intensity of fruits and vegetables, weight of products (Table 10.1).
For membranes, the chosen polymer materials differ by their productivity by several
orders of magnitude.To obtain comparable data on the formation of the gas medium, packagings were fabricated with membranes of different area. For polyamide, polyimide,
polypropylene and LDPE the area was 0.150.15 m2; for HDPE, LDPE+GKZh-94,
336
HDPE+LDPE, 0.100.10 m2; for PLP (Sigma), membranes based on PVTMS paper,
0.0304 m2.
In storage of fruits in a sealed tank without membranes the gas composition constantly
changed without reaching an equilibrium value. In packagings with membranes from polyamide and polyimide the gas medium changed in a similar way. This indicates that flows of
gases through membranes from these materials are insufficient to form gas regimes acceptable for maintaining the vital activity of fruits.
Table 10.1 Diffusion characteristics of polymer materials at 4C.
Polymer material
Polyamide
Polyimide
Polypropylene
LDPE
HDPE+LDPE (70:30)
HDPE+GKZh-94
HDPE
Cambric-based PDMS
Polycaprolactam-based
PDMS
Paper-based PDMS
PVTMS
Thickness,
x10 5, m
Diffusion coefficient,
D10 12, m2/s
Permeability, Q10 12,

m3/(sN)
O2
CO2
O2
CO2
2.5
4.0
2.0
6.0
3.0
5.5
4.0
15.0
12.3
0.20
0.39
1.14
7.89
9.78
16.23
16.61
0.032
0.069
0.71
5.76
8.71
12.05
11.50
0.0079
0.014
0.11
0.089
0.15
0.22
0.36
56.31
91.20
0.017
0.071
0.36
0.35
1.01
0.71
1.41
238.05
224.15
13.3
14.5
147.20
5623.00
537.10
2818.00
When using other types of polymer materials, the process of gas exchange of packagings with the environment has two characteristic stages: non-steady state and steady state.
The first period was characterized by a decrease in the content of oxygen and an accumulation of carbon dioxide. The intensity of change of the concentration and the duration of
the non-steady state period depend on the polymer materials used and variety features of
fruits. In storage of packagings with little-permeable membranes, the time of attainment of
the steady state was usually larger. For apples, a more intensive change of the gas composition was characteristic of carbon dioxide, which is due to the rates of transfer of these gases in polymers. The greatest absorption of oxygen and the accumulation of carbon dioxide
occur in packagings from polypropylene and low-density polyethylene. The use of membranes from PDMS on various bases and from PVTMS modified the gas medium insignificantly; despite the fact that their area is much smaller, the gas composition in packagings
with such membranes is close to the atmospheric composition.
Simultaneously, the kinetics of change of the gas composition in storage of apples in
packagings with membranes from various polymer materials was studied; the respiration
intensity of fruits, i.e., the amount of gas evolved or absorbed by a unit weight of fruits per
unit of time, was measured. This characteristic in the postharvest period depends on the
storage temperature and composition of the gas medium. For correct calculation of the container parameters, one should know the respiration intensity of fruits in the gas medium,
which formed in polymer containers as the result of the vital activities of fruits and selective
permeability of polymer materials. The method for determining the respiration intensity of
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337
fruits during their storage in polymer containers without violating the storage conditions
and air-tightness of containers was worked out.
Analysis of experimental data on the effect of diffusion, area of polymer material,
weight of products and respiration intensity of fruits with respect to oxygen and carbon dioxide on the composition of the modified gas medium indicates that the reduced performance of membranes should be used as the main process parameter determining the gas
composition. Methods of predicting the composition in storage of fruit-and-vegetable products, having the respiration intensity close to that parameter at the beginning of storage,
were proposed.
Prediction of the characteristics of gas selective polymer materials is carried out with
consideration for the composition of the gas medium, area and thickness of membranes, as
well as the ratio of the concentration of oxygen and carbon dioxide. Selective permeability
of polymer materials is determined by many factors, including by the molecular interaction
of the polymer matrix and a diffusing substance.
The required gas composition can be obtained in various ways using little-permeable
materials, for instance, polyethylene of 150200 m in thickness with high-performance
membranes, or using solid packaging material with the optimal ratio of the diffusion coefficient, area, thickness. Membranes from a paper support with the consecutively applied hydrophilic layer (of the composition containing polyvinyl alcohol and low-molecular-mass
additive) and the surface layer (from an organosilicon substance) were developed. Introduction of a low-molecular-mass additive makes it possible to obtain a layer of hydrophilic
polymer with the defect-free silicon film.
Despite the large economic and social effect of the use of polyethylene inserts with
gas selective membranes, they have not found wide commercial use, which is due to the
high labour intensity of assembling and operating such systems.
A multilayer fibrous material consisting of paper or paperboard with absorbability of
535 g/m and a polyethylene layer of 2060 m in thickness in between them was developed. The weight of the coating was 50 g/m2, which provided for a permeability of
4.6210 12 and 11.6810 12 m3/(sN) with respect to oxygen and carbon dioxide, respectively, at 25C. The material is used for fabricating bags 11.5 kg in capacity.
Block copolymers based on vinyl trimethylsilane, which are distinguished by the succession of arrangement of the blocks, molecular mass, chemical composition were used for
fabrication of gas selective membranes with high parameters. Using the methods of electron
microscopy and diffusion measurements, it was shown that siloxane block copolymers
manifest the phase inversion at a concentration of polymethyl siloxane blocks from 20 up
to 45%. The properties of these membranes depend on the morphology of supramolecular
structures. It was shown that membranes from block copolymers are characterized by a high
selectivity of gas separation.
Modified polydimethylsiloxane block copolymers. were developed for fabrication of
membranes. It was found that at a small molecular mass of polydimethylsiloxane about 350
the copolymer is a single-phase system with the glass-transition temperature of 125C. The
phase separation is observed at an increase of its molecular mass.
By varying the composition of block copolymers, the mechanical properties can be
changed within a broad range from rigid material with small elongation of up to several
percent to elastic material with high elongation.
Even in the absence of crosslinks, they behave as crosslinked silicon rubbers, which
is explained by their two-phase morphology; herewith, polysulfonyl blocks render a reinforcing action.
338
Gas permeability of block copolymers through the membrane increases 3.4 times as
the mass fraction of polydimethylsiloxane is increased from 30 up to 80%. Block copolymers can be used to produce membranes with selective properties in storage of agricultural
products, when their losses can exceed 60%. They can be used for creating an atmosphere
with a decreased concentration of oxygen and an increased content of carbon dioxide.
The method of storing fruits and vegetables in a regulated gas medium is based on the
use of membrane gas exchangers installed in sealed refrigeration chambers, and film polymer packagings equipped with gas-selective membranes.
It was found that polymer membranes in the shape of hollow fibres are the most rational and promising technical solution as compared with plane and asymmetric membranes.
Hollow gas-separating fibres based on block copolymers were produced; they differ
from the plane ones by a larger surface per unit volume.
The intensity of physiologo-biochemical processes in fruit-and-vegetable products,
quality and duration of storage depend on temperature-moisture regimes; to create and
monitor these regimes, various systems of maintaining a microclimate are used. Such systems differ by the methods of air exchange organization.
In Russian and Western practice, two types of ventilation are used: general mechanical
ventilation (circumfluent systems) its main drawback is the unevenness of the temperature-moisture field inside the stack and the system of active ventilation. These systems
are expensive and require significant operational expenses.
A system of flow ventilation of stacks and standard rack-mounted trays was proposed;
it is devoid of the main drawbacks of the circumfluent systems and active-ventilation systems. The cost of the construction part of such a system does not exceed that of circumfluent
devices; however, it enables a higher uniformity of air distribution in the entire volume of
the stored products.
The system provides for different temperature levels, drying of products, supply of air
in input ventilation of the stack. Such systems include the equipment for heat-moisture
treatment of the air, including the means for heating, cooling and drying. The ventilation
system contains the vertical main air duct, located in the butt-end part of the stacks with
regulated fittings connected with air ducts formed by trays of containers, air flow limiters,
installed in the opposite butt-end part of the stacks. In the main air duct, there are horizontal
partitions arranged to form alternating air supply and -exhaust sections, and the air flow limiter is made in the shape of a wall along the entire height of the stacks.
It is recommended to use to system of maintaining a microclimate, in which the mixture of incoming and recirculating air is processed in heat-exchanging devices to be fed to
the air-supply sections of the vertical main air duct. The alternating air-supply and -exhaust
sections operate as regenerative heat exchangers. Two-side ribs on the partitions make it
possible to increase the heat removal between the sections. The direction and consumption
of the air is regulated by fittings, which can be rotated inside the air duct. To prevent the
flow-over of the air into the stack, with a small number of containers along the length (up
to 1015), it is recommended to cover the sections with air-impermeable material in the
butt-end part.
The existing technologies of storing food products are characterized by a compromise
between the scientifically grounded and experimentally verified requirements to storage
conditions, on the one hand, and the possibilities for their realization, on the other hand.
Technologies can possibly be refined both by increasing the requirements to the quality of
products to be stored and by expanding the technical potential of storage facilities, improvement of containers, packagings and other technical means. To optimize the heat and mass
CHAPTER 10
339
exchange processes in the productstorage system, which determine the change of quality
of products in storage, use was made of the fundamental principles of irreversible thermodynamics. This makes it possible to establish relations between particular elements of the
system and consolidate them with account for the changeability of the parameters.
We studied the behaviour of the system with account for the structure, temperature level of storage, moisture content, intensity of the chemical processes, which determine a reduction of the parameters of quality, with the view to define the concept of the stability of
the system as the ability to maintain a certain state and return to it after admissible deviations of some parameters.
The change of entropy is considered as the parameter of change of the properties of a
stored product, in particular, the change of entropys components: entropy emerging inside
the system (product) and entropy brought from (released to) the external medium. Entropy
inside a product is minimal at an increase of the requirements to the quality of products to
be stored. A decrease of intensity of change of external entropy in the productstorage system is achieved by the localization of external effects in the storage subsystem.
Of prevalent significance was found to be the temperature level of storage, which reflects the intensity of heat exchange processes and, respectively, associated processes of
change of the quality of food products. Important factors are also a decrease of the amplitude of temperature variations in storage of food products, as well as the way the energy is
supplied to stored goods, provision of an even temperature field along the volume of the
storage facilities, i.e., the thermal inertia of the productstorage system.
An important role in storage of food products is played by mass (moisture) exchange;
what is more, for hygroscopic products, this is directly related to the change of their moisture content; for products in a packaging, its intensity largely determines its storageability.
For calculations and prediction of the mass exchange process, it is proposed to determine the zones of optimal temperature-moisture states of the air in the storage based on thermophysical and mass exchange characteristics of stored products.
With consideration of these parameters, an optimal temperature-moisture regime of
storage in a criterion form is provided for. Based on the theoretical and experimental studies, the following criteria providing for the optimal storage conditions were established: for
underground storage facilities with climatization systems, K is 0.960.98; for ground-based
heated storage facilities with conditioning and cooling systems, 0.940.96; for heated storages without forced ventilation systems, 0.900.92; for non-heated storages, 0.700.75.
One of the types of storage of food products is the use of antioxidants in the form of
biologically active additives to food. They are used for the correction of nutrition of modern
man, improvement of the quality and safety of food products. Introduction of biologically
active additives provides for the inhibition of oxidative processes in foodstuffs and increases their storage life. The most widespread antioxidants are ascorbic acid, tocopherols, beta
carotene, selenium. Formulations and technologies were developed to produce products enriched in the given biologically active additives, as well as iodine and iron. Iodine-treated
salt and beta carotene are added to vegetable oils. The content of biologically active additives in the end product provides for 1/32/3 of the daily requirement of an adult in essential
nutrients. It was shown that the use of antioxidants in biologically active additives prevents
oxidative spoilage, provides for an increase of the guarantee storage life. The use of these
compounds was found to render no negative effect on the organoleptic characteristics of
products.
A project of normative documents was worked out and hygienic certification tests
were performed with the aim to start manufacturing of products.
340
10.4 Methods of developing an optimal gas medium and the technology of

storage
The polyvinyl trimethylsilane (PVTMS) membrane manufactured by Kuskovo Chemical
Plant found use for storage of agricultural products. Depending on volumes of storage, the
membrane can be used in polyethylene bags with inserted gas-exchange devices (GED) for
8100 kg of fruits or vegetables, or in throw-overs from polyethylene with GEDs for
1,00030,000 kg of agricultural products.
A further increase of the storage volume requires the use of membrane units for creating a regulated gas medium in airproof refrigerating chambers. The units include a membrane module from the PVTMS membrane, a compressor and/or vacuum pump and the
control system for monitoring the composition of the gas medium. A relatively inexpensive
membrane gas-separating unit manufactured by the firm Klimbi contains one or more membrane module(s) of disk type 160 mm in diameter, 800 mm in length and 15 kg weight. The
size of the module can be reduced to 230 mm; it incorporates 30 membrane elements. A
compressor with the air flow of 50 m3/h at a pressure of 1.0 MPa requires 10 modules,
which provide for the oxygen content regulation limits of 38% and produce 1020 m3/h
of the required gasair mixture. The size of such a membrane device containing 10 modules
does not exceed 1 m3; the weight is 200 kg. The time of start and attainment of the regime
is 25 min; the operation period, no less than 5 years.
Klimbi membrane modules are characterized by the following parameters. At an air
pressure before the membrane 0.4 MPa; after the membrane, 0.1 MPa for a module including 30 elements (area, 1 m2) the feeding air flow is 1.0 m3/h; the target air flow, 0.5 m3/h
at an O2 content of 10%; at an O2 content of 3% for a module including 60 elements (area,
2 m2), 1.1 and 0.1 m3/h, respectively; at an O2 content of 10%, 1.8 and 0.7 m3/h; for a module including 90 elements (area, 3 m2), at an O2 content of 3%, 1.7 and 0.2 m3/h; at an O2
content of 10%, 2.6 and 1.0 m3/h; for a module including 110 elements (area, 3.8 m2), 2.2
and 0.3 m3/h, 3.3 and 1.3 m3/h, respectively. At an air pressure before the membrane
1.0 MPa and after the membrane 0.1 MPa for a module including 30 elements (area, 1 m2),
at an O2 content of 3% the feeding air flow is 2.0 m3/h, the target air flow, 0.4 m3/h, at an
O2 content of 10%, 3.4 and 1.7 m3/h, respectively; for a module including 60 elements (area, 2 m2), at an O2 content of 3%, 3.9 and 0.8 m3/h, at an O2 content of 10%, 6.7 and 3.4
m3/h; for a module including 90 elements (area, 3 m2), 5.8 and 1.2 m3/h, 10.1 and 5.1 m3/h;
for a module including 110 elements (area, 3.8 m2), 7.5 and 1.6 m3/h, 12.8 and 6.3 m3/h,
respectively. Performance of the PVTMS membrane for oxygen is 4600 l/m2 h MPa; for
nitrogen, 1400 l/m2 h MPa.
10.5 Efficiency of using polymer materials and protective coatings in

long-time storage of fruits
The problem of reducing the losses in long-term storage of fruits is very topical, as losses
due to microbial and physiological diseases in some years can reach 2030% (annual losses, 817% on average).
One of the most accessible methods of increasing the preservation of fruits is the use
of polyethylene throw-overs with gas selective membranes in refrigerated storages for creation and regulation of a modified atmosphere. The gas composition in polyethylene
throw-overs of 10 tons capacity is regulated using a gas selective membrane, grade
PA-160-S-3,1.
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341
The efficiency of this method of storage was tested on apples of Jonathan and Golden
Delicious varieties. The results obtained showed that both varieties are better preserved in
a modified gas medium than in usual atmosphere; herewith, Jonathan fruits had higher quality characteristics by the end of storage (Table 10.5.1).
Table 10.5.1 Quality produce yield and losses in storage of apples in common atmosphere and in
modified gas medium (MGM) (in brackets).
Variety
Jonathan
Golden Delicious
Storage time,
days
209 (209)
141 (209)
Standard
produce
yield, %
63.2 (88.7)
54.5 (83.2)
Losses, %
Physiological
diseases
natural
losses
caused
by rot
5.4 (1.2)
9.0 (1.4)
31.4 (10.1)
36.5 (15.4)
Spot disease ()
Withering ()
In storage in common atmosphere: temperature, (0 + 1)C; humidity, 85%; in storage in MGM:

temperature, (0 + 1)C; humidity, 90 95%; composition of MGM: CO2, 3.5%; O2, 10 16%; N,
79 83%.
When stored in the usual atmosphere, Jonathan fruits acquire spots, which increase
with time and merge. The spot disease leads to a significant decrease of the quality of produce and inflicts a considerable economic damage. During the tests, by the end of storage
the losses from this disease reached 40% under usual conditions, whereas no spot disease
was observed in MGM storage.
Apples of the Golden Delicious variety in storage under usual conditions strongly
wither, which is due to the biological features of the variety; these fruits have a thin skin
and weak wax coating. It is difficult to maintain an optimal moisture content required for
this variety. The use of polyethylene throw-overs with gas selective membranes made it
possible to increase the storage time of fruits by 68 days. Apples by the end of storage has
a fresh appearance and good taste qualities.
Studies of the biochemical composition of apples at the and of storage found that fruits
stored in MGM preserved their nutritive and taste qualities better (Table 10.5.2).
Table 10.5.2 Biochemical composition changes of apples in storage in common atmosphere and in
MGM (in brackets).
Variety
Jonathan
Golden
Delicious
Dry
matter,
%
Sugar,
%
Total
acidity,
%
Tanning
Vitamin
and
colouring
C,
mg % substances,
mg %
12.8
(13.0)
14.2
(14.6)
10.0
(10.5)
10.9
(11.0)
0.34
(0.48)
0.23
(0.26)
6.16
(8.80)
7.20
(9.20)
0.40
(0.60)
0.26
(0.30)
pH
3.37
(3.64)
3.64
(4.41)
Pectins, %
protopectin
soluble
total
0.30
(0.44)
0.34
(0.32)
0.33
(0.33)
0.39
(0.43)
0.63
(0.77)
0.73
(0.75)
Thus, the results of tests confirm the efficiency of storing fruits of Jonathan and Golden
Delicious varieties using polyethylene throw-overs with gas selective membranes. As
342
compared with the existing technology their storage life increases (up to 2 months), losses
from rot and natural losses decrease, high vendibility qualities of fruits are preserved.
Fruits of most varieties of pears as compared with apples are characterized by a lower
preservation, which is due to postharvest ripening processes. For their preservation, it was
proposed to use polyethylene containers of up to 500 kg in capacity, where the gas composition is regulated using a Sigma gas selective membrane. The tested varieties of pears include Vilyame, Krasny Kavkaz, Vere Vosk, Konferentsiya, Talgarskaya Krasavitsa, Nart,
Fevralskaya and Kyure (first and highest commercial varieties). By the example of the varieties Krasny Kavkaz, Konferentsiya, Nart and Kyure (Table 10.5.3), it is seen that using
MGM the duration of storage is increased by 1.52 months, natural losses are reduced 23
times, the yield of standard products (first commercial variety) in the first inspection
(1516 February) was 8498%. Fruits of the varieties Vilyame, Vere Vosk and Konferentsiya, when stored in MGM had no signs of physiological diseases; in the varieties Krasny
Kavkaz, Nart and Kyure the browning of the skin did not exceed 3.4%.
Table 10.5.3 Yield of quality produce and losses in storage of pears in common atmosphere and in
MGM (in brackets).
Variety
Krasny Kavkaz
(summer variety)
Konferentsiya
(autumn variety)
Nart
Kyure
Storage time,
days
Yield of
standard
produce, %
Losses, %
natural
losses
caused by rot
due to
physiological
diseases
81 (159)
81.7 (98.0)
3.5 (1.3)
10.8 (2.0)
14.3 ( )
138 (220)
70.9 (94.9)
4.7 (1.5)
26.8 (5.1)
2.3 ( )
95 (151)
143 (196)
49.3 (83.7)
81.9 (92.5)
2.5 (1.0)
4.4 (1.5)
25.9 (16.3)
14.8 (6.2)
24.8 (3.2)
3.3 ( )
Note: In storage in common atmosphere: temperature, (0 + 1)C; humidity, 85%; in storage in MGM:
temperature, (0 + 1)C; humidity, 90 95%; composition of MGM: CO2, 3.5%; O2, 8 10%.
When storing the fruits under usual conditions, damage from rot was from 10 up to
42%, withering losses reached 40% for the variety Fevralskaya, browning losses in the variety Nart were 25%.
Studies of the biochemical composition of fruits showed that, when stored in MGM,
fruits preserved higher taste and nutritive qualities.
The technology of storing pears using polyethylene containers gives a profit of 160 up
to 360 roubles per ton depending on variety.
With the view of further increasing the storage times and reducing losses in storage of
fruits in MGM, the possibility of using natural ceolytes and those saturated with preparations with fungicidal properties was studied. According to preliminary data, losses of fruits
from microbial and physiological diseases in storage in MGM in combination with ceolytes,
natural and saturated with sulfur dioxide, is by 0.68,3% lower than in storage in MGM
only.
Film forming coatings are being developed, which protect fruits from microbial and
physiological diseases. Polymer compositions based on polyvinyl alcohol and starch with
addition of a 4% CaC12 solution were tested. Fruits picked up from a tree were immersed
343
CHAPTER 10
into a solution for 1 min. Within 510 min, a thin film was formed on the surface of the
fruit. Air-dried fruits were put into boxes and placed into a refrigeration chamber. Fruits
were stored at a temperature of 0 + 1C and relative air humidity of 85%. The postharvest
treatment of pear fruits with water-soluble polymer made it possible to reduce the losses
from 1832% to 56% (Table 10.5.4). The biochemical composition of treated fruits indicates that film-forming coatings inhibit the maturation processes and preserve better the
structure of the fruits meat. Besides, the content of vitamin C and acidity are maintained
at a required level.
Table 10.5.4
Variety
Nart
Konferentsiya
Storage of pears treated with water-soluble polymer and not treated (in brackets).
Storage Standard
Losses, %
time, produce
days
yield,
caused
due to
natural
%
by rot
skin
losses
browning
125
(125)
125
(125)
94.3
(66.2)
95.5
(81.9)
5
(20)
3
(10)
0.5
(10)
()
0.2
(3.8)
1.5
(8.1)
Change of biochemical
composition of fruits
dry
matter,
%
total vitamin C,
acidity, mg/100 g
%
12.0
(10.4)
14.7
(12.1)
0.27
(0.27)
0.14
(0.13)
4.49 (4.49)
7.13 (6.79)
Thus, the use of polyethylene throw-overs, containers, protective coatings is at present

an accessible and efficient way to increase the time of storage of fruits and reduce losses.
344
11

Oligomer Compositions for
Protection of Transport
Containers
11.1 Corrosion resistance of coatings for transport containers

Polymer coatings are the main means of protecting metals from corrosion. However, the
mechanism of their protective action has been studied insufficiently, especially in biologically active media containing organic acids, enzymes, microorganisms and other components. This is due to the complexity of physicochemical processes occurring in the
formation and performance of coatings, as well as to the influence of various factors on the
protective properties: adhesion strength, internal stresses, barrier properties, nature of the
support and method of its surface preparation, composition of the aggressive medium etc.
These properties of coatings are determined not only by the chemical composition of polymer, but also by the specifics of structure formation in coatings, which determines the degree of inhomogeneity of coatings along the thickness of the film, level of its ordering,
character of distribution of the chemical bonds and polar groups, and therefore the swelling
capacity of coatings, rate of transfer of water and ions, direction of their movement, charge,
rate of destructive processes.
The set of properties of biochemically resistant anticorrosion coatings is determined
by their purpose and operating conditions. High requirements to the toxicology, as well as
to the effect on organoleptic characteristics and quality of food products are imposed on
manufactured Western and Russian coatings recommended for protection of equipment,
constructions and industrial facilities of food enterprises, as well as large-size tanks for processing, storage and transportation of food media.
Food media are biologically active compositions containing a set of various enzymes,
amino acids and other active biocomponents.
It was found that under the action of bioactivators the rate of decomposition processes
of polymer systems increases three and more times as compared with the rate of development of electrochemical processes under the action of heat and moisture. The cause of this
phenomenon is due to the fact that microflora uses polymer materials as food products, and
biodegradants formed in their vital activities, in particular, organic and inorganic acids, are
activators of corrosion.
346
Polymer coatings are the main means of protecting various materials from biodegradation under the action of microflora, photo- and thermooxidative destruction in the fabrication and operation of articles. However, manufactured polymers, owing to the heterounit
character of chains, broad molecular-mass distribution, conformational and configurational
set of macromolecules are characterized by an inhomogeneous imperfect supramolecular
structure caused by the existing methods of their synthesis.
A significant share of chemical and physical bonds, which determines the protective
properties and durability of polymer coating, is consumed on the formation of supramolecular structures and is not involved in the formation of their protective properties.
The studies of Russian and Western coatings we conducted using the method of mass
chromatospectroscopy, making it possible to determine the content of polymer coatings
components in food media, are indicative of a comparatively small service life of such coatings. Components present in coatings are found, depending on the chemical composition,
in several months. Herewith, there occurs a spontaneous local decomposition of coatings
to form micropores and microcracks under the action of internal stresses. Restoration of
coatings is associated with significant expenses. Studies by Western investigators have
found that expenses for the works on surface preparation, application processes and formation of coatings exceed more than threefold the costs of polymer compositions used.
In this connection, of great scientific and applied significance is the development of
the scientific bases of the formation and ageing of polymer coatings with account for the
effect of various physicochemical factors, such as the nature, concentration and character
of distribution of the functional groups in the polymer chain, the morphology of the supramolecular structure and its dependence on the formation conditions, the kinetics of increment of internal stresses affecting the durability of coatings.
The aim of the studies was to work out scientific principles of developing regularstructure composite materials based on oligomer and polymer systems, providing for the
biochemical resistance of polymer protective coatings and a high durability, more than
510 years depending on the operational conditions.
11.2 Structural conversions in hardening of thermosetting oligomers

At present, there are no generally recognized views of structural transformations that occur
during the hardening of thermosetting resins. The specific properties of these systems, in
accordance with various models of the structure of spatially crosslinked polymers are usually attributed to the formation of a continuous three-dimensional network by both covalent
and van-der-Waals bonds. Conversion of such products to a soluble state or making them
fluid at elevated temperatures and pressures is achieved by intensive mechanical impacts,
which stipulate the decomposition of chemical bonds.
Many theories pertaining to the structure of thermosetting resins assume the existence
of infinitely large three-dimensional molecules, whose size is limited only by the size of the
reaction vessel. This view of the structure of three-dimensional polymers is given, for instance, in works by Flory, who considered the static conditions of forming large molecules
in a multifunctional system. Views of the presence of a homogeneous network structure,
formed as the result of a chemical interaction of monomer or oligomer molecules, are in
contradiction with their mechanical properties.
Calculations of the strength properties of network polymers, based on such a model of
a gigantic three-dimensional molecule, differ greatly from real measurements. De Boer calculated the tensile strength of polymers from phenol-formaldehyde resins, accepting the
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hypothesis that only chemical bonds are involved in the formation of the three-dimensional
structure, and obtained magnitudes, which are 550 times as large as the real strength of polymers. Then, with consideration of steric factors, the calculation was carried out proceeding
from the fact that secondary bonds of the type of van-der-Waals ones emerge between individual structural elements. In this case, the tensile strength was only 5 times as large as
the experimental value. Howink assumes that, with the crucial role of physical bonds in the
formation of a three-dimensional structure, the discrepancy between the theoretical and experimental values of strength is due to the defects of the type of irregularity of the shape of
resin macromolecules. Other authors, who represent hardened thermosetting resins as a ball
of tangled macromolecules, arrive at similar conclusions.
The change of physicomechanical properties in the formation of coatings from oligomer systems is associated with the emergence of a continuous three-dimensional network.
Studies of the effect of the type of bonds on the character of thermomechanical properties, the elasticity modulus and equilibrium rubberlike deformation of three-dimensional
polymers based on phenol-formaldehyde resins, epoxy and other thermosetting film formers showed that a significant role in the formation of a three-dimensional structure in these
systems belongs to physical bonds. It follows from the thermomechanical curves of polymers with different contents of crosslinks that they are characterized by a significant rubberlike deformation, but do not pass into a viscoelastic state due to the presence of the
three-dimensional structure. The glass-transition temperature of three-dimensional polymers increases with the rise of the extent of hardening, which depends on the formation temperature. However, even at a high temperature (140C) the hardening is not complete, and
the three-dimensional network is thermally labile. This is expressed by the fact that, as
three-dimensional polymers are heated and a load is applied, part of the bonds forming the
network are destroyed, and new bonds are formed, whose number increases with the temperature increasing. The re-recording of thermomechanical curves for the same specimen
shows that the rubberlike deformation is preserved, though the glass-transition temperature
shifts to the region of higher temperatures, and the elasticity modulus increases. Experimental studies of structure formation in hardening of phenol-formaldehyde resins, conducted by V.A. Kargin and G.I. Slonimsky et al., indicate that at a given stress and temperature
not exceeding 220C, the destruction and repeated formation of intermolecular bonds is
possible. Hardened phenol-formaldehyde resin did not exhibit a capability of the emergence
and development of plastic deformations; at the same time, the change of its properties in
the repeated heating and deformation is indicative of the formation of a large number of
crosslinks. The calculation of the energy of bonds responsible for the formation of a
three-dimensional structure showed that these bonds do not exceed 25.1 kJ/mol and correspond to the energy of the hydrogen bond. The essential role of physical bonds in the formation of the three-dimensional network in thermosetting resins is indicated by the data on
the sharp decrease of their strength and elasticity modulus (more than 24-fold) during the
heating to higher than the glass-transition temperature. During the cooling of specimens to
the initial temperature, their strength is again restored. This is also accompanied by the reversible change of internal stresses at the repeated heating and cooling of specimens based
on thermosetting resins. The thermomechanical curves of epoxy polymers with various
contents of epoxy groups, hardened by polyethylene polyamine at 200C for 10 h, indicate
a high elasticity of three-dimensional polymers, which increases with the content of epoxy
groups decreasing.
These data suggest that the spatial structure of network polymers is formed by bonds
of both chemical and physical nature, in particular, hydrogen and dispersion ones. The
348
occurrence of chemical bonds stipulates the distinctive feature of network polymers their
infusibility and insolubility in organic solvents. However, the ratio of these bonds is such
that the structure of network polymers is thermally labile.
The rubberlike properties have also been found for other network polymers. A.A. Berlin and O.G. Selskaya have shown that the elasticity of polyester acrylates depends on the
flexibility of the ester block, which forms crosslinks in the three-dimensional network. An
increase of the length of the crosslink block in the three-dimensional polymer structure
leads to an increase of the segmental mobility of the chains, an increase of rubberlike deformation and a decrease of the glass-transition temperature. An increase of the rubberlike
deformation can be also achieved by a substitution in the ester block of phthalic acid by sebacinic acid; at the same time, the replacement of diethylene glycol by butylene glycol leads
to an increase of the rigidity of polymer and an increase of its destruction temperature.
Taking into account the discrepancy between the experimental and calculated data on
the physicomechanical properties of network polymers, A.A. Berlin with coworkers suggest that a real network polymer is a set of limited-size network aggregates, in which the
links of macromolecules are sterically linked by chemical bonds, and the aggregates themselves can be connected by both chemical and van-der-Waals or hydrogen bonds. Such a
model of an imperfect and inhomogeneous network structure was proposed by the authors
as the result of the studies of the polymerization kinetics of various-structure polyester acrylates using chemical methods of analysis, infrared spectroscopy and electron paramagnetic
resonance. From these data, it follows that in the hardening of oligoester acrylates in the
block even at very small degrees of conversion, when one would expect the formation of a
non-branched product, the entire product of polymerization consists of the three-dimensional polymer. In the initial stages of the process, such aggregates consist of branched macromolecules linked by scarce bridges and represent microregions of local immobilization
of liquid monomer or oligomer. The mobility of free radicals in such aggregates is extremely small as compared with the mobility of radicals outside these aggregates, so the chain
termination constant during the polymerization in the microregion would be lower than in
the bulk. This leads to a much larger rate of polymerization inside microregions than outside
them. These results suggest that, from the very beginning of the conversion, simultaneously
two processes occur in these systems, with different rate constants: one in the free liquid
phase to form a nonbranched product, and the other at a much larger rate on microregions
to form a network polymer. The ratio between the rates of these two processes can change
depending on polymerization conditions. With the length of molecules decreasing (less reactive end allyl groups), as well as in the presence of a chain propagation agent the ability
of the chains to form aggregates with a three-dimensional structure decreases, and the yield
of nonbranched products increases.
These regularities, and the mechanism of formation of a network structure proposed
based on them, are the most physically substantiated. The data supporting such a mechanism of structure formation in hardening of thermosetting film formers are presented in a
work, which discusses the presence of colloidal-size aggregates, separated by a structure
from lower-molecular-mass fractions easily removed by solvents, in hardened blocks from
epoxy, phenol-formaldehyde and other resins. Such structures do not represent one single
molecule, but consist of fine particles bound stronger owing to the high polarity of resins.
Leaching with solvents succeeded in revealing isolated structures of globular shape, of
8090 nm in size, in epoxy, phenol and other thermosetting resins. The existence of structures of such size was confirmed also by the method of small-angle X-ray scattering. The
number of particles and their size determine the properties of materials, because
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349
van-der-Waals forces are efficient at distances of no more than 0.5 nm between globules.
However, the methods used in those works did not make it possible to reveal the fine structure of particles and the character of their distribution in films.
Thus, already the first electron-microscopy studies have shown that all models of network polymers based on the emergence of a continuous molecular three-dimensional network are not substantiated physically. Neither a skeletal network nor large formations of
tangled macromolecules were found.
A systematic study was carried out of supramolecular structure of network polymers
with consideration of the effect of the chemical composition of film former, the nature of
the support and fillers and conditions of application and formation. For this purpose, use
was made of indirect methods based on studies of the kinetics of change of physicomechanical and thermophysical properties in the formation of coatings and films from monomer
and oligomer systems, and their supramolecular structure and thickness of the three-dimensional network depending on various physicochemical factors were studied directly.
Associates in oligomer systems were investigated by taking replicas from the surface
of fractures of oligomers instantaneously frozen from +20 down to 180C, as well as by
studying the structures of fine oligomer films applied by blowing a bubble or obtained on
the surface of mercury.
Studies of associates in model monomolecular oligomer systems by taking replicas
from a fracture of oligomers instantaneously frozen from +20 down to 100C found their
morphology to depend significantly on the flexibility of the oligomer block. Oligocarbonate
methacrylate with rigid blocks of grade OCEM is characterized by the occurrence of associates of anisodiametric type, apparently formed from unfolded molecules. For OCDM oligocarbonate methacrylate with flexible blocks, globular structures are observed, whose
emergence is related to the folding of clusters of molecules. The morphology and size of
these structural elements are preserved at their rapid heating from 20 up to 90C as the result
of polymerization. The effect of the structure of the oligomer block on the mechanism of
formation of associates was studied by comparing the data on the molecular mobility of
skeleton and end groups of the block depending on temperature. The data were obtained by
the method of 1H NMR, with the temperature dependence of oligomers heat conductivity
and the character of their structure.
The high-resolution NMR spectra within the temperature range of 20 up to +20C
were recorded on a RYa-2303 spectrometer with the proton stabilizer. The working frequency for 1H nuclei was 60 MHz. In the region of lower temperatures, the spectra were
recorded on a broad-line spectrometer with the working frequency of 22 MHz. A specimen
in an ampule 5 mm in diameter was placed into a thermostatted sensor. The mechanism of
structure formation in oligomer systems was studied by investigating the molecular mobility of the main constituents of the oligomer block by the NMR method.
The high-resolution NMR spectrum of OCEM oligomer at 22C had four lines, which
were rapidly broadened with the temperature decreasing. The assignment of the lines is given in Table11.1.
The line width in the spectra of investigated oligomers can be said to be determined
mainly by the type and speed of molecular motion (ppm). This is also confirmed by the obvious temperature dependence of the width of individual lines, which is determined by the
increasing role of dipole interactions during the cooling of specimens.
The motion of methyl groups is inhibited slower than that of groups -CH2 CH2-. This
is quite probable, as the rotation of the CH2 group relative to the single CC bond depends to a lower extent on the steric factors than the motion of the oligomer block on the
350
whole. Two lines from nonequivalent protons of the end vinyl groups are broadened in an
almost the same way as the line of the CH2 CH2 group of the block. As the intensity of
these lines is small, it is difficult to determine their width at a decreased temperature. At a
temperature lower than 5C, the NMR spectrum of OCEM does not resolve due to the
strong broadening of the lines. At this temperature, individual lines merge into one line with
a width of 1103 Hz. Presumably, here the oligomer block completely loses a possibility of
translational mobility. Herewith, the vibrational and rotational movements of individual elements are preserved.
Table 11.1 Assignment of high-resolution NMR spectra of oligomer OCEM.
Proton-containing group
of polymer
CH
CH2
CH2
Chemical shift, ppm
Possible area of shifts,

ppm
relative to
water signal
relative to
TMS signal
3.46
8.26
8.0 8.5
0.67
5.47
5.2 5.8
0.58
1.15
4.22
3.65
3.7 4.7
3.7 4.7
For the range of 5 to 196C, we recorded the first derivatives of the NMR absorption lines and plotted a dependence of the 2H second moment on temperature. It follows
from the said that the molecular motion in OCEM is totally inhibited at a temperature of
60C. At a further decrease of temperature (down to 196C) the NMR spectrum of
OCEM did not change.
The spectra of OCDM differ from those of OCEM by only the line with a chemical
shift of 6.3 ppm from TMS. This line, which is in immediate vicinity to the line of the
CH2 CH2 group is assigned to ethylene groups linked by an oxygen bridge. Thus, the
NMR spectrum quite corresponds to the chemical formula of OCDM. The mid part of the
oligomer block CH2 OCH2 has a smaller mobility as compared with the peripheral
part CH2 CH2. However, with the temperature decreasing to 5C the widths of the lines
of the groups CH2 CH2 and CH2 OCH2 coincide and change further in a similar
way. For OCDM the mobility of the main groups differs noticeably from that of the main
groups of the link. Here, probably, an increase of the length and of the general flexibility
of the oligomer block have their effects. At a temperature lower than 15C the spectrum
of OCDM does not resolve owing to the strong broadening of the lines. In OCDM, the molecular motion is totally inhibited at a temperature of 70 to 80C, i.e., 1012C lower
than for OCEM.
The mobility of molecules of oligomer at 20C is higher than that of OCDM and decreases with the decrease of length and flexibility of the oligomer block. Along with this,
at a temperature decrease the molecular motion is inhibited the slowest in the system with
the most flexible molecular chain. The difference of the temperature of transition to the rigid lattice is 1520C for OCDM and OCEM. The differences in the intensity of molecular
motion of these oligomers are observed both in the region of predominant translational mobility (down to 10 to 15C) and in the region of vibrational and rotational movement of
the oligomer chain.
When explaining the observed dependences, it is necessary to take into account the potential of associative structuring of oligomers.
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In the systems studied the width of the NMR lines can be determined not so by the
structural viscosity of the system as by the local viscosity of associated molecules, which
is determined by the instantaneous mobility of the chains. In turn, the local viscosity depends on the interaction of molecules. In the formation of associates from OCEM molecules, the preferable conformation is the unfolded conformation owing to a larger rigidity
of the oligomer block. On the contrary, the significant flexibility of OCDM admits a more
free globular shape of associates. In the former case, the adjacent molecules of the oligomer,
which form anisodiametric structures from parallel-stacked blocks, create larger hindrances
for the mutual mobility of molecules than in associates from folded clusters of molecules.
Indeed, the mobility of the CH2 CH2 links is higher in OCDM, and the general mobility of this system is preserved at lower temperatures.
A proof of two types of associates in these oligomers can be the comparative behaviour
of the end and skeleton CH2 groups. In OCEM, the end groups lose their mobility simultaneously with the skeleton groups. In OCDM, the end groups of CH2 preserve their mobility
longer than the skeleton ones. This is indicative of a more free packing of molecules and of
differences in the spatial barriers for the movement of the entire block and its end groups.
The folded conformation of OCDM molecules in associates should hinder the motion relative to the oxygen bridge in CH2 OCH2 groups.
11.3 Formation kinetics of coatings from polymerization oligomers

The specifics of polymer coatings formed from oligomer systems is that the process of hardening is associated with polymerization on the support; the polymerization is completed
with the formation of supramolecular structures, which make up a three-dimensional network. In this connection, the nature of the support has a significant effect on the formation
of coatings. In spite of the fact that the effect of the nature of the support on the properties
and durability of polymer and lacquer coatings has been known since long ago, in many
works the structure and properties of polymer coatings are not altogether correctly identified with the structure and properties of films and block materials, while the role of the support in the formation of the properties of polymer coatings has been studied insufficiently.
A widely used technique in studies of the formation of polymer coatings is the method
of studying the kinetics of increment and relaxation of internal stresses. The effect of various physicochemical factors on the formation of coatings, such as the chemical composition
of oligomers, nature of the support, strength of interaction at the filmsupport and
polymerfiller interfaces, application and formation conditions, was studied using this
method.
Studies of the formation of coatings from oligoester maleinate phthalates hardened by
styrene showed that at 20C internal stresses reach an ultimate value in 2030 days and do
not exceed 1.0 MPa for coatings 300 up to 1000 m thick. Internal stresses reach an ultimate
value much faster in hardening at 80C. Stresses emerging in hardening of polyester coatings are small. A sharp increment of internal stresses is observed in cooling of coatings subjected to thermal hardening. Similar regularities in the change of internal stresses were
found in the formation of coatings from other oligomer systems.
The most significant increment of internal stresses and a sharp decrease of the duration
of gelation are observed with the increase of the formation temperature up to the glasstransition temperature of polymers; at the subsequent increase of formation temperature, the
stresses change insignificantly. This is, apparently, due to an increase of segmental mobility
of molecules in this temperature range, which contributes to the formation of the largest
352
number of bonds between structural elements, to a slowdown of the relaxation processes

and an increment of internal stresses.
It is also noteworthy that there is no unambiguous dependence between the kinetics of
/shrinkage and the kinetics of increment of internal stresses. More than 7080% of the entire shrinkage is exhibited at the time of transition of the system to the gelated state, which
corresponds to the use of the largest number of functional groups involved in polymerization, and to the appearance of a temperature maximum on the thermometric curves.
Studies of the kinetics of hardening of unsaturated oligoesters by the method of IR
spectroscopy showed that polymerization in such systems at 20C is completed in 45 h
involving 5060% double bonds, and at 80C in 4060 min involving 8090% double
bonds. It would seem that at a significant use of double bonds at the initial stage of hardening the formation of a three-dimensional network structure is at the stage of completion,
and coatings and films should have the highest physicomechanical characteristics.
Based on the rheological, physicomechanical, thermophysical and structural data, it
was shown that in production of coatings from oligomers at the first stage of their formation,
local bonds are formed within a small number of molecules, which is accompanied with
physicochemical processes mainly in supramolecular structures; and at the second stage,
links between these structures emerge and a three-dimensional network is formed. At the
last stage, owing to the inhibition of the relaxation processes, a sharp increment of internal
stresses is observed.
Studies of the rheological properties of oligoester maleinate phthalates at various stages of hardening indicate that initial oligomers are Newton-type systems. In a certain period
of formation, not only an increment of viscosity is observed, but also a change of the character of the rheological curves, which is due to the transition of the system to a structured
state determined by the formation of a network structure. From the data on the kinetics of
consumption of the double bonds, on the increment of internal stresses, breaking strength,
elasticity modulus and viscosity in the formation of coatings from these systems, it is seen
that, despite the involvement of a significant number of functional groups in polymerization
at the initial stage, coatings are characterized by low internal stresses and other physicomechanical properties. A sharp increment of the latter is observed at the second stage, when
7080% of functional groups in the system is consumed.
The presence of the induction period in the formation of a three-dimensional network
is detected in studies of oligomer hardening by the NMR method. The use of NMR in such
studies is based on the difference (by several orders of magnitude) of the proton correlation
frequency of the nonhardened phase. This makes it possible to separate the absorption line
obtained at any time of hardening into two regions and, based on them, make a judgement
on the course of the reaction. From the data on the change of the first derivative of the absorption line and the proton spin relaxation time depending on the duration of hardening, it
follows that there is an induction period in the change of proton correlation frequency in
the formation of the three-dimensional network.
This character of structural transformations was observed in studies of the formation
of coatings from unsaturated polyesters in polymerization under an electron microscope
and in other conditions, in studies of the supramolecular structure at various stages of hardening of coatings from oligoester urethanes of different chemical composition, alkyd resins,
epoxides, as well as organosilicon oligomers. Thus, a peculiar feature of the formation of
coatings from monomer and oligomer systems is an induction period in the kinetic curves
of increment of internal stresses and mechanical properties. This period is observed in the
formation of coatings from film formers with prepared supramolecular structures, for in-
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353
stance, from dispersions of polymers. From the kinetic curves, it also follows that the rate
of increment of stresses increases with the decrease of thickness of coatings. This character
of change in the formation of coatings from oligomers could not be explained proceeding
from the views of a continuous three-dimensional structure from separate molecules in such
systems.
Inhibition of the relaxation processes at a certain stage of hardening of oligomers has
an effect on the kinetics of change of other properties, in particular, thermophysical properties. A relationship between the kinetics of change of the thermophysical parameters and
of internal stresses both in the formation and during the ageing of polymer coatings was
established.
The microstructure of polyester coatings from 25% oligoester maleinate solutions in
acetone was studied. Individual globular associates were revealed in such systems by the
fast freezing method. The action of an electron beam for 5 min has no effect in practice. A
15-min action of an electron beam reveals a fine globular structure, similar to that found in
hardened coatings by the method of slices. Subsequent irradiation reveals aggregation of
structural elements to form larger supramolecular structures. In 2025 min of formation,
streaked structures are observed along with globular structures. In 30 min of irradiation, the
film is observed to crack. Herewith, one layer of the coating is displaced relative to the other, which is due to the different structure of layers along the thickness of the film.
In a film 4050 nm thick, four layers with different structures are revealed. The decomposition process begins from the surface. The first stage of decomposition is the formation of streaked structures, which emerge as the result of a re-grouping of structural
elements in the rupture of links between individual globular formations. The structural elements are packed the most densely in the layer adjacent to the support. The structure of
this layer is revealed not clearly enough, only in some places. Nearer to the interface with
the air, the size of the structural elements increases, and their packing density decreases.
The number of layers with different structure along the thickness of the film depends on the
thickness and nature of the support. Subsequent irradiation and thermal hardening of these
preparations at 80C for 24 h revealed no additional changes in the structure of coatings.
Structural transformations in polymerization of coatings and free films, which were prepared according to the known method, were compared. A drop of oligomer was applied to
the surface of water; after its spreading and stabilization of the film, a net was put onto the
film and it was extracted by means of a microscope slide. Polymerization in this case proceeds unevenly along the area of the film. First, after 3 h of heating at 80C, there arise more
dense zones in the shape of bands, the fine structure of which is not revealed. In subsequent
irradiation by an electron beam, the process of structure formation begins inside these band
structures and near them. In 5 hours of hardening, the number of band formations increases;
herewith, globular structures emerge in the surface layer, which is accompanied with its simultaneous breakdown. In subsequent heating of films, the globular structure is revealed
more clearly as the result of the aggregation of structural elements. Heating of films for over
8 h and subsequent irradiation do not lead to the change of their structure. From comparison
of the structural data, it follows that primary structural elements in polymerization of coatings and free films are similar by their morphology and size. The character of secondary
supramolecular structures formed in subsequent polymerization is different. In films, the
globular structure is preserved, and in coatings chain-type structures are formed.
A structure from elements of anisodiametric shape is found in the formation of coatings from the same lacquer on wood. As in thin films, it was also inhomogeneous along the
thickness.
354
An important point for understanding the mechanism of formation of the three-dimensional network is the study of the kinetics of three-dimensional polymerization. In process
of the latter, the size of macrochains is given, their molecular-mass distribution, conformation of structural elements forming the supramolecular structure, packing density of macrochains and structural elements, and other characteristics. Knowledge of the complex of
these factors, which have a crucial effect on the properties of formed three-dimensional
polymers, is imperative. In the case of polyfunctional monomers and oligomers, singlingout of formed macromolecules appears possible first of all at the stages preceding the gelation of the system. The structural characteristics of diallyl isophthalate (DAIP) at different
stages of polymerization preceding the gelation were studied. The chosen object is convenient for studies of the initial stage of polymerization, as the extent of its conversion Pcr is
2025%, and polymerization proceeds via the stage of soluble polymer formation.
Polymerization of DAIP (boiling point 156158C at 133 Pa, Pd 293 = 1,5260) was
carried out in sealed ampules at 353 K in the presence of benzene peroxide (0.5 wt. %). After holding for a certain time, the ampules were opened and the forming polymer was isolated by addition of acetone followed by precipitation with methanol from 2530%
solutions. The completeness of sedimentation was controlled by adding distilled water into
the mother liquor. The precipitated polymer was filtered, washed again with methanol and
dried in a vacuum cabinet at 25C and 260500 Pa to a constant weight. The extent of
monomer-to-polymer conversion was calculated by the weight of the product obtained. For
qualitative characterization of molecular-mass distribution, use was made of gel-penetrating chromatography. Chromatography was performed on columns filled with polystyrene
gel; the permeability of the columns was 3103, 1104 and 1105, the solvent was tetrahydrofuran. The residual saturation in obtained specimens was controlled by the method of
ozonation and IR spectroscopy. Ozonation was performed on an ADS-2 instrument. The
concentration of solutions in benzene was 0.1%. When recording the IR spectra, the absorption band at 1610 cm 1, characteristic of valent vibrations in the phenyl nucleus, was used
as an internal standard; the change of the double bond in the allyl grouping was followed
by the decrease of intensity of the absorption band at 935 cm 1 (deformation vibrations of
CH in RCH=CH2) and 1645 cm 1 (valent vibrations of C=C). The viscosimetric studies
were performed in a Ubbelohde capillary viscosimeter at 203C. The initial concentrations
of solutions in benzene were 10 g/dl. The molecular mass of specimens at various stages of
polymerization were determined by the method of ebullioscopy and light scattering. Ebullioscopic measurements were carried out on an EP-68 precision ebulliograph; light scattering, on a Sofica photogoniodiffusiometer. The molecular and structural parameters were
calculated by the method of double extrapolation, intensity of scattering was measured
within the interval of angles 30150.
The high-resolution NMR spectra in specimens deuterated in chloroform and acetone
(concentration, 15% at 35C) were recorded on a Tesla D-487C spectrophotometer; the
working frequency for 1H nuclei was 80 MHz. The magnitudes of chemical shifts in -scale
were recalculated relative to the signal of hexamethylene disiloxane. The structure of films
from the sol fraction of the polymer was studied by the method of electron microscopy by
taking replicas from the surface of films subjected to oxygen etching. Internal stresses were
studied by the photoelastic method.
The result of studies of the parameters characterizing the sol fraction of DAIP polymer
and obtained at different stages of polymerization are presented in Table 11.2.
High-resolution NMR spectra contained the following signals (ppm): 5, DAIP; 4.61,
CH2O; 5.04, =CH2, trans); 5.25, =CH2, cis); 5.8, = CH2; 7.79, aroma. These data confirm
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CHAPTER 11
the chemical formula ascribed to DAIP. The NMR spectra recorded from the sol fraction
of the polymer, besides the above signals, were found to have signals 4.25 and 1.75, assigned to protons of methylene groups formed in the process of polymerization, respectively, in the groupings CH CH O
and CH CH2 CH .
Table 11.2 Molecular structural parameters of the sol fraction of DAIP polymers.
Parameters
Polymerization time, h
0.5
Yield, %
[], 102 dl/g
Kn
Residual unsaturation, %
MW 103
M 103
MW /M
A2, 105 cm3mol/g
(P)
1/2,
nm
1.7
3.7
3.5
4.0
7.5
4.5
11.5
4.8
15.0
5.4
2.4
40
19.5
7.3
2.6
1.3
35
26.9
6.2
4.3
1.1
30
53.5
9.0
6.0
1.2
25
135.0
8.4
16.0
1.1
10
143.0
11.0
13.0
195.0
154.0
65.0
169.0
8.0
177.0
70.0
224.0
19.0
220.0
The obtained NMR spectra were used to calculate the extent of residual unsaturation
of the polymers sol fraction at different stages of polymerization as a ratio of the areas of
the peaks corresponding to protons of nonreacting allyl groups to the total area of the peaks
characteristic of protons of nonreacting allyl groups and groups, which entered into the reaction
CH CH2 O .
The extent of residual unsaturation was determined as the ratio of nonreacting groups
to their total content (see Table 7.2). With the increase of the extent of conversion, it decreases from 40 to 10%. A similar dependence of the residual unsaturation was obtained
for the sol fraction of the polymer using the method of IR spectroscopy, as well as ozonation. This result is in contradiction with the data presented in one work, but coincides with
the results of other works.
The characteristic viscosity of solutions of the sol fraction of DAIP polymer increases
in good solvents (benzene, methyl ethyl ketone) with the advance of polymerization; the
observed nonlinear character of the dependence of characteristic viscosity on molecular
mass in logarithmic coordinates is, probably, due to the presence of nonbranched molecules
in the system. The values of the Huggins constant Kn calculated from the viscosimetric data
decrease starting with the specimen with the low molecular mass and then do not practically
change for all specimens of the polymer at a change of the duration of polymerization and
are equal to 11.3. This dependence of Kn on the duration of polymerization indicates the
worsening of the interaction of the forming polymer with the solvent, and the order of magnitude of Kn suggests a ball-like shape of macromolecules in polymer sol fraction in these
solvents. A decrease of the value of the second virial coefficient A2 at an increase of the
duration of polymerization is also indicative of the worsening interaction of macromolecules with the solvent with the extent of conversion increasing. From the data of Table 11.3,
it follows that for the number-average Mp and weight-average molecular mass, as well as
for the root-mean-square radius of inertia (R)1/2 the tendency of an increase is observed with
356
the increase in the duration of polymerization. The same applies to polydispersity (the ratio
Mw /Mn); the order of magnitude of the latter indicates the significant polydispersity of the
sol fraction of DAIP polymer. It should be noted that at an increase of the duration of polymerization up to 4 h, in some experiments the molecular mass was found to decrease,
which is, apparently, due to the fact that near the gelation point a partial crosslinking of macromolecules and their aggregation is possible to form the three-dimensional network. Herewith, the system becomes not completely soluble in benzene, there occurs a partial
delamination of the system, and the found molecular mass and other parameters coincide
with the parameters of specimens taken at earlier stages of polymerization.
Table 11.3 Properties of coatings from various film formers.
Binding
agent-based
polymer
Formation
Glass
temperature, transition
C
temperature,
C
Polyimide PM
Polystyrene
Polyethylene:
LDPE
HDPE
PVC
Polymethyl
methacrylate:
FL-50
NP-1
ED-20
Polyvinyl alcohol
Phenol formaldehyde
resin
Natural rubber
SKS-50
SKN-40
SKD-1-3
Butyl rubber
p,
E,
GPa
MPa
3.0 3.5
2.8 3.4
170
30
320
80
515
81
200
200
80
100*
80*
80
80
180
80
100
60
80
45
50
45
60 80
85
60
2.8
2.5
3.0
2.3 3.5
5.3
2.5
60
60
60
60
200
68
50
32
60... 95
67... 75
0.0013
b, Linear extension
MPa coefficient, C 1
2.0
1.5
0.510 4
0.710 4
7.5
4.0
2.0
(2.1 5.5)10 4
(2.2 5.5)10 4
2.010 4
76.5
21 28
30 3.5
40 90
63 120
40 50
8.0
3.0
3.5
12 20
2.0
15.0
0.710 4
0.410 4
(0.7 2)10 4
(0.4 0.6)10 4
(0.7 1.2)10 4
(0.1 0.9)10 4
10
8
7
1
20
0.4
1.0
0.8
0.5
1.5
0.52 0.79 22 29
0.15 0.25 0.8 16
39 59
2.1610 4
2.1610 4
1.510 4
1.810 4
1.9410 4
*Brittleness temperature.
From these data, it follows that the sol fraction of the polymer at each time moment of
polymerization includes a set of molecules of different molecular masses and different complexity, i.e., there are both linear molecules and branched molecules, with branches of different length. If the average residual unsaturation is distinct from 50%, this means that on
average macromolecules are branched, though in this case a partial consumption of double
bonds is possible as the result of the cyclization reaction, which has a negative effect on the
development of the extent of branching of DAIP macromolecules.
The change of the character of structural transformations of polymers sol fraction depending on the duration of polymerization was studied by the method of electron microscopy to elucidate the specifics of structure formation in polymerization of DAIP. The work
CHAPTER 11
357
adduces the data on the structure of DAIP films in polymerization at different stages. It was
found that after 0.51 h of polymerization against the background of the homogeneous
structure individual globular formations from 20 up to 200 nm in size are revealed. In subsequent polymerization, the poorly resolved structure of the polymer matrix, which includes larger structural elements, becomes sufficiently well resolved, and the predominant
type becomes a globular-type structure with globules 2030 nm in size; herewith, larger
structural formations, owing to their aggregation, acquire the shape of anisodiametric structures. The emergence of anisodiametric-type structures can be due to the fact that the extent
of branching and polydispersity of the system increase with the advance of polymerization.
Recorded electron diffraction patterns and data of differential thermal analysis indicate
that specimens have an amorphous structure. Studies of internal stresses in the formation
of coatings under room conditions from systems chosen at different stages of polymerization found that, with the polymerization time increased up to 4 h, internal stresses decrease
1.5 times. This is due to the change of the character of relaxation processes depending on
molecular mass and extent of branching of macromolecules.
Thus, sol fractions of polymers are characterized by a broad molecular-mass and structural distribution and contain molecules of various complexities. The higher-molecularmass fractions occurring in polymerization form supramolecular structures of different size
and structure. In the subsequent polymerization, a three-dimensional polymer with an irregular network is formed as the result of their crosslinking.
The incompleteness of the relaxation processes in the formation of polymer coatings
from oligomer systems greatly affects their properties. A significant feature of polymer
coatings is that phenomena occurring at the interface render a significant effect not only on
the character of structural transformations, but also on the rate of relaxation processes and
the properties of coatings. The restrained character of relaxation processes in the formation
of coatings, which is due to the emergence of local bonds between structural elements and
the adsorptional interaction of the film former with the surface of the support, is accompanied with a sharp increase of internal stresses. In this connection, we put forward internal
stresses as a criterion of incompleteness of the relaxation processes, which largely depends
on the specific features of structural transformations in the formation and ageing of polymer
coatings.
11.4 Causes of internal stresses in formation of coatings

Internal stresses emerging in the formation of polymer coatings are usually considered as
the mechanical characteristics, are calculated as a product of the elasticity modulus of polymer by the value of shrinkage or the difference of linear expansion coefficients in thermal
hardening.
Shrinkage of the polymer is implied to be a reduction of linear or volume sizes of specimens as the result of the removal of solvent, dispersion medium or advancement of the polymerization process. When determining internal stresses in the process of thermal
hardening of coatings, one considers the difference of linear expansion coefficients of the
polymer and the support (when using supports, which absorb the liquid phase), the difference of shrinkage of the coating and the support.
The incorrectness of this treatment of the causes of internal stresses in the formation
of polymer coatings was first indicated in the works by V.A. Kargin and A.V. Lykov with
coworkers. They had shown that internal stresses emerging in the formation of polymer
coatings depend significantly on the rate of relaxation processes and are determined not by
358
the entire shrinkage of the system, but only by the incompleted shrinkage, exhibited after
the solution passes into a gelated state. Our works showed that internal stresses depend on
the number, nature and distribution of local bonds and can be used as the main characteristic
in studies of the kinetics of formation and ageing of polymer coatings.
Shrinkage is a physical property of a material and, by itself, does not lead to the emergence of internal stresses. A uniform shrinkage along the thickness and area of the film is
not accompanied by the appearance of internal stresses. This takes place in the formation
of very thin films on non-adhesive supports. As the thickness of free films increases, they
begin to experience internal stresses as the result of nonuniform hardening determined by
the dissimilar solvent removal rate along the thickness of the specimen or a nonuniform advancement of polymerization. The value of internal stresses increases significantly in the
formation of films on adhesive supports, and it is the greater, the higher the strength of adhesion interaction is. The cause of this phenomenon is associated with the incompleteness
of the relaxation processes.
To reveal the role of shrinkage in determining the value of internal stresses, the physical nature of the phenomenon of shrinkage was studied and the way it is closely related to
and determined by the main regularities of the film formation process. Shrinkage of films,
as internal stresses emerging in them, does not depend on density, specific weight of polymer and final volume, but is determined by the factors affecting the rate of gel formation
of the solution or the rate of increment of viscosity in the process of film formation. In this
connection, internal stresses emerging in film formation are of a relaxation character, are
proportional to the volume of the solvent evaporated from gel, and will be the higher, the
more solvent the film contains at its transition to gel.
Using these regularities, changing the concentration of the initial solution or the
amount of solvent by the moment of gel formation in the system and formation of an adhesion bond, we developed the physicochemical routes of a sharp reduction of internal stresses
in polymer coatings.
Thus, not any change of linear size and volume of the film formed from polymer solutions leads to the emergence of internal stresses. Internal stresses are determined by
shrinkage of gels formed in the formation of coating, and begin to be exhibited after their
formation owing to the inhibition of relaxation processes. In this connection, internal stresses in coatings are affected by factors, which determine the rate of gel formation. Besides
the concentration of the initial solution, these factors include the effect of the nature of solvent and various structurizing additives.
Formation of coatings from monomer or oligomer systems, performed as the result of
their polymerization directly on the support, is also accompanied by the shrinkage of the
film. In this case, as in the formation of coatings from solutions of polymers, the values of
internal stresses are affected by only an insignificant part of the general shrinkage exhibiting after gel formation in the system. The rate of structure formation in such systems is determined by the number of functional groups involved in polymerization and the rate of
their use and, because of this, depends on the chemical composition of the film former and
accelerators of polymerization, on formation conditions.
Shrinkage of polymers also changes depending on the physical factors polymerization temperature, heating and cooling rates and nature of fillers. Internal stresses emerge
both in coatings formed on supports and in free films and block materials. The cause of the
emergence of internal stresses is the slowdown of relaxation processes in the system due to
the nonuniform hardening of individual layers owing to the dissimilar rates of polymerization, the temperature gradient or moisture content or the interaction of polymer with the
CHAPTER 11
359
surface of solids the support, fillers, reinforcing materials. For polymer coatings, the crucial effect on the incompleteness of relaxation processes is rendered by the interaction of
the polymer with the support. In the absence of such an interaction, internal stresses emerging in the coatings are insignificant. As the strength of interaction at the polymersupport
or polymerfiller interface rises, internal stresses sharply increase.
Internal stresses emerging in the formation of coatings render a significant effect on
the mechanical, adhesion, electrophysical and other properties of coatings and are a criterion determining their durability.
In this connection, for working out the physicochemical bases of forming polymer
coatings and developing the ways of reducing internal stresses, it is necessary to study the
effects of various physicochemical and technological factors on the value of internal stresses and the kinetics of their increment in the formation and ageing of polymer coatings.
Internal stresses as a criterion of incompleteness of relaxation processes depend significantly on the physical state of polymers. The effect of the physical state on internal
stresses is revealed the most vividly during the heating of polymers of the same chemical
composition up to a temperature lower and higher than the glass-transition temperature. We
present the data on the change of internal stresses during the heating of coatings with a
three-dimensional structure produced based on epoxy, phenol-formaldehyde resins and unsaturated oligoesters. Internal stresses were measured by the photoelastic method. It is seen
that at a temperature of 20C, i.e., lower than the glass-transition temperature, which for
coating studied is 4080C depending on their chemical composition, internal stresses are
315 MPa. When heating them up to 80C, i.e, higher than the glass-transition temperature,
we observed a gradual decrease of internal stresses down to 0.10.5 MN/m2.
Table 11.3 presents the data on the effect of the chemical composition and physical
condition of polymers on internal stresses in coatings, measured at 20C. It is seen that the
largest internal stresses emerge in coatings from polymers, which are in a glassy state at the
operation temperature, and especially in coatings with a spatially crosslinked polymer
structure. Comparative data for coatings from oligomers formed by thermal hardening of a
spatially crosslinked structure indicate that the largest internal stresses emerge in the formation of coatings from epoxy resins as compared, for instance, with polyester oligomers.
A sharp increment of internal stresses in the formation of epoxy coatings could not be explained by the differences in shrinkage or different linear expansion coefficients of the film
or support. The linear expansion coefficient of epoxy coatings of various chemical compositions, as is seen in Table 7.3, changes within the limits of (4565)10 6 C1, and shrinkage does not exceed 2%. For coatings based on unsaturated polyesters depending on their
chemical composition, the linear expansion coefficient is greater than (70200)10 6 C 1
(dimension, 1/C), and shrinkage in hardening is 1012%. The linear expansion coefficient
of coatings from elastomers, for instance, butadiene and its derivatives, is much greater and
changes within the limits of (130216)106. Internal stresses emerging in thermal hardening of coatings based on elastomers differ little from stresses emerging in their formation
at 20C.
All these indicate that the crucial role in determining the value of internal stresses is
played by the specifics of structural transformations in the formation of polymer coatings,
which determines the rate of relaxation processes. The character of structure formation in
a very general form is determined, first and foremost, by the molecular structure of film
formers and their conformation, specific features of supramolecular structures they form,
the number, nature and distribution of links in the formation of coatings.
A significant effect on the value of internal stresses is rendered by the molecular mass
360
of film former molecules, which affects their flexibility and conformation and structuralmechanical properties of the system.
Table 11.4 presents the composition and characteristics of dianic epoxy resins, widely
used in production of coatings, and the physicomechanical properties of coatings on their
basis, obtained in thermal hardening.
It is seen from the table that internal stresses decrease as the molecular mass increases.
It could be assumed that a decrease of internal stresses with the molecular mass of epoxides increasing is related to the decrease of the number of epoxy groups involved in polymerization, and to the formation of a less dense three-dimensional network. However, the
weak effect of the concentration of epoxy groups on the other physicomechanical properties
(elasticity modulus, breaking strength) indicate that the number of functional groups in the
molecule, which are capable of participating in polymerization, does not always determine
the density of the three-dimensional network in the formation of coatings.
The density of the three-dimensional network in epoxy coatings depends on the nature
of hardener and significantly affects the value of internal stresses. In coatings from epoxy
resins, hardened by isocyanates, the emerging internal stresses are 1.52 times greater than
using amine-type hardeners. The cause of this phenomenon is stipulated by the formation
of a denser three-dimensional network between the structural elements when using isocyanate hardeners.
Table 11.4 Physicomechanical properties of coatings based on epoxy diane resins.
Molecular
mass
Content of epoxy Content of hydroxyl

groups, %
groups, %
300 400
400 600
600 800
800 1000
1000 1400
1400 1800
1800 3500
24.8 21.5
21.5 14.5
14.5 10.10
10.0 8.0
8.0 6.0
6.0 4.0
4.0 2.0
0.1 0.8
0.8 2.5
2.5 4.6
4.6 5.1
5.1 6.0
6.0 6.5
6.5 6.8
b,
E, GPa
2.7
2.7
2.5
1.8 2.5
2.5
3.0
3.2
p,
MPa
MPa
10 20
8 15
5 10
24
24
13
12
30 40
30 40
25 30
20 25
30 34
30 34
30 35
It is known that in hardening of epoxy resin by isocyanates the hydroxyl groups of the
resin interact with isocyanate groups to form the urethane bond:
CH
OH + N
OR
CH
COOR
The epoxy group is also capable of interacting with isocyanate to form five-membered
cycles of 2-oxazolidones:
CH2
CH2
O
CH
CH2
N O
C
O
It is also not to rule out the possibility of interaction of the amide group formed by reaction I with epoxy groups of the resin. With this in mind, it can be assumed that, as the
CHAPTER 11
361
result of hardening of epoxy resin by isocyanates, a polymer with a greater density of the
three-dimensional network is formed, which contains no free functional groups. In the case
of using amine hardeners, the hydroxyl groups are not involved in the chemical interaction.
Hardening is performed as the result of the interaction of epoxy groups with primary and
secondary amines; epoxy resin hardened by amines has the structure represented by the following scheme:
O
NH2 + 2CH2
CH
CH2
[R
]n
CH2
CH2
CH
O
CH2
CH
CH2
[R]n
CH2
OH
R'N
CH2
CH
CH
CH2
CH
CH2
O
CH2
OH
[R]n
CH2
O
where R is alkyl or aryl radical of amine

CH3
R
group
C
CH3
OCH2
CH
CH2
OH
For this reason, epoxy coatings hardened by isocyanates are more stable to the action
of various aggressive media and swell in solvents less. At the same time, the number of
chemical bonds does not determine unequivocally the swelling ability of films and coatings
in solvents; the character of their distribution is important. Using amine hardeners, coatings
formed in 1 h at 20C and 2 h at 160C swell in alcohols less with the increase of the molecular mass of the resin. For coatings hardened by isocyanates under the same conditions
an inverse dependence of swelling on molecular mass is observed: the swelling decreases
with the decrease of the molecular mass. Thus, there is no one-to-one dependence between
the swelling and density of the three-dimensional network.
These data are also indicative of the significant effect of not only the number and
nature of bonds on the value of internal stresses, but also the character of their distribution
in the system. The absence of correlation between the density of the three-dimensional network, determined by the swelling method, and the value of internal stresses was also
observed for other oligomers.
Coatings have a characteristic inhomogeneous structure along the thickness of the
film. The structure of epoxy coatings of about 300 m in thickness, hardened on a glass
support at 80C, was studied. After hardening for 5 h, the coatings peeled off the support.
The character of delamination was controlled by the structure of the support and coating
layers bordering with the support. The structure was studied by the method of electron
microscopy by taking carbonplatinum replicas, as well as by layer-by-layer slices on an
ultratome.
362
A sharp change of the structure of epoxy coatings was observed in layers bordering
with the support and the air. Away from the border by 100200 nm, the structure of the
middle layers is stabilized and does not change significantly in passing from one layer to
another. At the interface with the support, a homogeneous globular structure was observed
owing to the adsorption interaction of oligomers with its surface. The size of globules is
1020 nm and coincides with the size of associates in epoxy oligomers. Away from the interface, the mobility of structural elements increases, they aggregate to form more complex
supramolecular structures.
In layers bordering with the air, secondary supramolecular formations significantly
worsen the protective and decorative properties of coatings. The architecture of secondary
supramolecular structures, their number, size and character of their distribution on the surface depend on the heterounit character of chains, molecular-mass distribution. In coatings
from epoxy dianic oligomers, for instance, E-41, with a broad molecular-mass distribution
from 600 up to 20,000 complex supramolecular formations are crater origination centres.
Studies of the mechanism of structure formation in solutions of epoxy oligomers found that
the cause of this phenomenon is due to the dissimilar solubility of various-molecular-mass
fractions in complex solvents, for instance, R-5, and the emergence of secondary supramolecular formations in oligomer solutions.
It was shown that in the centre of a crater there is a nucleus from more ordered and
densely packed structural elements. By the radii of the craters, spheres with various structures and clear-cut interfaces are observed. The architecture and structure of secondary supramolecular formations depend significantly on the nature of the support; data were
presented on the layer-by-layer inhomogeneity of the structure of epoxy coatings from oligomers with molecular masses of 400600, filled with titanium dioxide and formed at
80C. Along with the globular structure characteristic of epoxides, a fibrillar structure is
formed in layers bordering with the support, near the surface of particles of the filler. For
layers bordering with the air, owing to a larger mobility of structural elements, an ordered
structure from densely packed structural elements is found near particles of active filler. The
oriented layers of polymer, which enclose the filler particles, are joined by structural elements of the fibrillar type. The inhomogeneity of the structure along the thickness of the
film is also observed at the introduction of other active fillers in various concentrations. Oriented supramolecular structures of surface layers of coatings form a network. Formation of
an imperfect layer-by-layer inhomogeneous structure is observed in fabrication of protective coatings from epoxy oligomers with a higher molecular mass from 1200 up to 2000,
widely used for protection of equipment and production facilities in food industry. The
structure of an epoxy coating from oligomer E-41, hardened at 80C, of about 150 m in
thickness, was given.
The most chemically resistant cold-hardened epoxy polyamine coatings possess low
protective properties in biochemically active media even at short-term exposure. The cause
of this phenomenon is associated with the fact that formation of a three-dimensional structure is accompanied with the emergence of an inhomogeneous imperfect network with the
nonuniform distribution of chemical bonds in the system, of internal stresses commensurable with adhesion strength and stipulated by the incompleteness of the relaxation processes.
The use of special modifiers we developed makes it possible to reduce considerably
from 2 up to 10 times internal stresses, to increase adhesion of coatings, to increase their
durability, including in hardening under conditions of natural drying. It was found that the
use of epoxy compositions of nitrogen-containing surfactants as modifiers makes it possible
to significantly reduce internal stresses as the result of a decrease of adhesion strength at
363
CHAPTER 11
the polymersupport, polymerfiller interface. At an optimal concentration of surfactants,

as the result of forming a more ordered structure in coatings, an increase of the tensile
strength of films is observed. However, the worsening of adhesion is accompanied with a
decrease of the resistance of coatings to aggressive media. The use for modification of
epoxides of compounds with functional groups capable of interacting chemically with the
support and film former, causes, along with an increase of adhesion strength, a sharp increment of internal stresses.
With consideration of these regularities, modifiers based on nitrogen-containing oligomers with active functional groups with respect to the support and to oligomer with an
optimal degrees of branching of macromolecules were developed. The effect of the modifiers on the structure, physicomechanical and protective properties of coatings was studied.
The object of study were epoxy oligomers E-40 and E-41, as well as mass produced enamels
on their basis. A modifier was introduced into solutions of oligomers and enamel prior to
their application to metal. Hexamethylene diamine was used as hardener. The concentration
of modifier was varied within the range of 0.114%. Coatings were formed on steel degreased with white spirit; a layer of 80120 m in thickness was applied by pneumatic
spraying. The protective properties of coatings were assessed by the capacitanceresistance
method; the capacitance and resistance of painted metal in electrolyte were measured using
an a.c. bridge. As working electrolyte, use was made of a 1% solution of sodium chloride.
A 3% solution of lactic acid was used as a model medium due to the insufficient resistance
of epoxy coatings in organic acids. The protective properties of coatings were assessed by
the capacitance and resistance coefficients calculated as a ratio of respective electrophysical
parameters at frequencies of 20,000 and 2,000 Hz. The physicomechanical properties of
coatings (hardness, adhesion, impact strength) were determined by the standard methods.
Internal stresses were measured by the photoelastic method. The structure of coatings was
studied by electron microscopy.
It was found that good protective and physicomechanical characteristics are observed
at a modifier concentration of about 2%. The properties of coatings at an optimal concentration of the modifier are given in Table 11.5.
It is seen in the table that introduction of a modifier significantly improves the physicomechanical and protective properties of coatings, decreases internal stresses at a simultaneous increase of adhesion and durability.
Table 11.5 Effect of the modifying additive on the properties of epoxy coatings.
Properties
of coating
Relative hardness, arb.
units
Impact strength, J
Adhesion on Erichsen
tester, mm
KC
KR
G, Sm
Longevity, days
E-40
E-41
Enamel
Initial
Modifying
Initial
Modifying
Initial
Modifying
0.81
0.86
0.85
0.85
0.47
0.51
3.0
2.0
5.0
9.0
3.0
2.2
5.0
9.5
4.0
4.5
5.0
9.6
5.0
0.37
2.42
4.5
40
2.5
0.53
5.40
3.0
520
3.0
1.30
12.50
4.9
30
1.5
0.90
17.30
3.3
550
4.5
0.96
7.20
3.2
63
1.8
0.99
9.30
1.1
500
364
The effect of the concentration of modifier on the structure of coatings formed at 20

and 120C was studied. Coatings hardened at 20C were shown to have an inhomogeneous
globular structure with the size of globules 2540 nm; the globules formed aggregates and
anisodiametric structures 65250 nm in size with a loose packing of the structural elements.
With the coating formation temperature increased up to 120C, the diameter of globular aggregates is observed to decrease to 80 nm. Introduction of an optimal amount of modifier
contributes to a decrease of the globules size to 1020 nm and their aggregates size to
5080 nm, respectively, under conditions of hardening at 20 and 120C; the packing density of structural elements is also increased.
Formation of an ordered structure in coatings from modified compositions contributes
to a more uniform distribution of chemical bonds in the system, to a decrease of internal
stresses, improvement of the adhesion and protective properties of coatings. Introduction
of a modifier stabilizes the frequency dependence of the electrophysical characteristics of
coatings under conditions of their performance in a lactic acid solution.
The chemical interaction of modifier with epoxy oligomer was confirmed by the method of IR spectroscopy. This is expressed in a decrease of intensity of the absorption band
of epoxy groups in the region of 920 cm 1 and the emergence of an arm on the side of low
frequencies, as well as in a decrease of absorption intensity of nitrogen-containing functional groups in the region of 33003450 cm 1. Introduction of a modifier also contributes
to the acceleration of hardening after the stage of gelation.
A network of secondary supramolecular structures was shown to be formed in coatings layers bordering with the air. Using the method of oxygen etching and at a large magnification, the secondary structures forming craters were studied. The effect of coatings
formation conditions on the defect-formation mechanism, structure and properties was
studied. Studies of the kinetics of increment of internal stresses found that a specific feature
of coatings formation from epoxy oligomers with broad molecular-mass distribution consists in a jump-like change of properties and the occurrence of induction periods at particular stages of formation. In formation of coatings at 20C, minor internal stresses emerge
at the initial stage, and only in 5 h they begin to increase to an ultimate value, which is observed in 10 days. With the formation temperature increasing up to 90C, the stresses
change jump-like, in three stages, which are characterized by different rates. The same number of periods is observed in hardening of coatings at 120C. They differ by the value of
initial and final stresses. The kinetics of changes of internal stresses in the formation of coatings is correlated with the polymerization kinetics at various hardening conditions.
Studies of the defects by the optical method with magnification from 70 up to 500
found that their size changes from 0.1 up to 1.5 mm. Craters have an oval, oblong or round
shape. When changing from smaller to larger magnifications, it is seen that a defect is inhomogeneous and consists of various regions in the shape of spheres assembled around a
centre and having clear-cut boundaries. In the centre, there is the most dense part the nucleus whose shape can be different and whose size is from 0.1 up to 0.25 diameter of a
crater. The nucleus is transparent for light beams and occupies a certain volume. To be able
to see its particular parts, it is necessary to change the focal distance. At a larger magnification, it is easy to see the structuredness of the centre of a defect and the differences in the
structure of its individual parts. The defects nucleus is not a particle of dust or other foreign
body getting inside in application of the coating. The latter form defects in the coating,
which are essentially different by their structure.
Thus, the specifics of structure formation in coatings from epoxides with a comparatively high molecular mass is that complex supramolecular formations emerge in the
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365
surface layer of the film at the boundary with the air. The formations consist of radial rings
with different morphologies of the structural elements, size and density of packing.
To study the crater formation mechanism, epoxides were fractionated into individual
monomolecular fractions by the method of liquid adsorption chromatography. Silica gel
KSK-2 was used as adsorbent; the fractions were dissolved in acetone. The molecular mass
of the fractions was determined by the method of light scattering. The molecular mass of
the fractions increases, as their number rises from 150 up to 2,000.
Coatings obtained from the monomolecular fractions of epoxy oligomer are observed
to have a homogeneous globular structure. The size of structural elements increases with
the molecular mass of the fractions increasing; herewith, coatings are observed to have no
defects.
To prevent aggregation of structural elements and emergence of crater-formation centres, we developed methods of modifying epoxy oligomers by compounds with the mesomorphic structure of the type of PCOA (P, aromatic radical; A, aliphatic radical). The
proposed modifiers with the regular arrangement of aromatic and aliphatic radicals with active functional groups, in accordance with the StewartBrigleb model provide for the local
interaction of modifier with film former and the surface of solid bodies. The scientific principles of developing a regular structure using structure-forming modifiers made it possible
to produce coatings with high performance properties and durability.
As the result, it was found that:
protective and decorative polymer coatings are distinguished with a diversity of properties depending on their purpose and operating conditions;
requirements to the increase of protective properties and durability of materials constantly rise in connection with the necessity to provide for the ecological safety of the population; in connection with increased technogenic emissions, which pollute the atmosphere,
soil and water and contribute to the development of pathogenic microflora.
Degradation of polymer materials under the action of microflora is three times faster
than due to other factors accelerating the corrosion processes. The cause of this phenomenon is due to the consumption of components of polymer compositions by microorganisms,
which excrete enzymes, organic and inorganic acids strong activators of the decomposition of practically all materials: metals, concretes, wood, polymers, etc.
The development of the scientific principles of increasing the durability of polymer
coatings is inseparably related to the studies of the specific features of the structure formation mechanism and the development of scientifically substantiated methods of normalizing
the supramolecular structure.
The normalizing is meant to be the development of scientific approaches, which make
possible the use of the largest number of active functional groups in macromolecular film
formers in the formation of the three-dimensional network.
A major part of functional groups (more than 50%) are consumed in hardening of polymer systems for the formation of complex supramolecular structures practically not involved in the formation of the three-dimensional network, which determines the
performance properties of coatings.
A criterion of homogeneity and imperfection of the network in the formation of coatings are internal stresses, which depend on the rate of the relaxation processes at various
stages of structure formation.
The effect of various physicochemical factors (nature of the film former, regimes of
formation, molecular mass) on the value of internal stresses in the formation of coatings
was studied.
366
The scientific principles of creating a homogeneous regular ordered structure were developed, which make it possible to considerably increase the protective properties and durability of coatings. Methods of modification based on the use of compounds with the
mesomorphic structure and regular arrangement of aromatic and aliphatic radicals with active functional groups were proposed. In accordance with the StewardBrigleb model,
compounds with the mesomorphic structure provide for the local interaction of modifier
with film former and the surface of solid bodies. Scientific principles of developing a regular structure using a structure-forming modifier make it possible to obtain coatings with
high performance properties.
11.5 Effect of the nature of hardener and initiator on the formation and
The change of the concentration and nature of the polymerization hardener and initiator
makes it possible to regulate the hardening kinetics of coatings and their properties.
It is known that the dependence of internal stresses and other physicomechanical properties of films on the amount of hardener in the system is nonmonotonic and exhibits a maximum corresponding to the formation of the largest number of crosslinks. In this
connection, a decrease of internal stresses by changing the amount of hardener is accompanied with the worsening of other physicomechanical properties of films. For instance, the
strength of specimens from polyester resins is greatly affected by the amount of added initiator and accelerator of polymerization, which is related to the different degree of hardening. At the same time, the larger the rate of hardening, the greater the initial strength is (but
the smaller the strength after ageing is). It follows from these data that the extent of hardening is not the only factor determining the strength and durability of coatings and films.
From the experimental data presented further, it follows that the strength properties of network polymers correlate with the change of internal stresses emerging in the formation and
ageing of specimens. The effect of the concentrations of initiator and accelerator on internal
stresses and physicomechanical properties of specimens from polyester resin elasticity
modulus, breaking strength and bending strength was studied. To prepare specimens,
polyester resin with various concentrations of initiator and accelerator was poured into
molds 5, 50 and 120 mm in size. The specimens were hardened for 3 days at 18C. Cumene
hydroperoxide was used as a polymerization initiator. The reaction was accelerated by addition of a 8% styrene solution of cobalt naphthenate. Internal stresses were measured by
the photoelastic method. The ultimate value of internal stresses essentially depends on the
Table 11.6 Dependence of internal stresses in polyester resin specimens on material of the molds.
Amount of
accelerator, %
8
6
8
8
8
8
Amount of initiator,
%
3
3
1
2
3
4

Steel
Glass
Fluoroplastic
6.24
10.5
3.60
7.60
4.00
1.61
3.84
5.04
0.76
0.56
1.80
3.90
2.80
2.01
Hardening time,
days
1.5
1.5
3.0
3.0
3.0
3.0
CHAPTER 11
367
material of the mold (Table 11.6). The lowest internal stresses emerge in hardening of the
resin in molds lined with fluoroplastic. With consideration for this, the further results were
obtained for specimens hardened in such forms.
From the concentration dependence of internal stresses on the content of polymerization accelerator, it follows that internal stresses are maximal in the presence of 1012%
accelerator in the system.
For various batches of the resin, differing by the content of styrene, the maximum
shifted to the side of the lower content of accelerator. A similar nonmonotonic dependence
of the concentration of accelerator was also observed for the elasticity modulus, which was
studied by the dynamic method on an impulse-excitation unit. The frequency of oscillations
was 800 kHz; the division value of scan, 0.2 s.
The elasticity modulus was calculated according to the equation
2 1 ( 1 + ) ( 1 2 )
E = C p ----------------------------------------------- ,
1
where C is the speed of sound; p is density; is the Poisson coefficient. From the analysis
of the data, it follows that internal stresses correlate with the change of the elasticity modulus depending on the content of the polymerization accelerator. In the concentration dependence of internal stresses on the content of polymerization initiator, a maximum is
observed at its 3% concentration in the system. The amount of accelerator in these experiments was 8%. At this concentration of initiator, the maximal values of other physicomechanical characteristics are observed: elasticity modulus, hardness, tensile strength and
bending strength of coatings. These parameters correlate with the change of internal stresses, which is stipulated by the most complete use of functional groups under these conditions
of polymerization and the formation of the largest number of chemical crosslinks.
The optimal amount of polymerization initiator and accelerator depends on the chemical composition of polyester lacquers, as is seen from the data on the dependence of internal stresses on initiator and accelerator concentrations in the formation of coatings at 80C
from oligomaleinate phthalate lacquer PN, which contains triethylene glycol diester of
methacrylic acid as the polymerizing solvent. Specimens were hardened in the presence of
initiator (mixtures of cumene hydroperoxide and cyclohexanone) and accelerator (a styrene
solution of cobalt naphthenate); the dependence of internal stresses on initiator and accelerator concentrations in the system is nonmonotonic, as for coatings from oligoester PN.
The maximal rate of hardening is at 2% initiator and 4% accelerator.
However, more stressed specimens are distinguished by a lower resistance to ageing.
The presence of high internal stresses, reaching 2535% of the breaking and bending
strengths, leads to spontaneous breakdown of specimens. A decrease of internal stresses by
regulating the content of initiator and accelerator of polymerization is accompanied by a
considerable worsening of other physicomechanical properties.
With consideration for this, of great interest for regulating the properties of coatings
are studies of the effect of hardeners nature on the properties of coatings. The effect of various hardeners on the properties of coatings from epoxy oligomers was studied the most.
Epoxy resins are oligomer systems with a low molecular mass, characterized by the presence of epoxy (ethylene oxy) groups with a molecular mass 43, having the shape of threemembered oxygen-containing cycles. In ring opening, this group is capable of interacting
with the labile atom of hydrogen in amines, amides, acids, alcohols or phenols to form a
hydroxyl group.
368
Polyamines with the molecular mass of 3701000 are used for hardening dianic epoxy
resins. Di- and polyamines interact with epoxides to form network polymers:
H2C
CH2
R'
H2C
CH2
CH2CH R CHCH2N
OH
OH
R' NCH2CH
OH
CH2
CHCH2 N CH2
OH
H2C
R'
N
CH2
Aliphatic polyamines diethylene triamine (H2N(CH,)2NH(CH2)2NH2), triethylene

triamine (H2N(CH2)2NH(CH2)2NH(CH2)2NH2), hexamethylene diamine (H2N (CH2)f
NH2) are widely used as hardeners.
Along with polyamines, oligoamides with molecular masses of 2,000 up to 5,000 are
widely used for hardening epoxides.
Oligoamides are obtained by interaction of dimerized fatty acids of drying oils with
polyethylene polyamines. Along with secondary free amino groups, they contain more
Table 11.7 Effect of the nature and concentration of hardener on the physicomechanical
parameters of films from ED-20.
Content of
hardener, %
Strength of glueing, MPa
b,
E, GPa
, %
Tg, C
2.4
5.1
4.0
4.6
3.5
7.4
60
74
80
88
83
80
60
4.3
4.8
5.9
5.0
4.3
5.0
42.0
55
75
97
87
75
62
34
MPa
Steel
Copper
TEPA
Titanium
Hardening (150C, 4 h)
5
6
8
10
15
20
25
50
68 C
77 C
82 C
68 C
56 C
26 A
28 A
29 A
10
15
20
25
30
40
45
50
60
5C
24 C
37 C
26 C
22 A
27 A
23 A
21 C
PO-300
71 C
74 C
77 A
36 A
28 A
18 A
2A
5A
59 C
70 C
86 C
59 C
52 M
49 A
48 A
44 A
38
52
56
46
38
46
38
58
1.66
2.40
1.43
1.43
1.60
1.44
2.01
Hardening (120C, 2 h)
51
52
53
47
39
46
15
2.84
2.70
2.48
1.96
1.26
1.76
0.75
Note: A, adhesion breakdown; M, mixed breakdown; C, cohesion breakdown.
CHAPTER 11
369
reactive primary amino groups arranged by the ends of the chain. Reactive oligoamides are
prepared with excess amine with respect to dimers of fatty acids to increase the content of
amino groups in the chain. Owing to their larger molecular mass as compared with amines,
polyamides are nonvolatile and nontoxic.
The nature of hardener renders a significant effect on the physicomechanical and adhesion properties of epoxy coatings. As seen in Table 11.7, a combination of high adhesion
strength and cohesion strength is observed at an optimal content of the hardener. Epoxy
coatings hardened by tetraethylene pentamine (TEPA) exhibit higher physicomechanical
and adhesion properties as compared with coatings hardened by polyamide resin PO-300
a production of the interaction of polyamides with di- and trimerized acids of plant oils.
IR spectroscopic studies of the consumption of epoxy groups depending on the concentration of PO-300 indicate a nonmonotonic character of this dependence. The maximal
consumption of epoxy groups was observed at a concentration of 35% and corresponds to
the highest physicomechanical characteristics of coatings. Herewith, the consumption of
epoxy groups is greater than that calculated from the reaction of maximal addition of epoxy
groups to amine groups. This is, probably, due to the catalytic polymerization of epoxides
in the presence of tertiary atoms of nitrogen present in polyamide resin.
The regularities of increment and relaxation of internal stresses depending on the temperature of hardening of films and the nature of hardener were studied.
The object of study was epoxy resin ED-20. Hexamethylene diamine and phenol-formaldehyde resin were mixed with epoxy resin as solutions; the former, in ethyl alcohol; the latter, in acetone. After formation of coatings for 14 h at 110C and, respectively,
2025 h at 70C internal stresses reach ultimate values in all cases. The measurement of
internal stresses was performed by the photoelastic method. At room temperature the stresses relax in accordance with the Shvedov equation (Fig. 11.1). The relaxation time depends
on the nature of a hardener. The highest value of the relaxation time (81 h) is observed in
the formation of coatings in the presence of polyethylene polyamine; the lowest (50 h), in
the presence of hexamethylene diamine. In films hardened by phenol-formaldehyde resin
the relaxation time was about 76 h.
Figure 11.2 presents a concentration dependence of internal stresses on the content of
polyethylene polyamine for epoxy coatings formed at 110C for 15 h. It is seen in the figure
that stresses change nonmonotonically. The maximal values of internal stresses were found
at a hardener concentration of 68%. This indicates that the formation of a maximal amount
of chemical bonds is prevented not only by the deficiency of hardener but also by its excess.
This is also confirmed by the data on the change of the hardness of coatings depending on
the concentration of hardener.
During the formation of coatings in the presence of phenol-formaldehyde resin, internal stresses are observed to increase monotonically with the concentration of hardener increasing (Fig. 11.3).
The critical thickness, at which a spontaneous delamination of coatings under the action of internal stresses is observed, also depends on the nature of hardener. Figure 11.4 presents the data on the change of internal stresses depending on the thickness of formed epoxy
films. It is seen in the figure that films hardened by polyethylene polyamine peel off at a
significantly smaller thickness than in hardening by hexamethylene diamine. Herewith, in
all cases delamination was accompanied with the breakdown of the surface layers of the
glass support.
The effect of the concentration and the nature of hardener on internal stresses in coatings from various epoxy resins was studied. The objects of study were epoxy resins ED-20,
370
logG
1.4
1.0
0.6
2
0.2
48
144
240 Time, h
Figure 11.1 Kinetics of relaxation of internal stresses in epoxy coatings from ED-20 formed with
hexamethylene diamine (1), phenol-formaldehyde resin (2) and polyethylene polyamine (3).
b, MN/m2
N, GPa
0.20
6
0.15
10
15
Polyethylene polyamine, %
20
Figure 11.2 Effect of the concentration of polyethylene polyamine in ED-20 on hardness (1) and
internal stresses (2).
ED-16, ED-casting and E-33 with epoxy numbers, respectively, 25.75, 18.3, 8.15, 10.22%.
Phthalic anhydride, metaphenylene diamine, polyamide with amine number 216 were used
as hardeners. The film-forming mixtures were prepared by introducing the hardener into the
resin heated up to 100110C or dissolved in mixed solvents (acetone, xylol, cellosolve).
The data on the kinetics of increment of internal stresses in the formation of coatings
at 130C from epoxy resins ED-20 and ED-casting, mixed with various amounts of phthalic
anhydride, and their relaxation during the storage of specimens under standard conditions
were given. It is seen that the rate of increment and the maximal value of internal stresses
depend on the composition of the film former. The largest magnitudes of these values are
observed at a 67% content of hardener in terms of the initial ratio. The relaxation periods
CHAPTER 11
371
b, MN/m2
8
6
4
2
20
Figure 11.3
60
100
Phenol formaldehyde resin, %
Effect of the concentration of phenol-formaldehyde resin in ED-20 on internal stresses.
14
3
b, MN/m2
10
200
400
600
Film thickness, m
800
Figure 11.4 Dependence of internal stresses on the thickness of coatings from ED-20 hardened by
hexamethylene diamine (1), phenol-formaldehyde resin (2), polyethylene polyamine (3).
also depend on the composition of the film former. The sharpest decrease of internal stresses is observed at a lowest content of anhydride.
During the change of the ratio between resin and hardener, the ultimate internal stresses emerging after the formation of films, change nonmonotonically. During the formation
of coatings from ED-20 with metaphenylene diamine, ED-16 and ED-casting with phthalic
anhydride, the largest value of internal stresses is observed at equivalent ratios between epoxy groups of the resin and functional groups of the hardener. In the hardening of films by
phthalic anhydride, the losses of this hardener as the consequence of the lyophilization were
taken into account.
Figure 11.5 presents the data on the effect of the content of metaphenylene diamine on
the extent of swelling of films from resin ED-20. The minimal extent of swelling is observed at an equivalent ratio between the epoxy groups of the resin and the functional
372
Degree of swelling, %
30
20
10
Figure 11.5
10
20
Effect of metaphenyl diamine on the swelling of coatings from ED-20.
groups of the hardener. From the comparison of the data of Figs. 11.4 and 11.5, it is seen
that coatings with the greatest degree of hardening correspond to systems with maximal internal stresses.
To produce epoxy coatings resistant to the action of alkali, water, acids and high temperatures up to 250300C, resol phenol-formaldehyde, urea- and melamine-formaldehyde
resins are used as hardeners. They are added in the amount from 20 to 30 weight fractions.
Coatings are hardened at high temperatures (150200C) as the result of interaction of methylol groups of resol phenol-formaldehyde resin with epoxy groups. In the case of using
butanolized phenol resins, butoxyl groups react with hydroxyl groups of the resin at a temperature greater than 180C. Table 11.8 presents data on the effect of the nature of hardeners
on the value of internal stresses in 10200 m-thick epoxy coatings hardened at 120C.
Table 11.8 Effect of the nature of hardener on internal stresses in 120 m-thick coatings from
ED-20 formed at 120C.
Hardener
Polyethylene polyamine 6%
Polyamide PO-300 30%
Hexamethylene diamine in equivalent ratio
Phenol formaldehyde resin at a ratio 1:1
Phenol formaldehyde resin at a ratio 1:0.3
Butanized phenol formaldehyde resin 1:0.3
Phthalic anhydride 67%
Metaphenylene diamine 15%
Ultimate b,
MPa
Quasi-equilibrium b,
MPa
10.0
7.0
4.0
6.0
4.0
2.5
4.0
5.0
6.0
5.0
3.0
4.0
3.0
2.0
3.0
2.3
Polyethylene polyamine, hexamethylene diamine, phenol-formaldehyde resin, phthalic anhydride, metaphenylene diamine, butanized phenol resin were used as hardeners. The
greatest internal stresses emerge in hardening of epoxy coatings by polyethylene polyamine. A considerable decrease of internal stresses is observed in hardening of coatings by
butanolized phenol resin.
373
CHAPTER 11
By example of coatings from higher-molecular-mass epoxy resins, the most resistant

to aggressive media were shown to be coatings hardened by diisocyanates to form a urethane bond owing to the interaction of hydroxyl groups and isocyanate groups:
OH + O
Besides this main reaction, which proceeds at room conditions, at high temperatures
(180200C) epoxy groups interact with isocyanates to form additional chemical bonds.
As hardeners of epoxy resins, use is usually made of 2,4-toluylene diisocyanate (product 102T) and its mixture with 2,6-toluylene diisocyanate at a ratio 65:35 (product 65T), as
well as hexamethylene diisocyanate.
CH3
CH3
NCO
NCO
102T
NCO
OCN
NCO
CH3
NCO
NCO
65T
Coatings hardened by isocyanates are characterized by a denser three-dimensional network as compared with epoxy coatings hardened by polyamines. This provides for their
greater stability to aggressive media.
Anhydrides of organic acids are used as hardeners to produce heat-resistant coatings.
Methyl tetrahydrophthalic anhydride is applicable for increasing the acid resistance and
thermal resistance of coatings:
HC
CH2
C
H3C
CH
CH
CH2
O
C
O
C
O
In the process of hardening, the anhydride interacts not only with epoxy groups of the
resin but at a higher temperature also with hydroxyl groups. The structure of hardened resin
can be represented by the following scheme:
CH3
CH2
CH
OC
OC
CH2
CH
CH2
CH2
CH3
CH
CH2
R
C
CH3
CH2
C
CH3
CH2
CH
CH2
374
16
1
2
b, MN/m2
12
4
4
10
, h
Figure 11.6 Kinetics of internal stresses in hardening of epoxy coatings from EDT (1, 4) and EKhD
(2, 3) phthalic anhydride (1), methyl tetrahydrophthalic anhydride (2), diamet X (3), triethylene tetraamine (4).
It is seen in Fig. 11.6 that hardening of epoxy resin ED-20 modified by glycidyl ester
of diethylene glycol (DEG-1) of the following structure is accompanied with a significant
increment of internal stresses.
O
[CH2
CH
CH2
(CH2)2
O(CH2)2
(CH2)2
O
CH2
(CH2)2
CH
CH2CH
CH2
CH2]n
O
A significant decrease of internal stresses takes place when using primary and secondary di- and polyamines, in particular, triethylene tetramine, as hardeners in coatings from
dianic resins modified by DEG-1. Interaction of amines with the resin proceeds via epoxy
groups to form coatings with the network structure:
R'
N
CH2
R
N
CH
R'
OH
CH2
CH
CH
CH2
OH
R'
OH
CH
CH2CH
R'
OH
CH2
OH
CH
CH2
R'
OH
CH2 CH R'
CH
R'
OH
OH
CH2
...
R is the hydrocarbon residue of amine

R'
CH2
C(CH3)2
CH2
The presence of ether bonds, in contrast with compounds with ester groups provides
for a high stability of coatings to the action of alkalis, and the significant number of
375
CHAPTER 11
hydroxyl groups in the chain creates a high adhesion of coating. A relationship was found
to exist between the nature of hardener used in production of coatings from epoxy resin
ED-8 with 810% of epoxy groups and the density of the three-dimensional network affecting the internal stresses and other properties of coatings (Table 11.9). The data of the
table indicate that the density of the three-dimensional network, calculated by the equilibrium rubber-like elasticity, increases in hardening of oligomer ED-8 by cycloaliphatic and
especially aromatic anhydrides. This is accompanied by a slowdown of the relaxation processes and an increment of internal stresses.
Table 11.9 Effect of the nature of hardener on internal stresses (b), subchain between
3-dimensional network nodes (Mc), glass transition temperature (Tg) and ultimate elongation () of
coatings based on epoxy resin ED-8.
Hardener
b, MPa
Mc
Tg, C
, %
Phthalic anhydride
Methyl tetrahydro phthalic anhydride
Hexahydro phthalic anhydride
Succinic anhydride
Adipic acid polyanhydride
Sebacic acid polyanhydride
Paraphenylene diamine
Metaphenylene diamine
Benzidine
3,3-Diamino diphenyl sulfone
Dicyane diamine
4.6
3.2
4.2
2.1
1.2
0.6
5.0
4.8
3.9
3.6
2.9
523
720
813
1310
1980
2410
621
780
838
1010
1410
110
75
90
70
46
38
104
99
96
92
89
3
10
4
21
38
42
4.9
5.3
5.8
6.2
1.3
Internal stresses decrease using aliphatic polyanhydrides. Their magnitude is the

smaller, the longer the aliphatic chain in the structure of the hardener is. During the hardening by both anhydrides and amines, one reveals a regularity in the decrease of internal
stresses at an increase of particular functionality, molecular mass of the hardener and the
extent of branching of its structure.
Regularities in the change of internal stresses depending on the nature of hardener correlate with other properties of coatings the glass-transition temperature, relative breaking
elongation.
The nature of hardener also renders a significant effect on the properties of coatings
from chlorine-containing epoxy resins EKhD, which represent a product of the interaction
of epichlorohydrin with 3,3-dichloro-4,4-diamino diphenyl methane Diamet X.
O
Cl
CH2
CH
CH2
CH2
CH
CH2
Cl
CH2
CH2
CH
CH2
CH2
CH
CH2
Figure 11.7 presents the data on the kinetics of increment of internal stresses in the formation of coatings by the stepwise regime (100C, 3 h; 120C, 3 h; 150C, 3 h; 170C, 3 h)
from epoxy resin EKhD in the presence of the hardener Diamet-X
b, MN/m2
376
16
12
12 , h
10
Figure 11.7 Kinetics of internal stresses in the formation of coatings from cyclic epoxides UP (1),
UP-632 (2), UP-639 (3).
NH2
CH2
NH2
and iso-methyl tetrahydrophthalic anhydride I-MTHPA

CH2
CH
C
H2C
O
C
O
C
O
CH
CH
CH2
It is seen that in the presence of Diamet-X the coating hardens at lower temperatures
with lower internal stresses than in the introduction of the hardener MTGFA.
A sharp increment of internal stresses is observed using aromatic hardeners to produce
coatings from alicyclic epoxy resins (Table 11.10).
Table 11.10 Characteristics of alicyclic epoxides.
Oligomer
Structural formula
3,4-Epoxy hexahydrobenzal-3,4- epoxy-1,1bis-hydroxymethyl

cyclohexane (UP-612)
CH2
324
28 30
306
28 32
436
19 21
O
CH2
3,4-Epoxy cyclohexyl
methyl-3,4-epoxy cyclohexane carboxylate
(UP-632)
bis-3,4-Epoxy cyclohexyl methyl adipinate
(UP-639)
CH2 CH O
2
CH
CH2 O
Mole- Content
cular of epoxy
mass groups, %
CH2
O
CH2 C O
CH2
HC2
O
CH2
CH2
O
O
CH2
CH2 C
O
(CH2 )4C H2C
377
CHAPTER 11
As seen in Table 11.11, the value of internal stresses in coatings from these resins also
depends on the thickness of the three-dimensional network.
Table 11.11
Structural mechanical properties of coatings based on alicyclic epoxides.
Oligomer
b, MPa
Mc
Tg, C
, %
UP-612
UP-632
UP-639
12.0
9.8
6.8
310
631
797
230
250
150
1.5
2.0
5.0
Characteristics of hardeners
Name
Structural formula
Phthalic anhydride (PA)
C
C
Methyl tetrahydro phthalic

anhydride (MTHPA)
Hexahydro phthalic anhydride (HHPA)

Succinic anhydride
O
O
Sebacic acid polyanhydride
O
(CH2 )4 C
O
O
(CH2)8 C
O
Metaphenylene diamine (MPDA)
154.00
32.0
43.0 85.0
47.0 91.0
NH2
H2N
Paraphenylene diamine (PPDA)
NH2
H2N
Benzidine
NH2
H2N
3,3-Diamino diphenyl sulfone
64.0
90.00
166.09
130.5
O
CH2 C
O
CH2 C
O
Adipic acid polyanhydride
148.11
C
C
H3C
Molecular
Melting
mass
temperature, C
H2N
108.00
63.0
108.00
64.0
188.00
123.0
236.00
169.0
84.60
207.0
NH2
SO4
Dicyane diamine
H2N C
NH
NHCN
378
However, the use of anhydrides of organic acids in common epoxy resins is made difficult due to their low solubility under room conditions. To decrease internal stresses in the
formation of coatings, ester acids with different chain structure were used as hardeners. Depending on the nature of trifunctional ester acid used for hardening epoxides, the properties
of coatings changed. With the length of branchings increasing, elasticity went up. However,
if the hardening of films based on glycerol tricebacinate was performed not at 120C but at
200C, their elasticity was smaller than for triadipinate-based films formed at 120C. This
is due to the fact that at a higher temperature, along with the reaction between carboxyl and
epoxy groups, a side reaction probably proceeds between carboxyl and hydroxyl groups
formed as the result of the first reaction. This, in turn, leads to an additional crosslinking.
Coatings were formed from compositions consisting of equal volumes of 6085%
alcoholacetone solutions of ED-20 and, respectively, 70% acetone solutions of glycerol
trisuccinate, triadipinate and tricebacinate at a ratio of 1:1.
From the data on the kinetics of increment and relaxation of internal stresses, and
change of hardness in the formation of coatings from these compositions under conditions
of heating at 120C followed by holding at 20C, it follows that compositions based on
glycerol trisuccinate and triadipinate harden well under these conditions, and compositions
with glycerol tricebacinate very slowly; therefore the formation of coatings from them
was performed at 200C.
Table 11.12 Physicomechanical properties of films and coatings from copolymers of various
molecular compositions and epoxy resin.
Composition
Copolymer 1
Copolymer 2
Copolymer 3
ED-20
P, MPa
E, GPa
, %
A, MPa
Strength margin
25.2
34.3
21.5
60.0
1.5
2.4
1.2
2.4
1.4
0.7
2.2
7.0
15
15
13
18
49
9
8
The largest internal stresses emerge in coatings hardened by glycerol trisuccinate. The
results of these studies suggest that, as the length of branchings of ester acids hardening epoxy resin increases, internal stresses decrease, and the elasticity of coatings increases. If the
length of branchings is larger than the optimal value, which takes place in the presence of
glycerol tricebacinate, there is no hardening of the resin at 120C. With the formation temperature increased up to 200C, coatings based on this composition exhibit the highest
physicomechanical properties. This is indicated by the data presented in Table 11.12. Coatings from the first two compositions spontaneously break down at 200C in the process of
formation due to their high brittleness.
Coatings based on glycerol trisuccinate and tricebacinate hardened under optimal conditions can be used within a broad range of thicknesses without spontaneous decomposition
and delamination.
A specific feature of coatings based on glycerol tricebacinate is that, with the high adhesion, breaking strength and hardness preserved, they exhibit comparatively small internal
stresses.
The further decrease of internal stresses at the preservation of their high adhesion and
strength properties can be performed by ordering the structure of polyester epoxide molecules. To elucidate the effect of the structure regularity of the molecules on the properties
of coatings, studies were carried out to investigate polyester epoxy and silicon-containing
379
CHAPTER 11
polyester aminoepoxy film formers of regular and irregular structure. Synthesis of the polyester epoxy systems was performed according to the scheme:
C[CH2OC(CH2)nCOOH]4 + 2CH2 CHCH2OROCH CH2
O
O
O
C
CH2OC(CH2)nCOCH2CHCH2OROCH2CHCH2OC(CH2)nCOCH2
O
OH
OH
Hydroquinone diglycidyl and diphenylol propane diglycidyl were used as the diglycidyl component.
Organosilicon polyester amidoepoxy compositions were obtained in two stages. At the
first state, tetraadipine pentaerythrite was condensed with bis-(phenyl aminomethyl)-tetramethyl disiloxane according to the scheme:
O
H2O
C[CH2OC(CH2)4COOH]4 + 2 HNCH2 Si(CH3)2OSi(CH3 )2CH2NH

C
CH2OC(CH2)4C NCH2Si(CH3)2 OSi(CH3)2CH2N C(CH2)4COCH2

O
The obtained polymers containing phenylamino methylsilyl, carboxyl groups were

converted by interaction with diglycidyl esters to copolymers with regular distribution of
carbon atoms in the network. The physicomechanical properties of copolymers of the following chemical composition were studied:
1
CH3
C
CH2OC(CH2)4COCH2CHCH2O
O
OH
OCH2CHCH2OC(CH2)4CO
OH
C
CH3
CH2
O
CH3 CH3
CH2OC(CH2)4C NCH2SiOSiCH2NCH2CHCH2OROCH2CHCH2C(CH2)4COCH2
O
CH3 CH3
OH
OH
Copolymer 3 is a product obtained by condensation of pentaerythrite with adipic acid

and diglycidyl ester of diphenylol propane at a simultaneous charging of the components
and was distinguished by the irregularity of the structure.
To elucidate the effect of the composition and structure of molecules of copolymers
on the properties of coating, the kinetics of increment of internal stresses and other
380
13
b, MN/m2
10
8
6
4
2
3
4
6
12
18
24
48 72
, h
Figure 11.8 Kinetics of internal stresses in the formation of coatings from ED-20 (1) with polyethylene polyamine, copolymer 1 (3), 2 (4) and 3 (2) at 160C.
E, GPa
0.6
2.4
Hardness
0.4
0.5
1.6
0.3
0.2
0.8
0.1
0
5
10
15
20
25
30 Time, h
Figure 11.9 Kinetics of change of the elasticity modulus (1 3) and hardness (4 6) in the formation of coatings at 160C from copolymer 1 (2, 4), 2 (1, 5) and 3 (3, 6).
parameters (Figs. 11.8 and 11.9). From these data, it follows that the ordering of the structure of molecules contributes to a 23-fold decrease of internal stresses as the result of relaxation processes during the structuring of the system. Coatings from regular-structure
copolymers are also distinguished by the stability of the properties. They feature a minor
relaxation of stresses in storage of specimens under room conditions (Table 11.13).
From the data on the change of the elasticity modulus in the formation of coatings from
the same copolymers, it follows that the elasticity modulus reaches a constant ultimate
value in 1015 h.
Table 11.13 Effect of the composition of hardeners on the physicomechanical properties of
coatings.
Hardener
Glycerol trisuccinate
Glycerol triadipinate
Glycerol trisebacinate
T, C
, %
E, GPa
P, MPa
A, MPa
120
120
120
6.0
1.5
2.5
0.9
0.4
1.2
15
5
35
13
10
15
CHAPTER 11
381
Coatings from copolymer 2 harden the most rapidly at 160C. The character of the dependence of internal stresses on film thickness for copolymers of different chemical composition is linear.
Coatings from regular-structure copolymers, along with small internal stresses, are
distinguished by a high adhesion strength. From the comparison of the properties of coatings produced from different copolymers and resin ED-20, it follows that internal stresses
in coatings from compositions 1 and 2 are 410 times smaller than in coatings from epoxy
resin hardened by polyethylene polyamine. Herewith, epoxy coatings break down at a comparatively small thickness of about 400 m, whereas for films based on copolymers this
value of internal stresses is achieved at a thickness of 2500 m. This is indicative of a much
greater margin of their strength.
11.6 Biodeterioration of container/packaging materials

The storability of protective coatings depends on the efficiency of measures on protection
of constructions from corrosion, ageing and biodeterioration. It is known that most processes of metal corrosion and polymer ageing are associated with the impact of microorganisms.
According to the data by foreign investigators, damage from direct biodeterioration exceeds
3% of the volume of industrial products. More than 50% of all corrosion processes are related to the action of microorganisms. According to expert estimates, the cost of damage at
present exceeds 40 billion dollars.
In this connection, protection of lacquer-and-paint materials and coatings from premature degradation as the result of microbial and fungal action is an important economic problem.
Such materials as polymers, lacquer-and-paint materials and coatings, cements, concretes, metals etc. find wide use at agroindustrial complex enterprises. Practically all of
them are subject to biodeterioration caused by bacteria and microscopic fungi. The most
aggressive biodegraders of agroindustrial materials are molds.
Molds are widespread in all over the world. They are present in soil, water and air.
Most molds possess the propagation energy. Owing to their microscopic size, spores can
penetrate into invisible cracks and pores in the material. Spores of molds are capable of adsorption on the smooth surface. At the initial stages, they can use components of various
pollutants (dust, residues of fats, oils, greases etc.) available on the surface of materials as
sources of nutrition. Then, in the absence of elements of nutrition, the enzymic apparatus
of the mold rearranges to enable it to use new substrates as sources of nutrition.
Development of molds requires organic carbon and nitrogen, as well as mineral substances (biogenic elements P, Md, Ca, S, Fe and others), though their requirement is so
small that even particles available in the dust are sufficient. Many sources of carbon can be
assimilated by molds. Practically any carbon-containing compound (including those that
are poisonous for some molds) can be a source of nutrition.
The optimal temperature for the propagation of all species of molds is within the range
of 24 to 30C; molds in the vegetative stage die at a temperature higher than 80C and lower
than 10C.
The mold growth rate depends on the water absorption ability of a coating and the
moisture of the ambient air. Water is the main constituent part of the cell body of molds.
Nutrients arrive to the cell in a dissolved form, so for the mold to normally develop the environment should contain a large percentage of water. Fouling of the most diverse materials
by molds is due to the excess of moisture and high air temperature in the environment. An
382
optimal medium for the development of molds has pH 48. Strongly acidic and strongly
alkaline media are fatal for the bacteria.
Mold formation in a material is also affected by air flows and aeration. If materials are
moist, the air flow dries them and inhibits or stops the growth and development of molds.
Molds are typical agents of oxidative fermentation. It can occur only in the case when
microorganisms have special enzymes reductases promoting the incomplete degradation of hydrocarbons in the presence of oxygen of the air. As intermediate products of this
biochemical process, organic acids are formed (gluconic, fumaric, tartaric, malic, oxalic,
succinic and citric), which cause corrosion of metals and organic materials, erosion, reduction of weight, change of coloration, loss of strength etc.
Biochemical reactions caused by molds together with bacteria can be divided into two
groups:
1) anabolic (energy-consuming) processes, which lead to the formation of living matter and cell material and to the assimilation of nutrition;
2) catabolic (splitting) processes, which proceed with the evolution of energy.
In anabolic processes, molds (bacteria) make use of the components of material; namely these biochemical processes contribute to deterioration (microbial corrosion).
Catabolic processes form aggressive metabolites, whose action is called the secondary
corrosive process.
One of the most widespread materials used by various enterprises are lacquerand-paint materials and coatings. Lacquer-and-paint materials and lacquer-and-paint coatings used under conditions favourable for the growth and development of molds and bacteria (high temperature and air moisture) can be subject to microbial deterioration. Its
characteristic features are gray-green, brown and other colour spots and blooms of molds
and bacterial mucus on painted surfaces in places with increased humidity; cracking, exfoliation and delamination of coatings; formation of lumps and holes and other kinds of deterioration.
Biodeterioration of lacquer-and-paint coatings is usually combined with the damaging
action of other external factors atmospheric moisture with dissolved chemical substances,
sun light, elevated temperatures, etc., causing the ageing of materials. Processes of ageing
and biodeterioration can occur simultaneously or not coincide in time, but in most cases
they are complementary to one another, accelerating and aggravating the degradation of
materials and deteriorating their performance and decorative properties.
The main agents of microbial deterioration of lacquer-and-paint coatings are molds.
Bacterial damage is more rare and manifests itself in the form of colourless or coloured mucous deposition. Microorganisms, deteriorating lacquer-and-paint coatings, are often represented by fungi of the genera Aspergillus, Penicillium, Fusarium, Trichoderma,
Alternaria, Cephalosporium, Pullularia; bacteria of the genera Pseudomonas and Flavobacterium. The species composition of the molds deteriorating lacquer-and-paint coatings is specific for each particular soil and climate zone. It is made up by the species, which
make the community characteristic of soils of this or that zone.
Molds develop on lacquer-and-paint coatings by either consuming the components of
coatings or substances polluting the surface of lacquer-and-paint coatings. Deterioration of
lacquer-and-paint coatings occurs as the result of the mechanical impact of mold mycelium
on the coating and under the action of metabolites excreted by micromycetes in their vital
activities (organic acids, amino acids, enzymes etc.). The latter were also found to cause a
decrease of the physicomechanical characteristics in lacquer-and-paint coatings, such as the
elasticity modulus, tensile strain and relative breaking elongation.
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383
Biodeterioration of lacquer-and-paint coatings occurs more often under conditions of

moist tropical and subtropical climate, as well as in constructions and premises with increased humidity and temperature (enterprises of meat-and-dairy industry and canning industry, live-stock farms, pools, baths, etc.) Here they can inflict the greatest amount of
damage. However, even under conditions of a moderate climate, especially when the operating rules are violated, microbial decay can inflict a considerable amount of damage. In
regions with dry climate, such kind of deterioration is very rare.
One should distinguish between deterioration of lacquer-and-paint materials (especially of water-emulsion paints) by microorganisms at the stage of production (storage) and
biodeterioration of hardened lacquer-and-paint protective and decorative coatings applied
to supports. In the former case, microorganisms get into semifinished lacquers and paints
in the process of their production (with raw materials, water from the air of production premises, etc.); in the latter, spores of molds and bacteria precipitate on the surface of fabricated coatings from the environment, which is largely contributed to by various pollutions.
Characteristic features of biodeterioration of some water-soluble emulsion paints can
be the change of colour, gas formation (bulging of containers), appearance of foreign smell,
liquefaction and finally gelation.
Biostability of ready-prepared lacquer-and-paint coatings largely depends on their
composition, chemical nature of the polymer bonding adhesive and pigments. Biostability
is also affected by other components of lacquers and paints (solvents, thinners, stabilizers,
hardeners etc.), as well as by material to which the coating is applied, by the support. Thus,
coatings on wood are preserved better than on metal or silicate construction materials. On
ferrous metals, they are often less biostable than on nonferrous metals.
Biostability of lacquer-and-paint coatings also depends on the hydrophobicity of the
coating and the distribution of moisture condensate on the surface of material. The higher
the hydrophobicity of the coating, the greater its mold resistance is.
One should distinguish between the mold resistance of lacquer-and-paint materials and
that of lacquer-and-paint coatings. Cases are known when a lacquer-and-paint material resistant to the action of micromycetes was deteriorated by molds in the system of lacquer-and-paint coatings; and the other way round, a mold-nonresistant lacquer-and-paint
material exhibited biostable properties. This is, probably, due to the fact that the mold resistance of the system of lacquer-and-paint coatings depends on the composition of all its
components the support, the primer, the coating. Therefore, to be able to give recommendations on the performance of lacquer-and-paint coatings from the point of view of their
mold resistance, it is necessary to study the biostability of not only individual components
of the system of lacquer-and-paint coatings, but of all the system as the whole.
The peculiar features of mold corrosion of lacquer-and-paint coatings on metals was
studied. As supports, use was made of aluminium alloys D16, AMg, AMts and A1-9 covered with primers EF-0137, VL-02 and AK-070. The supports were coated with enamel:
ML-12 (grey), ML-165 (silver), KhV-518, PF-115 (black), EF-1118M, FP-5246, PF-178.
As the result of the studies, it was found that systems of lacquer-and-paint coatings, where
the supports were alloys D16 and AMts, were more subject to damage by molds irrespective
of the variant of the experiment. An exception was the specimen of AMts with enamel
PF-178, on which the growth of molds did not exceed 1 point. The least damaged were specimens of the alloy A1-9 at the application of primer EF-0137. The authors of that work note
that the difference in the mold fouling of metal specimens coated with lacquer-and-paint
coatings is rather difficult to explain, because the molds are not in direct contact with metal
and are on the surface of the protective coating. However, there are data on the high
384
vulnerability of aluminium alloys D16.

Studies of micromycete deterioration of lacquer-and-paint coatings on metals found
that enamels applied to aluminium and titanium alloys were affected by micromycetes to
various degrees. Such systems of lacquer-and-paint coatings as A1-9 + primer EF-0137 +
enamel ML-12 (grey), T-5 (titanium alloy) + primer VL-02 + enamel EF-1 I 8 and VT-10
+ primer VL-02 + enamel EF-1118 exhibited the highest resistance to molds.
Film-forming substances mainly determine the biostability of lacquer-and-paint materials and protective coatings on their basis. A crucial factor here is, on the one hand, the
chemical structure of a polymer film former and, on the other, its physical properties both
in nonhardened and hardened state (swelling capacity, moisture-holding capacity, hardness,
smoothness of the surface, porosity etc.).
A relationship between the chemical structure of film formers used and the growth rate
of a number of widespread strains of molds was established.
Out of the number of investigated film-forming substances, synthetic film-forming
polymers (thermoplastic and thermosetting) possess the best biostability. The mold biostability of these coatings decreases in the following sequence: epoxy, polyurethane,
melamine alkyd, organosilicon, pentaerythritol-modified phthalic. An increased rate of
hardening of the film-forming substance, decrease of the water absorption ability, roughness and porosity of the film contribute to the increase of mold resistance. Smooth glossy
uniform films are more stable because they are less contaminated, and spores of molds adsorb on them less.
Among natural film formers, the most widespread are drying oils oils of plant origin
(flax, cotton, hemp-seed, sunflower, tallow etc.). All of them possess a relatively low mold
resistance, because they are a good nutritive substrate for microorganisms. Considering the
relation between the drying rate and the mold resistance, the quick-drying Chinese wood
oil, which contains glycerides of fatty acids with several conjugated double bonds, is attributed to the best oils. Slowly drying oils, such as flax, soybean, cotton-seed etc., which represent glycerides of fatty acids with double nonconjugated bonds, are considered to be less
biostable.
Organic impurities decrease the biostability of oils; for this reason, oils used in fabrication of lacquer-and-paint materials are refined. The characteristic consequences of the deterioration of vegetable oils by molds are a significant decrease of their viscosity, an
increase of acidity and, as the result, a worsening of the polarization capability, i.e., the rate
of forming the film and its protective properties.
Of natural resins used as film formers in lacquer-and-paint materials, shellack varnish,
wood rosin and copal possess an increased resistance to microbial deterioration. The resistance of wood rosin to the action of micromycetes is associated with the presence of terpenes, which possess fungicidal properties, as well as with the formation of acidic products
in the film during the production of the protective coating.
Bitumens used as film formers have insufficient biostability. To increase the biostability, the composition of bitumen lacquers and bitumen protective coatings is supplemented by phenolic, maleic and other synthetic resins.
Thermoplastic synthetic resins used for production of quick-drying lacquers form solid
coatings, as a rule, with high biostability. Biostable resins include indene and cumarone resins, chlorinated rubber, polystyrene and its copolymers with butadiene, copolymer of vinyl
chloride with vinyl acetate etc.
A widespread polymer bonding adhesive is the polyvinyl acetate dispersion. Paints,
coatings, mastics, primers and other materials on its base are mold-nonresistant.
CHAPTER 11
385
Noplasticized dispersions are affected by molds stronger than plasticized ones. Not only
coatings from polyvinyl acetate paints are mold-nonresistant, but also the liquid paints
themselves, which in the process of storage are affected by molds and bacteria. Herewith,
their viscosity decreases, gaseous products are formed, etc.
Thermosetting synthetic resins (glyptal, pentaerythritol-modified phthalic, epoxy, silicon, urea-formaldehyde etc.) used in hot- and cold-hardened lacquers and enamels possess
a high biostability; what is more, some of them even exhibit fungicidal properties. Coatings
from them are distinguished with a high hardness, smoothness and low permeability, which
contributes to the increase of biostability.
Water-soluble film-forming substances (represented by cellulose derivatives and protein compounds: dextrin, gum, gelatin, albumin, casein, etc.) are deteriorated by molds.
Their decreased biostability is associated with inherent hygroscopicity and capability of
swelling. Under humid conditions, microscopic fungi often deteriorate casein, dextrin and
other water-emulsion glue colours.
In contrast with organic water-soluble film formers, inorganic film formers possess a
high biostability. An example of such film formers is liquid glass used in production of silicate paints.
Another important component, which determines the biostability of lacquer-and-paint
coatings, is pigment. Pigments confer the required colour and covering capacity to the paint,
regulate viscosity, improve the resistance to solar radiation and water resistance of the coating. Owing to the increased hardness, pigment particles mechanically hinder the growth and
development of mycelium. They can also have a toxic effect on molds and other microorganisms.
Zinc oxide, copper oxide, barium metaborate and some other pigments possess fungicidal properties and, therefore, increase the biostability of lacquer-and-paint coatings. At
the same time, such pigments as chalk, chrome yellow, titanium dioxide, aluminium powder, chromium oxide, carbon black do not possess biocidal properties by themselves; however, oil paints on their base possess an increased fungal resistance. Oil paints with
pigments of antimony and lead oxides, lithopone (a mixture of ZnS and BaSO4 in the form
of fine powder) are distinguished by a lower mold resistance. Titanium dioxide and lead
titanate, introduced into lacquer-and-paint materials, produce coatings yielding to deterioration by molds. Zinc oxide mixed with lead oxide communicate a better biostability to a
protective film of lacquer-and-paint coatings than zinc oxide mixed with lead carbonate.
A number of inorganic pigments and fillers, for instance, talcum, graphite, muscovite
mica reduce the resistance of lacquer-and-paint coatings to microbial deterioration.
One of the factors causing the corrosion of metals and alloys in the atmosphere, in contact with water and soil is microbial action. Biodeterioration of metals and metal constructions is commonly called biocorrosion.
It was found that during the growth on materials directly contacting with metals (tissue, lacquer-and-paint materials, fuel), microscopic fungi can enhance the corrosion of metal constructions. The action of microorganisms on metals can be different. First of all,
corrosion of metals can be caused by aggressive microbial exometabolites mineral and
organic acids and bases, enzymes etc. They create a corrosion-active medium, in which, in
the presence of water, corrosion proceeds according to the usual laws of electrochemistry.
Colonies of microorganisms can create overgrowths and films of mycelium or mucus,
under which corrosion pits can develop as the result of the electrical potential difference at
various regions of the metal surface and assimilation of metal ions by microorganisms
themselves.
386
Metal corrosion caused by bacteria can proceed under aerobic and anaerobic condutions.
Active aerobic corrosion agents are iron bacteria, thionic bacteria, nitrifying bacteria
and some others, which form corrosion metabolites.
Under anaerobic conditions, metal corrosion is accelerated in the presence of dinitrifying and especially sulfate-reducing bacteria. The basis of microbial action on metals is an
electrochemical process.
It was found that the mechanism of the corrosion process of iron, which involves
sulfate-reducing bacteria, is related to cathodic depolarization. In the process of metabolism, sulfate-reducing bacteria consume hydrogen atoms formed on the surface of corroding
metal and, thus, perform cathodic depolarization in the absence of oxygen.
The mechanism of anaerobic corrosion involving sulfate-reducing bacteria can be presented in the form of the following reactions:
Anode reaction
4Fe
8H2O
4Fe2+ + 8e;
8H+ + 8OH;
Cathode reaction
8H + + 8e
8H.
Cathode depolarization involves the participation of bacteria:

SO42 + 8H
S2 + 4H2O.
Corrosion products
Fe2+ + S2
FeS;
3Fe(OH)2.
3Fe2+ + 6OH
The general reaction:

4Fe + SO42 + 4H2O
FeS + 3Fe(OH)2 + 2OH
The action of fungi on metals often leads to the deterioration of electrical and physicomechanical parameters of articles, in which these metals are used. A decrease of strength
in various grades of steel, aluminium, titanium and copper alloys is observed at the action
of fungi on them.
Efficient biocides, their peculiar features and the mechanism of their action in polymer
coatings of various chemical composition were reviewed.
Among the basic methods of protecting materials from biodeterioration by microorganisms, the following can be singled out:
1. Mechanical elimination of pollution.
2. Maintenance of the correct sanitary-hygienic and temperature-moisture regime
(20 > t C > 60; humidity no less than 80%, aeration).
3. Physical methods (bacterial filters, electromagnetic and radioactive irradiation, UV,
ultrasound, electrochemical protection, etc.).
4. Hydrophobization of the surface.
5. Prevention of the penetration of microorganisms to the object of biodeterioration
(sealing, air purification, vacuum, biocide gas medium).
CHAPTER 11
387
6. Removal of one of the elements required for microbial growth (use of chelate compounds of iron and magnesium, binding one of the metals required for microbial growth).
7. Biological protection (antagonism, competition of microorganisms, negative
homeostasis of fungi and bacteria).
8. Development of materials with preset properties by their biostability (for one or
several components of material to possess biocide properties).
9. Chemical means of protection (biocides). The use of biocide compounds is one of
the most efficient and widespread methods of protection.
Biocides used for eradication of microorganisms should not worsen the performance
properties and toxicological safety of coatings.
11.7 Effect of the polymerization initiation method on the formation and

Along with chemical initiation of polymerization, a great effect on the formation and properties of coatings is rendered by the method of power supply in hardening of the systems.
The most widely used methods for this purpose are convection heating, radiant heating and
ultraviolet radiation.
Effects of various ways of power supply on the formation and properties of polyester
coatings were studied to choose optimal conditions of hardening. Convection heating was
carried out using two regimes, usually used in the industry: at 60C for 8 h and stepwise
40 min at 60C and 40 min at 80C. Radiant-heat infrared drying of polyester coating
applied to glass supports was done under ZS lamps (power 500 Wt). The averaged results
of the studies are given in Table 11.14.
Table 11.14 Dependence of internal stresses on the method of hardening of coatings
from lacquer PE-220.
Hardening technique
Convection
Stepwise convection
Radiant heating

1.3
2.0
3.0
The largest internal stresses emerge in hardening of coatings by infrared beams. The
simultaneous impact of heat and infrared radiation accelerates the polymerization process
and contributes to the nonuniform hardening of coatings, probably, due to the low permeability of infrared radiation.
With the thickness of coatings increased, the influence of the method of power supply
on the value of internal stresses decreases (Fig. 11.10).
The observed regularities in the change of internal stresses depending on the method
of hardening do not depend on the nature of the support and were also observed for polyester
coatings formed on various kinds of wood. In the formation of coatings on wood, radiant
heat was carried out stepwise: first at a heating-surface temperature of 100C and the distance of 100 mm from the heater; heating time, 30 min. At the second stage, the heating
was performed at a heating-surface temperature of 180C for 5 min at the same distance
from the heater. In all methods of hardening, the coatings were formed to the same hardness.
The breaking strength of films was determined at the loading rate of 14 mm/min. With
consideration of these data, a conditional reserve of the cohesion strength was calculated,
388
b, MN/m2
7
1
2
3
6
5
4
4
3
2
1
12
15
, h
Figure 11.10 Kinetics of internal stresses in hardening of polyester coatings by infrared illumination (1, 3) and by the convective method (2, 4) at a film thickness of 200 m (1, 2) and 100 m (3, 4).
and the accelerated test of the durability of coatings hardened by various methods was carried out.
The reserve of strength determined in this way is a conditional characteristic and
makes it possible to obtain relative data on the efficiency of using this or that method of
hardening, as the value of strength depends on the loading rate.
Accelerated tests for durability consisted in alternation of low temperature 40C for
1 h and 60C also for 1 h in repeating cycles (Table 11.15). Coatings with the highest internal stresses were the least durable. Based on these data, the convection method of drying
Table 11.15 Dependence of internal stresses (b), breaking strength (p) and longevity () of
coatings, formed on nuts, on the hardening method.
Hardening technique
p, MPa
b, MPa
Strength margin
Longevity, cycles
Convection
Stepwise convection
Convection at increased moisture
content (50 min at 90C)
Radiant heating
13.3
11.2
16.6
1.8
3.0
2.6
7
4
8
14
2
10
10.3
11.0
can be recommended. The most efficient method is hardening under the action of ultraviolet
radiation. The specific feature of this radiation is that it easily penetrates through the lacquer
coatings and causes their uniform hardening in the bulk. PRK-2 lamps were used as a source
of radiation. In this method of formation, hardening of coatings from various polyester lacquers occurs in 1015 min at a small value of internal stresses, by an order of magnitude
smaller than in the convection method. This method is especially efficient in the formation
of coatings from cold-hardened lacquers characterized by a relatively low adhesion.
CHAPTER 11
CO,%
100
389
3
60
20
10
30
50
, h
Figure 11.11 Change of the number of CO groups of the polyester in ultraviolet radiation of nonfilled coatings (1); filled with aerosil (2); with aerosil modified with 2% (3), 10% (4) and 39% (5)
octadecyl amine (ODA).
Hardening under the action of ultraviolet radiation is observed to improve the adhesion
and physicomechanical properties of coatings.
Using the method of IR spectroscopy, it was found that in this method of formation
the time of utilizing double bonds of unsaturated polyester and styrene is reduced to 1015
min. The cause of this phenomenon was determined by an additional initiation of polymerization under the action of ultraviolet radiation as the result of the increase of the number
of free radicals. Polyester coatings are characterized by a high degree of permeability for
ultraviolet radiation, up to 8 mm.
The mechanism of formation of polyester coatings under the action of ultraviolet radiation in the presence of photostabilizer was studied. Octadecyl amine (ODA) was used as
a photostabilizer; its NH groups interact with hydroxyl groups of the surface and under definite conditions can enter into interaction with CO groups of the polyester.
The rate of formation and decomposition was assessed by the change of the intensity
of the absorption band of polyesters CO groups in the process of irradiation and the change
of internal stresses, which were determined by the photoelastic method.
Studies of the structural transformations in ultraviolet irradiation of coatings filled
with aerosil showed that in filled systems particles of aerosil are sites of forming more ordered secondary supramolecular structures, which emerge as the result of the interaction of
polyesters CO groups with OH groups of the surface of the filler to form hydrogen bonds.
In the presence of the filler, the structure of polyester coatings is more resistant to the action
of ultraviolet radiation.
In modification of the fillers surface by 2% ODA, the rate of decomposition sharply
increases as the result of interaction at the polymerfiller interface (Fig. 11.11).
In the complete substitution of NH groups of the modifier for OH groups of the surface
of aerosil as the result of adsorption of ODA by the surface of the filler in the amount greater
than the monomolecular layer, part of the modifier at the treatment of specimens with a solution of polyester resin, probably, leaves the surface of the filler and can interact with polyester to form a hydrogen bond between NH groups of the modifier and CO groups of the
resin. This is indicated by a sharp increase of the arm on the side of the low frequencies at
the absorption band of CO groups, observed earlier for systems containing aerosil modified
by 10% ODA.
390
Introduction of excess modifier with respect to OH groups of the surface of aerosil

leads to the further, even sharper, decrease of the rate of decomposition under the action of
ultraviolet radiation.
The effect of ODA on the molecular processes in ultraviolet radiation of nonfilled
coatings was studied to elucidate the role of ODA in structural transformations during the
formation and ageing of polyester coatings. Table 11.16 presents the data on the change of
the number of CO groups in polyester coatings containing 110% ODA at various stages
of ultraviolet radiation. With the irradiation time increasing, the intensity and halfwidth of
the absorption band of valent vibrations of polyesters carbonyl groups change. A decrease
of intensity of the absorption band of CO groups in the process of ultraviolet radiation indicates complex oxidative conversions in coatings, probably due to, as in the case of thermal
decomposition, the formation of volatile oxidation products evolving in the bulk.
Table 11.16 Change of optical density of the absorption band of polyester CO group depending on
the radiation time and concentration of ODA.
Content of ODA in
polyester, %
1
2
3
Radiation time, h
0
1.382
1.329
1.054
0.558
6.5
0.419
13
1.151
0.088
0.403
26
0.570
0.396
31
0.477
0.028
0.277
46
0.316
0.083
The rate of these processes and the change of the number of interacting functional
groups were assessed as the ratio of the differences of optical densities in the maximum of
the initial absorption band and the absorption band after irradiation to the initial optical density. Data on the change in the amount of carbonyl groups in the process of ultraviolet radiation of the polyester coating are presented. In the first 5 h of irradiation more than 50%
of all CO groups of the polyester are degraded. Further on, the rate of the process sharply
slows down, and it is totally completed in 100 h of irradiation. At the introduction of 1%
ODA into polyester coatings, the rate of oxidative processes in ultraviolet radiation sharply
slows down and makes only 10% in 10 h of decomposition.
At a further irradiation, the rate of decomposition increases, remaining much lower
than the rate of oxidative processes in nonmodified polyester coatings.
With the content of the modifier increased up to 2%, the rate of decomposition of polyester molecules increases as compared with nonmodified coatings; in 10 h of irradiation, it
is 90%. At a significant content of the modifier in the system, the transparency of specimens
decreases, and the rate of decomposition of polyesters CO groups slows down insignificantly as compared with coatings from nonmodified oligoester. This character of change of
the decomposition rate is associated with the fact that particles of ODA at an optimal content of modifier under the action of ultraviolet radiation interact with polyester to form a
hydrogen bond between CO groups of the resin and NH groups of the modifier. This is indicated by a sharp increase of the halfwidth of the absorption band of the carbonyl groups
in the process of ultraviolet radiation of coatings as compared with an increment of the halfwidth of the absorption band of the same groups in the absence of ODA. At a further increase of the content of ODA, the absorption halfwidth of polyesters CO groups slightly
decreases, which is, probably, due to the restricted amount of NH groups of the modifier,
the same way as with OH groups of aerosil. Therefore, the further increase of the content
391
CHAPTER 11
of ODA contributes to the aggregation of modifiers particles and a worsening of its interaction with the polyester.
The greatest increase of the halfwidth of the absorption band of CO groups in the presence of 1% ODA is observed in the induction period. A slight decrease of the rate of decomposition at a large content of ODA in the system (in the amount of 10%) is, probably,
due to a decrease of the transparency of coatings with respect to ultraviolet radiation.
The interaction of the polyester with the modifier added in an optimal amount contributes to an increase of the durability of coatings under conditions of ultraviolet radiation.
Along with the intensity of the absorption bands of carbonyl groups in the process of ultraviolet radiation of polyester, one also observes a change in the intensity of the absorption
bands of ethers and esters. The rate of conversion of these groups is much greater than of
CO groups and depends on the content of ODA in the system (Table 11.17). These groups
Table 11.17 Change of optical density of the absorption bands of ester groups depending on the
radiation time and concentration of ODA.
Content of ODA
in polyester, %
Irradiation time, h
0
6.5
13
21
26
Ether bond 1140 cm

0
1
2
10
0.328
0.502
0.466
0.462
0.202
0.100
0.149
0.070
0.224
0.060
0.130
0.055
0.170
0.054
0.114
0.130
0.048
Ester bond 1300 cm

0
1
2
10
0.415
1.048
0.852
0.852
0.403
0.156
0.255
0.122
0.434
0.090
0.209
0.092
0.355
0.065
0.193
0.269
0.066
0.109
0.045
0.0057
are, apparently, involved in the formation of hydroperoxides, which are degraded in the process of irradiation. We failed to record the emergence of hydroperoxides by the method of
IR spectroscopy, probably, due to the high rate of their degradation.
Figure 11.12 presents the data on the kinetics of change of internal stresses in polyester
coatings. In the presence of ODA, the rate of increment of internal stresses is greater than
in nonmodified coatings, both in thermal hardening and in ultraviolet radiation, which is
indicative of faster polymerization processes. Herewith, the value of internal stresses in
hardening under the action of ultraviolet radiation is 1.52 times smaller than in thermal
hardening (Fig. 11.12). The formation process under the action of ultraviolet radiation proceeds much faster and is practically complete in 3060 min after the onset of irradiation,
whereas in coatings hardened at 80C it is complete in 4 h. In irradiation for more than 20
h, internal stresses are increased but to a significantly lower degree than in coatings obtained in thermal hardening.
It is seen from the data adduced that a sharp increment of internal stresses at a content
of 2% ODA in the system, as well as of the halfwidth of absorption of carbonyl groups and
the rate of their conversion, are observed only at the action of ultraviolet radiation and are
not found in thermal hardening of the coatings.
392
a
b, MN/m2
4
3
1
3
2
1
4
8
b, MN/m2
50
100
200
600 , h
2
3
1
1
4
40
80 , h
Figure 11.12 Kinetics of internal stresses in polyester coatings non-modified (1) and modified with
1% (2), 2% (3) and 10% (4) ODA: a, hardening at 80C in the presence of an initiator and an accelerator followed by UV irradiation; b, without catalysts under the action of UV irradiation.
The second feature of the processes proceeding in polyester coatings in the presence
of a modifier is that they are exhibited most efficiently at a strictly definite content of the
modifier in the system (in the amount of 2%) irrespective of the method of its introduction
(whether the modifier is introduced directly into the solution of polyester or together with
the filler). This is, probably, due to the fact that formation of coatings, the same way as their
ageing, is the most efficient at a certain content of hydroperoxide in the system, which in
the given case is regulated by the content of ODA in the polyester. At its direct introduction
into the polyester, the rate of increment and relaxation of internal stresses in the process of
ultraviolet radiation is much greater than in coatings filled with aerosil codified by ODA.
An increase of the rate of chemical conversions in modified nonfilled coatings as compared
with filled ones is, probably, due to the more uniform oxidative processes along the thickness of filled coatings as the result of their greater permeability for ultraviolet radiation, because in more thin films used for recording IR spectra of filled and nonfilled systems these
differences in the rate of oxidative processes are less essential.
From the adduced data, it follows that ODA is a regulator of the rate of hydroperoxide
formation in the system under the action of ultraviolet radiation; at a definite content in the
system, it can on the one hand harden polyester coatings without introducing usually
used initiators and accelerators of polymerization and on the other hand sharply decrease the rate of ageing of polyesters as the result of the interaction of NH groups of the
modifier and CO groups of the polyester to form a hydrogen bond.
From the data on the structure of polyester coatings hardened as the result of initiation
of polymerization by various methods, it is seen that the most ordered homogeneous structure is obtained at the initiation of polymerization by ultraviolet radiation.
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393
Taking into account these regularities, methods of modifying epoxy resins by acrylic
monomers were proposed, which also make it possible to produce rapidly hardened coatings with ordered structure providing for a sharp reduction of internal stresses and high performance properties. The statement of this problem is due to the fact that epoxy resins are
widely used in industry for production of coatings, glueing layers of sealants, bonding adhesives in production of materials and articles for various purposes owing to high adhesion
and physicomechanical characteristics.
However, coatings produced based on epoxy oligomers also have a number of essential drawbacks. The process of hardening of epoxides is comparatively slow and even at
high temperatures is completed in several hours. The high adhesion of epoxides to the surface of solid bodies is accompanied by a sharp inhibition of the relaxation processes in the
formation of coatings and the emergence of significant internal stresses, in some cases commensurable with the value of adhesion.
A decrease of internal stresses in the formation of epoxy coatings by introducing plasticizers and regulating the temperature regime of hardening leads to the simultaneous worsening of adhesion and strength properties of coatings.
A characteristic feature of epoxides is also that they form coatings with a globular
structure inhomogeneous along the thickness and area of the film and significantly dependent on the nature of the support.
With consideration for this, of great practical importance is the development of methods of modifying epoxides and the physicochemical routes of their hardening providing for
the formation of a homogeneous structure and a decrease of internal stresses in coatings.
Modification of epoxy resin ED-16 was carried out by etherification of methacrylic acid in
the medium of butyl methacrylate and methyl methacrylate taken at a ratio of 1:1 and making 50% of the weight of etherifying components. Dimethylalanine was used as a catalyst.
The results of the kinetic studies indicate that the etherification of epoxy resin under these
conditions is a second order reaction. Hardening of coatings was carried out by the method
of photopolymerization under the action of ultraviolet radiation.
The coating formation process was studied by the yield of the gel fraction using the
method of IR spectroscopy by the change of intensity of the characteristic band of vibrations
of the group CH2=C in the region of 16001640 cm 1, as well as by studying the kinetics
of increment and relaxation of internal stresses and by the change of the physicomechanical
properties. The change of the properties in photopolymerization was compared with the
character of structural transformations at various stages of hardening of the coatings, which
were investigated by the method of electron microscopy using oxygen etching of specimens.
The adduced data on the dependence of the yield of the gel fraction on irradiation time
for an epoxyacrylic composition with 60 and 75% etherification indicate that the character
of the curves is identical, and the major part of chemical bonds involved in the formation
of the three-dimensional network emerge after 1 min of irradiation. The polymerization process is totally completed in 3 min of irradiation, after which decomposition of the polymer
begins. The yield of the gel fraction in films from epoxyacrylic oligomers is 9798.5%.
The extent of etherification of epoxy esters has an insignificant effect on the rate of
polymerization and the yield of the gel fraction. This conclusion is also supported by the
data on the studies of the coating formation kinetics by the method of IR spectroscopy.
Data on the kinetics of photopolymerization of epoxy acrylic oligomers in the production of coatings of various thicknesses were presented. It is seen that at a thickness of 10
m the formation of coatings studied by the change of intensity of the absorption bands of
394
1
2
1.0
Adhesion, MPa
Internal stresses, MPa, MPa
2.0
4.0
2.0
4
3.0
5
1.0
2.0
Impact strength, Nm
5.0
1.0
0
0
1
2
3
Irradiation time, min
Figure 11.13 Dependence of adhesion strength (1, 2), impact strength (3, 4), internal stresses (5, 6)
for epoxy coatings with the etherification degree of 60% (1, 3, 5) and 75% (2, 4, 6).
the double bonds in the region of 16401660 cm 1 is completed in 30 s of irradiation. With

the thickness of the film increased up to 40 m, the formation of the three-dimensional network is completed in 2 min.
Figure 11.13 presents the data on the kinetics of change of the physicomechanical parameters in photopolymerization of epoxyacrylic oligomers. It follows from the figure that
most parameters for all systems reach a maximum in 3 min of irradiation.
Comparison of the regularities of change of the physicomechanical characteristics
with the kinetics of polymerization indicates the absence of correlation between the rate of
polymerization and the rate of formation of chemical bonds in the formation of the threedimensional network responsible for the mechanical properties of coatings. The absence of
such a correlation was also observed in studies of the mechanism of formation of the threedimensional network in thermal hardening of coatings.
It is also noteworthy that, with the extent of etherification of epoxy esters increasing,
the physicomechanical characteristics and the rate of their increment in the process of hardening are decreased.
To understand the mechanism of formation of the three-dimensional network in photopolymerization, the supramolecular structure of coatings at various stages of hardening
was studied. The structure of coatings from epoxyacrylic oligomers at various stages of
their photopolymerization on metal and glass supports was presented. An inhomogeneous
structure was found to emerge in coatings on metal in 2 min of irradiation. Along with globules of about 10 nm in diameter, larger structures of anisodiametric type emerge, and also
separate areas are observed, the structure of which is not revealed. A homogeneous network
structure from densely packed anisodiametric structural elements was observed after irradiation for 3 min. An increase of the photopolymerization time leads to the breakdown of
anisodiametric structures.
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395
The process of structure formation proceeds slower for coatings on a glass support,
which is distinguished by a smaller adhesion to epoxyacrylic oligomers. After 2 min of irradiation, the structure of coatings under these conditions is revealed not clearly; only individual supramolecular formations of about 5 nm in diameter are observed. In irradiation
for 3 min, an inhomogeneous structure from globules of 1520 nm in diameter and their
aggregates are revealed. A further increase of irradiation time causes the structure to decompose.
Under deep-conversion conditions of thermal hardening of coatings at 100C for 2 h,
a globular-type structure of about 3040 nm is formed; herewith, the surface layers of coatings are found to have secondary supramolecular formations, which deteriorate the decorative and protective properties of coatings and are characteristic of coatings from oligomer
systems with the statistical distribution of functional groups, obtained in thermal hardening
of oligomers, in the oligomer block. Formation of this structure is accompanied with a sharp
increment of internal stresses.
From the adduced data, it follows that the process of photopolymerization, the same
way as that of thermal polymerization, is multistage and proceeds via the stage of supramolecular structures formation at the initial stage of hardening. From the analysis of the kinetic data, it follows that at the onset of irradiation the polymerization proceeds within a
small number of molecules and is accompanied with the formation of supramolecular structures. At a further irradiation, in the formation of coatings on supports with high adhesion,
structural elements get oriented and a homogeneous network structure from anisodiametric
structural elements is formed.
A sharp increment of the physicomechanical parameters is observed at the second
stage and corresponds to the formation of chemical bonds between supramolecular structures.
An increase of the extent of reetherification of epoxy esters to higher than the optimal
value (60%) leads to the worsening of intermolecular interaction in the system and to the
formation of an inhomogeneous imperfect structure, consisting of globules and their aggregates, in the process of irradiation. This is indicated by the data for coatings from epoxyacrylic compositions with a 75% reetherification of epoxy ester.
Comparison of the specific features of structural transformations in the formation of
coatings using various physicochemical methods of hardening is indicative of the significant advantages of photopolymerization. Unlike thermal hardening and along with the considerable rate of hardening up to a high extent of conversion, it enables production of
coating with a homogeneous structure and higher physicomechanical characteristics.
11.8 Studies of the possibility of using stabilized radicals in protective

coatings
Works on chemical reactions have since long ago mention free radicals, i.e., molecular fragments with very small lifetime and high reactivity, characterized by the presence of an unpaired electron.
However, due to a high activity of radicals, their concentration in reacting chemical
systems is extremely small, and their lifetime is, as a rule, 10 3 10 10 s. Chemists have
always tried to obtain stable radicals, resistant under usual conditions, which would exist
as individual substances. Organic stable radical paramagnetics of various chemical classes
have been synthesized, including the most known of them diphenyl picryl hydrazyl. Unfortunately, all of them decomposed comparatively rapidly, were poorly soluble and
396
unstable to oxygen; what is more, many of them could be obtained by complex and not easily accessible syntheses. Those radicals found no use in practice.
In 1970s, researchers at the Institute of Chemical Physics, USSR Academy of Sciences
developed a new class of organic paramagnetic substances nitroxyl radicals of the following structure:
X
where X are the substituents of a very diverse structure, for instance,

CH2 CH2 CN
CH2
H, Cl, Br, CN, OH, COOH; NH2; NH3+ ; O
CH2
; N
etc.
CH2 CH2 CN
To date, several hundred of this class of substances have been synthesized; all of them
are paramagnetics in solution, in the gas phase, crystals and in the melt. Nitroxyl radicals
have a simple chemical structure, are stable within a broad temperature range from 270
up to +250C, are resistant to oxygen, alkali and acids, soluble in most liquids and organic
solids (the solubility can be easily regulated by changing the substituent X). The lifetimes
of these radicals under usual conditions are many years and decades.
The first nitroxyl radical was synthesized and isolated by O.L. Lebedev and
S.N. Kazarnovsky. The significance and prospects of the new class of radicals was appraised by M.B. Neiman, who initiated these works at the Institute of Chemical Physics,
USSR Academy of Sciences.
New and simple methods for the synthesis of radicals have been proposed; they were
found to possess a unique property the ability to react without affecting the unpaired electron, i.e., preserving the paramagnetism.
The ability of radicals to preserve the paramagnetic centre enables the synthesis of new
paramagnetic materials polymers, antibiotics and other drugs, in particular, anticancer
preparations. The same ability opened an exceptional possibility of introducing the already
prepared radicals into other molecules, which in this case become radicals and acquire paramagnetic properties. The potential of assembling paramagnetic molecules of any structure
is practically unlimited.
An exceptional contribution to the chemistry of nitroxyl radicals was made by
M.B. Neiman and E.G. Rozantsev; reactions without affecting unpaired electron
(NeimanRozantsev reactions) are broadly used by chemists and biochemists all over the
world. Dozens of NeimanRozantsev reactions have been developed; organometal radicals
containing thallium, mercury, iron and other substances have been synthesized; paramagnetic polymers have been obtained. Individual polyradicals of the type of R and , in which
paramagnetic fragments R are joined by bridges into a united molecular system, have been
developed; the number of unpaired electrons in such systems n = 2, 3, 4 and more.
Along with reactions without affecting the paramagnetic centre, nitroxyl radicals participate in typical radical reactions: at elevated temperatures they break loose atoms of H,
Cl and other elements and attach themselves to multiple bonds; attach many active radicals
CHAPTER 11
397
leading chemical reactions; the latter property of accepting active radicals is of special interest. It is essential that even if chemical reactions affect unpaired electron and are accompanied with the loss of paramagnetism, the paramagnetic centre is easily regenerated and
paramagnetism is restored by simple chemical actions.
The causes of unusual stability of nitroxyl radicals consist in, first, the sharing of unpaired -electron between atoms of N and O and a reduction of its energy level; second, in
a strong spatial screening of the paramagnetic centre by four bulky methyl groups.
The ability of nitroxyl radicals to trap other active particles opened large vistas for using radicals in chemical technology as inhibitors and regulators of the processes of polymerization, oxidation, epoxidation etc.
Nitroxyl radicals and their molecular precursors sterically hindered amines (SHA)
are used as nontarnishing light-protective additives, which protect polymers from degradation and extend the service life of polymer articles (especially films and fibres). By their
quality, new light stabilizers significantly exceed the best Western specimens; processes of
their production have been developed.
Generalizing the works on the use of nitroxyl radicals and SHA as stabilizers of polymer, the following basic directions of research can be singled out:
1. Development of methods for the synthesis of multifunctional stabilizers, which contain in one molecule a fragment of both SHA or nitroxyl radical and a UV adsorber, organic
phosphite, sterically hindered amine, thioester, derivatives of metals, especially nickel, etc.
Introduction of UV adsorber fragments is usually expressed in an enhanced efficiency
of photoprotective action owing to the different synergic mechanism between the UV absorber and antioxidant, and fragments of UV adsorber can quench the excited state of nitroxyl responsible for the photochemical change. Introduction of an additional group of
antioxidant is mainly associated with the necessity to increase the stability of material in
the process of its use.
2. Works to obtain compounds including several sterically hindered amines or nitroxyl
fragments. The mechanism by means of which the efficiency of photostabilizers with two
or more sterically hindered fragments increases has not been established. Empirically, the
efficiency of nitroxyl in the inhibition of thermal oxidation of polypropylene was observed
to increase with the rise of the number of paramagnetic centres in the molecule. The efficiency of thermal stabilizers of biradical type increases when the distance between the paramagnetic centres decreases.
This phenomenon is observed, probably, owing to the reaction of alkyl radical, which
is formed in the interaction of polymer with nitroxyl of another nitroxyl group. This reaction
sterically hinders the initiation of oxidation by nitroxyl radical. There is no satisfactory explanation to the increase of the efficiency of photostabilizer with the rise of the number of
NH groups, because polyradicals are formed in the photooxidation of sterically hindered
amines.
3. Stabilizers of high compatibility with polymers were synthesized; several fragments
were introduced into the stabilizer, for instance, alkyl substituents provide for a high efficiency of photostabilizers for polyolefins. Some characteristics of the structure of stabilizers, apparently, contribute to their accumulation in the sites of photooxidation. This is
especially applicable for polypropylene, which is oxidized inhomogeneously.
4. Methods for the synthesis of stabilizers from sterically hindered amines were being
developed with the aim to reduce the costs and use accessible raw materials.
The mechanism of action of photostabilizers of polymers from sterically hindered
amines evoked a great interest after numerous reports of their high efficiency.
398
At present, the following methods are used for protection of polymers against photooxidation:
1. Use of substances to be added to the polymer composition, which first adsorb UV
radiation and then release adsorbed energy in the form not destructive for the polymer.
These components called UV adsorbers protect the polymer against UV radiation by direct
adsorption.
2. Incorporation of substances, which can catalyze non-radical degradations of hydroperoxides, into the polymer.
3. Incorporation of substances, which can deactivate the photoexcited state, into the
polymer.
4. Use of substances (antioxidants) capable of trapping free radicals propagating as the
result of oxidation, by means of which oxidized chains are disrupted.
Sterically hindered amines, nitroxyl radicals and products of their conversion can not
act according to the mechanism of screening UV beams or quenching photoexcited states.
Their action is mainly due to their involvement into the oxidation processes, which take
place in photooxidation of polymer. Thus, they act as radical-trapping antioxidants. But a
number of important features distinguishes them from usual aromatic antioxidants (phenols
or amines), which are weak polymer photostabilizers.
Several reactions can be involved in providing protection for the polymer against photodegradation. The contribution of each of the processes depends on the nature of polymer
and oxidation conditions. The time within which sterically hindered amine is converted into
nitroxyl in polypropylene is small as compared with the induction period. At the same time,
piperidines and respective nitroxyl radicals are almost equal by the efficiency of stabilization of polymers. In rubber, which is oxidized more readily than polypropylene, nitroxyl
radicals are much more efficient than sterically hindered amines. The reaction of the subsequent conversions of nitroxyl radicals is given below:
> N.O + P.
> OP
(1)
OH
> N O + OH
OH
(2)
N
O
> N.O + PH
>NOH + P.
> N.O + POOH

> N.O + PH
hV
>NOH + PO.2
>NOH + P.
(3)
(4)
(5)
The antioxidative action of nitroxyl radicals is due to their ability to react to alkyl radicals as in reaction (4). Owing to their reactivity to alkyl radicals, nitroxyls are the best photooxidative inhibitors than inhibitors of other classes.
In view of the above said, of great scientific interest is the problem of increasing the
durability of lacquer-and-paint coatings by introduction of nitroxyl radicals and their precursors sterically hindered amines into the anticorrosion composition.
The first stage of the work was to study the possibility of introducing the nitroxyl
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399
radical tanol of the formula (6) and SHA the diammonium salt of methylene disalicilic
acid (7) and DTG-5 (8).
The best solvent from those studied (acetone, toluene, ethyl alcohol, butyl acetate, ethyl cellosolve, butyl alcohol) for substances (6), (7) and (8) was found to be ethyl cellosolve.
Modifying additives were added to EP enamel in the amount of 0.5, 1.0, 1.5, 2.0 weight
fractions per 100 weight fractions of enamel.
The anticorrosion coating was formed on plates at room temperature for 24 h and at
80C for 2 h. Modifying additives without hardener were found not to promote the formation of coatings.
O
H4NO
OH
O
CH2
ONH4
(6)
ONH4
(7)
OH
O
H4NO
OH
O
CH2
C
OH
H3C
S
CH3
CH3
(8)
In application of coatings, an incomplete moistening of plates was observed. The results of preliminary tests showed that introduction of additives (6) and (7) contributes to a
1.52-fold decrease of internal stresses in formation of coatings at 80C and an improvement of their protective properties.
400
12
Biochemically Stable
Coatings for Protection of
Transport Containers
12.1 Coatings based on Ftorlon copolymers

An increase of adhesion of ftorlon coatings to metals is, as a rule, related to the growing
sophistication of their production process: high-temperature treatment or use of intermediate primers based on other polymers, which affects adversely the properties of the systems
of coatings separately and as a whole.
One of the ways of increasing the adhesion of coatings based on various fluorinecontaining copolymers to metal supports is chemical modification of the metal surface prior
to the application of coatings. Three types of polyfunctional silanes, the molecular structure
of which contains ethoxyl and amine groups, were studied as such modifiers. Modifiers
AGM-9, AGM-3, ASOT-2 are silanes containing, respectively, three ethoxyl groups and
one amine group; at the same number of ethoxyl groups two amine groups (primary and
secondary); the molecular structure of ASOT-2 includes nine ethoxyl and seven amine
groups.
Ftorlons of grades F-42L, F-32L were used as polymers. Coatings were hardened on
carbon steel and aluminium.
Chemical modification of the surface of the support leads to a significant increase of
the adhesion strength of coatings. The disruption forces of films exceed 30004000 N/m,
i.e., are commensurable with their mechanical strength, which is 3040 MPa; herewith,
delamination is of a cohesion character. Coatings applied to a nonmodified metal surface
peel off at 1015 N/m.
Adhesion of coatings to steel in corrosion-aggressive media was studied at different
temperatures. The results of the studies indicate a high stability of adhesion of coatings applied to the modified metal surface. In the absence of chemical modification of the metal
surface, the stability of adhesion of the same coatings does not exceed 2 h in cold media
(293 K) and 15 min at 363 K; in a 3% HCl solution the stability of adhesion was 12 min.
An increase of the stability of adhesion by 23 orders of magnitude and more not only
in pure water but also in electrolytes indicates the formation of a chemosorption adhesion
bond. The stability of adhesion of ftorlon coatings is maximal in the case when the modifier
contains the largest amount of functional groups.
The smaller the number of functional groups, especially ethoxyl groups, in the modifier is, the faster adhesion of coatings to steel decreases, and also the smaller its stability is.
402
At the maximal functionality of the modifier, the dependence of adhesion on temperature

is observed to be extreme.
Polyfunctional siloxanes containing ethoxyl and amine groups in the molecule are adsorbed on the metal surface from solutions in accordance with the Langmuir adsorption isotherm. This character of adsorption indicates the chemical nature of the interaction of amino
alkoxysilanes with the surface of metals.
The practical realization of the proposed method consists in the following. The metal
surface prepared predominantly by shot blasting is treated with a solution of modifier at a
concentration of 520 wt. % in toluene, acetone or another solvent, active with respect to
the modifier. The solution can be applied to the surface by dipping, spraying or by a brush
after drying for 2040 min. Excess modifier is removed by the solvent, and the surface is
again dried for 2040 at 291296 K. To the prepared metal surface, the solution is applied
by spraying, by a brush or by dipping the coating, and the surface is dried for 1 h under the
same conditions.
Using the above modifiers, adhesion is increased 2030-fold. With respect to the depletion of the efficiency of increasing adhesion, amino alkoxysilanes can be arranged in the
following sequence: ASOT-2 > AGM-3 > AGM-9. In this sequence, the functionality of
amino alkoxysilanes decreases, i.e., the content of ethoxyl and amine groups in the molecular structure goes down.
We developed structure-forming modifiers, which make it possible to increase the adhesion strength of ftorlon coatings to metal several tens of times. Their peculiar feature is
that they provide for a significant improvement of the performance properties of coatings
when introduced in small amounts (up to 2%) directly into the composition. These compounds belong to the class of polyfunctional structure formers. In their presence, a homogeneous supramolecular structure is formed in coatings along the thickness of the film with
regular alternation chequerwise at the interface of structural elements with chemical and
physical bonds. Modifiers structure formers sharply reduce internal stresses and increase durability of coatings operated under various conditions.
12.2 Structure of modified Ftorlon coatings

Modification of thermoplastics by reactive oligomers is a promising method of obtaining
novel materials possessing the properties of thermoplastic and thermosetting polymers. Developers of such materials should primarily take into account the process compatibility of
the component on condition that oligomer plays the role of a temporary plasticizer. However, at more advanced stages of conversion owing to the hardening of oligomer, the interaction between the polymer and oligomer components becomes more complicated.
A cold-hardened lacquer ftorlon epoxy composition of grade LFE-42K based on ftorlon F-42L and chlorine-containing epoxy resin EKhD in combination with amine-type
hardener AF-2 was studied.
It was found that films from a solution of EKhD have one temperature jump-like transition between 58 and 73C in the region of devitrification of hardened resin. The film from
lacquer LF-42L has two transitions in the region between 77 and 94C in the form of an
endothermal peak at 142C assigned to the melting temperature of copolymers crystalline
structure.
Introduction of resin with hardener into lacquer LF-42L has a significant effect on the
temperature and thermophysical values of transitions. At a maximum content of oligomer
in the composition, the glass-transition temperature of films increases by 13C, and the
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403
melting temperature decreases by 6C. With the rise in the content of hardened oligomer,
a decrease of the melting heat from the heat capacity in the devitrification region is observed. In compositions with nonhardened resin, similar structural changes are not observed. Therefore, in polymerization of the resin the segmental mobility of copolymers
macromolecules decreases, and various defects, including stresses in crystals, are formed.
Based on the structure studies, ftorlon and the epoxy composition, irrespective of the
aggregate state, were found to be a microheterogeneous system, with the resin localized as
individual particles, which represent microaggregates, and unevenly distributed in ftorlon.
This conclusion made based on the results of electron-microscopy and X-ray studies
enables considering this composition as a filled polymer, where the filler is rigid oligomer
EKh resin, and the matrix is copolymer of tetrafluoroethylene with vinylidene fluoride.
A higher strength of composite materials at a temperature increase as compared with
initial ftorlon can be explained by the ordering of their structure, as the result of increased
crystallinity, observed in heating of specimens to a temperature higher than the glasstransition temperature of hardened EKhD.
12.3 Coatings based on modified and ladder polyphenyl sesquioxanes

Ladder polyphenyl silsesquioxane polymers possess a number of valuable properties. By
thermal resistance, chemical resistance and elasticity they exceed polymers of the similar
composition, having no regular ladder structure. The composition and structure of monomer molecules, from which organosilicon polymers are obtained, predetermine the characteristic features of their properties.
The cohydrolysis reaction of various organochlorosilanes makes it possible to change
within a wide range the ratio between radicals framing the silicon atom and to obtain cohydrolysis products with a large diversity of properties. The formation of coatings based on
rigid-chain ladder polymers, aimed at the development of compositions for heat-resistant
coatings with a given set of physicomechanical properties, was studied.
To increase the adhesion of ladder polymers, various amounts of vinyl groups from
1.5 up to 8% were introduced into the cycle. With their number increasing, adhesion increases monotonically and at a concentration of 8% is three times larger. Along with this,
to increase adhesion of coatings to the support, it was treated with organosilicon fluoropolymers containing various active groups. The best results were obtained using organosilicon
compounds with labile hydrogen atom as a sublayer; herewith, along with an increase of
adhesion, internal stresses were observed to decrease and durability of coatings to increase.
Formation and ageing of coatings from polyphenyl silsesquioxanes with the molecular
mass of 500,000 with different concentrations of vinyl groups in the main chain, which were
introduced to increase adhesion of coatings, was studied. Coatings were obtained from solutions of polymers in toluene. The formation of coatings was investigated with account for
the kinetics of increment and relaxation of internal stresses, adhesion and supramolecular
structure. Thermal ageing of coatings was performed at temperatures from 200 up to 600C.
For the electron-microscopy study of the structure of organosilicon compounds, used was
made of the method of ion bombardment of the preparations. The object of study were nonmodified and modified polymers filled with 50% aluminium powder (Table 12.1).
The content of dimethylsiloxane links in polymer was regulated by changing the ratio
of components entering into hydrolytic co-condensation. An increase of the concentration
of dimethylsiloxane links in the polymer leads to an increase of its elasticity and to a simultaneous decrease of the thermal stability of materials.
404
Table 12.1 Effect of the concentration of vinyl groups of the sublayer on adhesion and ultimate
internal stresses.
System No
1
2
3
4
5
Concentration
of vinyl groups
Adhesion, MPa
Nonfilled
coatings
Filled
coatings
Nonfilled
coatings
Filled
coatings
0.5
0.7
1.1
1.7
0.8
1.0
1.5
2.1
1.5
0.7
1.1
1.7
2.1
1.7
2.1
4.5
5.8
7.0
2
5
8
8 + sublayer
A number of polymers with an average building block was obtained. Parameter n

changed within the limits of 1.5, 1.0, 0.5, 0.25.
C6H5
Si
O
C6H5
Si
O
CH3
O
SiO
CH3
It was found that the formation of coatings based on polyphenyl siloxanes with n from
0.25 up to 1.0 is accompanied with the spontaneous cracking and delamination of coatings.
It was shown that, with the concentrations of methylsiloxane links increasing, adhesion and
strength of coatings also increases 2.53 times. The lowest internal stress, not exceeding
0.5 MPa, was found to emerge in coatings from oligomer with n = 1.5. With the concentrations of methylsiloxane links decreasing, internal stresses increase and so does the coating
formation time to more than 2 h. Using rheological methods, it was shown that introduction
of dimethylsiloxane links into the copolymer contributes to the structuring of the composition. Deterioration of coatings from polymer with a small concentration of methylsiloxane
links is determined by the slowdown of the relaxation processes as the result of a sharp increment of viscosity of the composition; herewith, the rate of gel formation slows down.
The different character of structural transformations in the formation of coatings from
copolymers with n from 0.25 up to 1.5 renders a significant effect on their supramolecular
structure. A globular structure with globules 1012 nm in diameter was observed in coatings with n = 1.5, whose formation is accompanied by a a small rate of increment of viscosity. With the concentration of methyl groups decreasing, at n = 0.5 the size of globules
increases up to 3050 nm; herewith, their number per unit of surface increases significantly. Formation of coatings from copolymers with small n is accompanied with their cracking.
To improve the physicomechanical properties, they were filled with aluminium powder. At the introduction of 10% pigment, the adhesion strength of coatings from copolymers
with a small concentration of methylsiloxane links (up to 0.5) increases up to 1.5 MPa.
However, this value of adhesion is insufficient and coatings peeled off spontaneously in the
process of formation under the action of internal stresses. In coatings with a concentration
of methylsiloxane links up to 1.0 and 1.5 internal stresses were smaller respectively, 1.0
and 15 MPa, which, owing to a larger adhesion, evoke no spontaneous delamination of coatings. A significant increase of adhesion is observed in coatings with 50% aluminium
powder.
CHAPTER 12
405
Unlike nonfilled coatings, the critical thickness, at which coatings spontaneously peel
off, is observed for pigmented materials to be shifted to a value of 500 m.
In contrast to nonpigmented coatings, which exhibit the largest adhesion when using
copolymers with the maximal concentration of methylsiloxane links (1.5), when aluminium
powder is added, adhesion increases with the decrease of the concentration of methylsiloxane links in the homologous series of copolymers. The greatest adhesion strength of about
12 MPa is observed for coatings from copolymer with a small concentration of methylsiloxane links equal to 0.25. With their content increasing from 0.5 up to 1.5, the adhesion
strength of coatings changes insignificantly from 8 to 7 MPa.
In the presence of pigment, unlike nonfilled coatings, the effect of concentrations of
methylsiloxane links changing from 0.5 up to 1.5 is insignificant; herewith, internal stresses
change within the limits of 3 to 2.5 MPa. A sharp increment of stresses, more than two
times, is observed with the decrease of the concentrations of methylsiloxane links to 0.25.
Thus, in the presence of aluminium powder the adhesion and cohesion strengths of
coatings increase significantly at various concentrations.
The effect of the filler on the supramolecular structure of films with different parameters n was studied to elucidate the role of aluminium in the formation of the properties of
coatings. It was found that initial particles of aluminium powder have a plate-like structure
of various thicknesses along the area of the particle. In nonfilled coatings, the structure of
polymer is not exhibited. However, in coatings from polymer with n = 1.5 the distribution
of the filler is more uniform than in coatings with small n, lower than 0.5. Structural transformations leading to the emergence of a globular structure 1015 nm in diameter, with the
size of the globules approaching that of the structural elements of the support, contribute to
a better interaction at the interface to form a larger number of chemical bonds responsible
for the adhesion strength.
The further increase of adhesion was performed by modification by compounds with
hydroxyl groupings. The cause of this phenomenon is due to the crucial role of active
groups
Si
O , involved in the chemical interaction of particles of filler and the support
in the formation of adhesion/cohesion bonds. This effect is also achieved by using pigments
with the regular distribution of active functional groups on the surface of particles.
12.4 Photohardenable epoxy acrylates for protection of transport containers

Experience of investigating polarized oligomer systems has shown that coatings formed by
polymerization directly on the support are distinguished with higher physicomechanical
characteristics and resistance to aggressive impacts than coatings obtained from polymer
solutions. The efficiency of using these coatings from oligomer-monomer systems without
solvents increases using accelerated methods of drying: accelerated electrons (AE), ultraviolet (UV), infrared (IR) radiation. Their use not only contributes to the increased quality
of a coating, the decrease of labour and energy expenses for drying, the reduction of the
drying to seconds, but for the most part also partially solves the problem of protection of
the environment. According to the literature data, in the UV method of hardening no more
than 2% of applied material gets to the atmosphere, whereas usual methods release up to
60% of applied substances and solvents to the atmosphere.
It should be noted that, of all radiative methods of hardening, the method of UV drying
is the most promising owing to the simplicity and low cost of equipment. A UV unit does
not need large production facilities. All these advantages contributed to the development of
406
the chemistry of photopolymerized oligomers. To date, a very large number of photopolymerized compositions have been proposed and found application in furniture trade, printing
industry, paper industry, radioelectronics industry, metal working industry.
12.5 Physicochemical bases of developing photohardenable coatings

Polyfunctional oligomers with -bonds are usually used as bonding adhesive of photopolymerized compositions capable of forming coatings with high adhesion to the support
and large density of the three-dimensional network.
When modelling photopolymerized compositions for coatings, the functionality of oligomers is determined by the need to provide for, on the one hand, a high rate of polymerization by the radical or ion mechanism and, on the other, adhesion of the coating to the
substrate and formation of the three-dimensional network.
The photopolymerization rate depends on the kind of crosslinking groups and their activation energy.
The efficient value of activation energy of any polymerization process is determined
by the equation:
E = 1/2 Ein + Eg 1/2Et,
where Ein is initiation energy of the process, Eg is energy of the polymer chain growth, Et
is polymer chain termination energy.
In photopolymerization, Ein = 0. Therefore, the photopolymerization energy is determined by the relation:
E = Eg 1/2Et .
According to the data by Bagdasaryan, the chain growth energy of most alkenes is
within the limits of 49 kcal/mol. Herewith, vinyl monomers of the type of methyl acrylate
and methyl methacrylate have the minimal energies of activation and chain growth
4.24.5 kcal/mol.
The use of low-molecular-mass monomers of the type of methyl methacrylate for production of photohardened coatings is associated with significant problems. On the one
hand, acrylic monomers, though are low volatile (boiling temperature, 100150C), evaporate in photopolymerization on the open surface. On the other hand, in polymerization of
acrylic monomers the structure is consolidated and the specific volume decreases by
2021%. However, in one application protective coatings are known to be produced on
metal and wire by photopolymerization of low molecular mass acrylates in the gas phase at
a rarefaction of 10 3 10 5 mm vapours. But the presence of a short-wave region (200 nm)
in the spectrum of ultraviolet radiation often leads to adsorption of low-molecular-mass
dimers and trimers from the gas phase to the support, which deteriorates the quality of the
polymer coating. The use of a system of filters, which rule out the short-wave part of the
spectrum, is not always efficient for preventing polymerization in vapours prior to the sedimentation of monomer on the support. For this reason, films obtained in irradiation are often rather soft and have a linear structure. Studies of polymethyl methacrylate films
produced by photopolymerization showed that the mean chain length L = 10 nm, which
makes 15 monomer units. The use of non-polyfunctional oligomers leads to the formation
of polymers of the three-dimensional structure, possessing the stability at increased
CHAPTER 12
407
temperatures, a larger hardness in combination with elasticity, resistance to corrosion and

atmospheric effects. Herewith, for polyfunctional oligomers the rate of photopolymerization is much higher, the polymerization rate of oligocarbonate acrylates and oligoester acrylates noticeably increases with the increase of the content of the methacrylic groups. What
is more, acrylic monomers are polymerized at a much larger rate than methacrylic monomers, and, as the length of the molecular chain increases, the polymerization rate does
down.
At the same time, an increase of the molecular mass of polyfunctional oligomers is efficient from the point of view of forming coatings with the largest rate of relaxation processes, which leads to a decrease of internal stresses.
From the theoretical point of view, a positive effect of reducing stresses can be
achieved by internal plastification by comonomers or copolymers. When choosing comonomers, one should take into account Mayer theory, according to which the elasticity of polymer is determined by the multivariance of macromolecular conformations, the ultimate
magnitude of which, according to the laws by Gut, Mark and Kun, is directly proportional
to the square root from the number of bonds between carbon atoms. The literature mentions
the use for these purposes of esters of -, -ethylene-unsaturated acid and mono- or polybasic alcohol with the number of carbon atoms from 1 up to 18 of normal or iso structure,
for instance, 2-oxyethylene methacrylate, mono-2-hydroxyethyl(methacrylate), mono(2-hydroxyethyl)itaconate, methyl-2-hydroxyethyl itaconate, methyl-2-hydroxypropyl
maleate, octyl-2-hydroxypropyl maleate, trimethacrylate neopentyl glycol etc.
To produce polymerized systems forming coatings with small internal stresses,
Nechols and Flowers recommend to dissolve polymer in monomer.
The use of a 1030% solution of polymethyl methacrylate in monomer considerably
reduces the shrinkage by decreasing the exothermic effect of polymerization. Using this
modification grafting at a respective choice of ready polymers (acryl/vinyl series or rubbers), it is possible to succeed in obtaining a product, which gives a coating with reduced
shrinkage stresses at ultraviolet radiation of the coating. The literature describes photopolymerized compositions based on saturated polymer in a solution of acrylic monomer, polybutylene and copolymer of polybutadiene in a solution of styrene, polyvinyl butyral in
ethylene-unsaturated solutions, in which the polymerization process is performed by the
method of modification grafting.
When considering a theoretical model for photohardened coatings, the major requirement to any coating is its high adhesion to substrate. In adhesion of polymer to metal, the
role of the chemical nature of adhesion proves to be instrumental. This dependence is determined by the type of active polar groups, their number and donoracceptor properties of
the functional groups. Depending on the character of the functional groups, the interaction
of oligomer with the metal support in photopolymerization can proceed by the type of a covalent bond between electrons of labile hydrogen atoms (hydroxyl, carboxyl, amine group)
and d-orbit electrons of metal or by the type of an ionic bond.
Formation of an ionic bond is characteristic of metals with oxide layer. Most often,
this type of bond is realized in contact of metals with carboxyl-containing and hydroxylcontaining polymers. Various chemical bonds can emerge between the metal surface coated
by a hydrated oxide layer and functional groups of polymers.
For instance, epoxy resins can react with the metal surface according to the scheme
>Me
OH + CH2
O
CH
Me
CH2
CH
OH
408
Carboxyl-containing polymers can interact with the metal surface by forming bonds
of the type:
MeO + RCOOH
Me
OCOR
as well as iondipole type bonds

MeO H OCOR
Isocyanates, by reacting with surface films of oxides and hydroxides on the surface of
metal, can form bonds of the type:
MeOH + O
Me
NR
NHR
O
MeO
MeO + O
NR
MeO
R
or
Coordination-type bonds can also occur in the polyamidemetal system:

MeO
CH2
CH2
The existence of such bonds is possible at the polymermetal interface in the cases,
when adhesion is determined by trivalent nitrogen. A rather widespread type of interaction
at the polymermetal interface should be considered to be iondipole interaction and hydrogen bonds.
Depending on the purpose of coatings and the nature of the support, a great diversity
of photopolymerized bonding adhesives with various types of reactive functional groups
are manufactured at present. Known Western photopolymerized compositions are usually
solutions of polyester unsaturated resins in readily copolymerized ethylene monomers in a
mixture with photoinitiator. The content of polar (carboxyl, hydroxyl, amino, isocyanate)
groups in the bonding adhesive depending on the purpose of the coating is regulated in the
process of formation in the polycondensation reaction by changing the concentration and
chemical composition of the components.
Thus, bonding adhesives for printing plates are known to be produced using lightsensitive compositions based on polyamides, mixtures of polyacrylates and polyesters with
isocyanate groups in a solution of copolymerized acrylic monomers, sometimes containing
products of partial etherification of polyester polyols of acrylic or methacrylic acid, N-(oxymethyl)acrylamide or N-(oxymethyl)methacrylamide. For production of letterpress printing plates, use is made of compositions based on mixtures of block copolymers in solutions
of unsaturated polyol esters. Blocks of copolymers are monovinyl acrylene polymers and
dienic polymers, for instance, styrenebutadienestyrene. For the same purposes, as well
as for polygraphic lacquers, inks and coating, use is made of mixtures of polycondensation
products of unsaturated polybasic acids, and polybasic alcohols and copolymerized monomers of a mixture of haloid-containing polymers with end carboxyl groups and double
CHAPTER 12
409
bond-substituted nitrile and nitro groups; mixtures of products of interaction of epoxy resins
with -, -unsaturated mono- or dicarboxylic acids with acrylates of mono- or polybasic
alcohols.
Earlier, printing plates were fabricated using photopolymerized compositions based
on acidic and mixed cellulose esters of oligoester acrylates and oligocarbonate acrylates and
copolymerized monomers with ethylene bonds.
The number of patented photopolymerized compositions for protective coatings in the
recent 5 years increased significantly. There is a UK application for the composition and
process of producing photopolymerized compositions for protection of aluminium surface.
The basis of the composition is unsaturated polyester, which is produced by a two-stage
etherification of copolymer of ethylene oxymonomers, first with -, -unsaturated carboxylic acid, and then part of carboxyl groups is epoxidized by monoepoxyvinyl monomer. The
coating mixture contains about 50% of organic solvents, which requires a preliminary drying of the coating with hot air. The coating hardened by ultraviolet light for 3 min does not
dissolve in acetone for 92%. To produce protective coatings with rubberlike properties, use
can be made of a photohardened liquid polymer composition based on polyene polythiol
and an accelerator of photohardening. The presence of several side and end functional carboxyl and mercato groups provide for adhesion to metal.
Based on the polyenepolythiocol system, aqueous protective and decorative paints
were developed, which can be applied to metal without a primer. The coatings harden and
dry under the action of ultraviolet rays for 130 min. There are polyene-polythiocol compositions, which contain diallyl maleinate and toluylene diisocyanate and harden under the
light of an ultraviolet lamp (power, 5 kWt) in the presence of benzophenone and phosphoric
acid. The viscosity of the compositions is 120180 poise, pH 4.55.5. Coatings on tinplate
10 m thick irradiated for 35 s are characterized by gloss and high abrasion resistance.
There is an application of aqueous dispersions of polymers produced by emulsion polymerization of vinyl esters, acrylates, methacrylates, styrene, acrylonitrile and their mixtures with other unsaturated monomers to be used as aqueous protective paints crosslinking
under the action of light.
Coatings based on compositions from light-sensitive N-containing synthetic resin are
characterized by a high mechanical strength and water resistance. The resin includes a polymer, which contains nitrogen in the form of quaternary ammonium salt.
The recommended composition is well soluble in water. For protective coating of metal foil and sheets, it is proposed to use lacquers based on polyester dissolved in unsaturated
aliphatic monomer, compositions based on saturated polymer in a solution of acrylic monomer. Coatings based on epoxy materials are characterized by high adhesion, thermal stability and weatherability; such coatings are products of modification of epoxy resins of
ethylene-unsaturated acids. In the automatic line, the moist coating is hardened in one run
under a quartz lamp of 200 Wt, placed at a distance of 5 cm; the passage speed, 7 m/min.
For coatings of metal, there is a composition of vinyl resin hardened by photoirradiation. The composition contains (A) 260% wt. % of the salt of 2- or 3-valent metal of unsaturated mono- or dicarboxylic acid and (B) 9840 wt. % of an unsaturated compound
with 0.512 polymerized unsaturated bonds per unit with molecular mass 1000. Coatings
based on this composition are distinguished with high chemical and mechanical properties.
Photohardened coatings based on vinyl resins are known to be produced using a solution
(in vinyl monomer) of unsaturated acrylic resin obtained by a 3070% polymerization of
unsaturated monomers with anhydride groups with vinyl monomers. There are patents for
polyester compositions modified by fatty acid and isocyanate, compositions based on
410
copolymers of unsaturated methacrylic acid, its alkyl ether and polyester, polysiloxane
compositions containing polysiloxane with haloid phenyl and haloid alkylene radicals and
end ethylene-unsaturated bonds and crosslinking solvents.
A patent was applied for a composition based on the polycondensation product of
-,-dioxydimethyl polysiloxane (molecular mass 758) and methacryloyl oxypropyl trimethoxysilane. Polysiloxane compositions are characterized by high protective properties
and are used for protection of aluminium sheets.
12.6 Photochemical processes and structural transformations in formation

of coatings under the action of ultraviolet light
Formation of coatings from oligomer systems is related to the polymerization reaction immediately on the support, therefore, the thickness of the film and the nature of the support
have a significant effect on the polymerization kinetics, structure and properties of coatings.
The effect of the nature of the support is evident from the adsorption interaction of the oligomer with the support to form supramolecular structures in the boundary layer of the liquid
phase prior to the onset of the polymerization process.
It was shown that these structures perform the role of blocks and blanks in the formation of coatings. Data of studies suggest that formation of coatings from oligomer systems
proceeds stepwise via the stage of the formation of supramolecular structures followed by
the establishment of stronger bonds between these structures. Depending on the nature of
oligomer, of the support and structure-forming conditions, the number of bonds and the
character of supramolecular structures change in polymerization; in turn, they are responsible for the physicomechanical properties and durability of coatings.
Formation of coatings under the action of ultraviolet radiation is a specific process,
characterized by the primary photochemical act. Absorption of a light quantum by oligomer
causes the initiation of polymer chain growth.
The rate of photochemical initiation (Vin) is directly proportional to the intensity of absorbed light and equals to
Vin = 2Ja,
where is the quantum yield of initiation, determined by the number of pairs of radicals
formed during the absorption of one light quantum and Ja is the number of light quanta (einsteins) absorbed per unit of time (second) in unit volume (litre);
J0 = J0 [M],
where J0 is the intensity of the light quantum incident to the monomer, is the coefficient
of extinction for a certain wavelength of absorbed light, [M] is the concentration of
monomer.
In the case of using photoinitiators, which under the action of the light quantum split
to radicals initiating the photopolymerization of monomers with -multiple bonds, the initiation rate is determined by the equation:
Vin = 2 J0 [],
where [] is the concentration of the initiator.
The rate of the entire photopolymerization process Vg is then equal to
CHAPTER 12
411
Vg = kg [M](Vin /2kt)1/2,
where kg and kt are the chain growth and termination constants.
Substituting the values of the photopolymerization initiation velocity Vin and taking
into account the LambertBuger law, we obtain the equation for the photopolymerization
rate:
[ ]b
)
J 0 ( 1 e
V p = k p [ M ] ----------------------------------------kt
1/2
As the last equation shows, the rate of photopolymerization is proportional to the concentration of the photoinitiator. However, one observes here not only the quantitative dependence. Studies showed the efficiency of photopolymerization to depend on the
photoactivity of the initiator.
A high activity of photolytic homolysis is characteristic of carbonyl compounds, for
instance, ketones:
O
O
R
R'
C + R'
benzoin and its esters:

C6H5
C6H5
CH
C6H5
OH
CH
OCH3
C6H5
C + CHC6H5
O
C6H5
C6H5
OH
C + CHC6H5
O
OCH3
disulfides, sulfochlorides, derivatives of naphthalene and xanthone, organometal and other

compounds absorbing in the near ultraviolet region.
The reaction of photopolymerization can be initiated by photosensitizers. In contrast
with initiators, they are only carriers of electron excitation energy.
The most active photosensitizers are benzophenone and its derivatives, anthraquinone
and its haloid- and nitrosubstituted derivatives, fluorescein, eosine and other dyes.
The photopolymerization sensitization process consists of a number of successive elementary acts.
I. Under the action of photons of light due to the transition of valence electrons from
n orbitals to antibinding p* orbitals, the photosensitizer molecule z passes into an excited
state:
z + h
z*.
The direction of the spin of paired electrons changes, and the molecule passes from
the stable singlet state (complete spin S = 0 and the spin quantum number J = 1) to the triplet
state (complete spin at the parallel direction of spin vectors S = 1 and J = (2S) + 1 = 3).
II. The electron excitation energy of the photosensitizer is spent by nonradiative
412
triplettriplet transition for the excitation of polymerized monomers M.

z* + M
z + M*.
In this way, the triplet state of the sensitizer is quenched, and the unpaired electron is
transferred to the antibinding orbital of the monomer.
III. The formed monomer radical initiates polymerization according to the scheme:
M* + M
M M* + M
M M*;
M M M* etc.
This process will continue up to the establishment of an equilibrium in the system,

when the chain will simultaneously grow and be terminated due to recombination and disproportionation.
IV. Owing to the increase of viscosity in the system at the final stages, the chain growth
rate drops down and the probability of termination increases.
Herewith, a dead polymer is formed according to the scheme:
Mn1 M* + M
Mn + M* or Mn1 M* + Mn1 M*
M2n
At the primary stage of initiation by benzophenone and its derivatives with the absorption band in the region of 360 mm of the photopolymerization of vinyl monomers, there
occurs the photoreduction of the light-sensitive substance to form a respective semipinacol
radical. Studies by Granchik et al. showed that the monomer inhibits the yield of semipinacol radical. Using the method of pulse photolysis, the authors recorded the decay signals
of semipinacol radical in methyl methacrylate solution. By means of laser methods, vinyl
monomers were found to be efficient quenchers of the triplet state of benzophenone. The
authors believe that this explains the decrease of the yield of semipinacol radical in the presence of methyl methacrylate. Herewith, the deactivation of the triplet state is assumed to be
performed by way of donoracceptor interaction of the excited benzophenone molecule
with the molecule of methyl methacrylate.
The effect of the donoracceptor interaction of the excited benzophenone molecule
with the molecule of vinyl monomer is enhanced in the presence of amines, which play the
role of a photoreducer.
Herewith, the rate of polymerization of vinyl oligomers increases significantly, especially in the presence of tertiary amines.
When studying the hardening processes of unsaturated polyester resin based on fumaric and maleic acids and polyols in a solution of styryl with a viscosity of 1545 poise at 20C
and acid number of 32 mg KOH/g on a film 24 mm in thickness, E. Mleziva and
V. Chermak found the following substances to possess the greatest photoinitiating activity
(in the order of the rate of decrease): benzoin isopropyl ester, benzoin n-amyl ester, 2-chloride of 1,4-dibutyl naphthalene sulfonic acid, benzoin isobutyl ester, benzoin n-butyl ester
and benzoin methyl ester.
Benzoin itself is characterized by a low capability of photoinitiation. For the class of
sulfochlorides, excluding naphthalene derivatives of sulfides and ketones, the time of photopolymerization with the power source a high-pressure mercury lamp with the voltage
of 125 V at a distance of 30 cm (from the film) was of the order of 10003000 s. Works
by Western scientists showed that the mechanism of photoinitiation using benzoin and its
derivatives consists in the formation of radicals, differing in their energy state, as the result
of photolysis under the action of light quanta. Using NMR and IR spectroscopy methods,
413
CHAPTER 12
an intramolecular hydrogen bond in the benzoin molecule was found; this is assumed to increase the activation energy of benzoin photolysis:
O
C
OH
O
h
HO
C + CH
O
C
OH
C +
CH
Radicals formed from benzoin under the action of light quanta should, in the opinion
of the authors, overcome the energy of the hydrogen bond to be able to exit the cell, and
only those that exited the radical cell are capable of initiating polymerization.
The high photolytic activity of benzoin derivatives was established by the company
E9 du Pont de Nemours, but the firm Bayer AG was issued a patent for benzoin esters of
secondary alcohols, which, besides the high photopolymerization initiation rate, provide for
the stability of polyester resin compositions in storage.
Studies of the photopolymerization rate of trimethacrylic ester of pentaerythrite adipinate and triacrylic ester of pentaerythrite (PETA) under the action of irradiation by a DRSh
high pressure mercuryquartz lamp at a film thickness of 3 m by the method of gel fraction also showed that benzoin esters have the highest activity (Table 12.2). Using triethanolamine as a reducer and the photoinitiator trigonal, we succeeded in reducing the rate of
PETA polymerization to 1 s. Tests of the coatings obtained showed them to be elastic, mechanically strong and resistant to the action of acidic and alkaline media.
Table 12.2 Activity of photoinitiators.
Photoinitiator
Benzoin
Formula
C6H5 C CH C6H5
Polymerization rate, sec

7 20
PETA
300
89
77
34
10
900
480
8
600
180
5
O OH
Benzoin methyl ester
C6H5 C
CH C6H5
O OCH3
Trigonal
C6H5 C CH C6H5
O OR
Benzophenone
Michlers ketone
Mixture of benzophenone
and Michlers ketone (1:2)
C6H5COC6H5
[(CH3)2NC6H5]2CO
414
(continued)
Table 12.2 Activity
of photoinitiators.
Photoinitiator
Anthraquinone
-Chloroanthraquinone
-Chloroanthraquinone
Butyl anthraquinone
Androne
Dibenzyl ketone
Benzyl chloride
2-Nitrophenanthrene
Formula
Polymerization rate, sec
C6H4(CO2)C6H4
C6H4(CO2)CH3Cl
C6H4(CO2)CH3C4H9
C6H4COCH2C6H4
C6H5CHCOCHC6H5
C6H5CHCl
C6H5
C CH C6H5
NO2 NO2
Toluene sulfochloride
Dinitrodiphenyl
Diazo diethyl aniline
C6H5CH2SO2Cl
C6H5NO2C6H5NO2
C6H5N NC2H4C6H5NH2
7 20
PETA
420
49
49
126
1600
50
77
115
6
17
63
1800
75
34
600
365
23
600
2000
8
2000
55
The efficiency of photopolymerization is also determined by the nature of oligomer

and its structure (Table 12.3). Studies of the reactivity of oligoester acrylates also showed
that trimethacrylic ester of pentaerythrite adipinate is the most polymerized oligomer.
Table 12.3 Photopolymerization rate of acrylic monomers.
Monomer, oligomer and its commercial grade
Structural formula*
Polymerization rate, s
Oligoester acrylates
Methacrylic ester of diethylene glycol phthalate
MFF-2
Methacrylic ester of triethylene glycol phthalate
MGF-9
Dimethacrylic ester of glycerol phthalate
TMGF-11
D
M
P
T
D
P
P
T
70
M
M
70
25
M
Trimethacrylic ester of pentaerythrite adipinate
7 20
M
M
Ad
M
Dimethacrylic ester of
triethylene glycol TGM-3
tetraethylene glycol TGM-4
polyethylene glycol M-6600, TGM-13
Methacrylic ester of ethylene glycol carbonate
OKM-1
Ad
10
M
P
T M
40
Te M
42
M PeE M
15
E M
15
415
CHAPTER 12
Table 12.3 Photopolymerization

rate of acrylic monomers.
(continued)
Monomer, oligomer and its commercial grade
Structural formula*
Polymerization rate, s
Methacrylic ester of diethylene glycol carbonate

OKM-2
M D
D M
20
Methacrylic ester of triethylene glycol carbonate

OKM-3
M T
T M
35
Methacrylic ester of tetraethylene glycol

carbonate
TGM-4
Chloroacrylate
35
Te M
Te C
M
T M
CCl3
Cl3C
15
Monoacrylic ester of diethylene glycol carbonate

OKA-2
D A
Monoacrylic ester of triethylene glycol carbonate

OKA-3
T M
Triacrylic ester of pentaerythrite

Tetramethacrylic ester of pentaerythrite
Trimethylol propane triacrylate
Urethane acrylates
PDI-4AK
PPG-4AK
OUA-2000T
3
11
26
13
13
10
Aminated acrylates
Diethylamino ethyl methacrylate
M
Chloroethyl methacrylate
Et N
Et
35
Et
68
Et
Cl
Dimethylamino ethyl methacrylate
Et
Me
55
Me
Cyano-ethyl methacrylate
CN
40
Trimethacrylic ester of triethanolamine
(M ET)3N
45
CH2 CH CH2
O
45
Glycidyl methacrylate
Note: Photopolymerization rate was determined by the time of irradiating films 3 m thick by
DPSh-500 lamp radiation, during which time a coating achieved a maximum extent of hardening as
determined by the gel fraction method. Designations: M, methyl acrylate; P, phthalate; E, ethylene
glycol; D, diethylene glycol; T, triethylene glycol; Te, tetraethylene glycol; G, glycerol; Pe,
pentaerythrite; Ad, adipinate; C, carbonate; A, acrylate; Et, ethyl; Me, methyl.
416
Using the kinetic methods, the activity of phenylene diacrylates (PDA), phenylene
dimethacrylates (PDMA) and isomers of amino esters acryloyl aminophenyl acrylate
(ACAPA) and methacryloyl aminophenyl acrylate (McAPMA) of the general formula was
assessed:
O
O
CH2
R
CR
NH
CR
CH2,
H (ACAPA) or CH3 (McAPMA).
The photopolymerization reaction was initiated by 5 wt.% of benzoin isoamyl ester under a DPSh-500 mercury lamp in dimethylformamide solution. Using the EPR and IR spectroscopy and dilatometry methods, it was shown that derivatives of acrylic acid are the most
active in photocrosslinking reactions; what is more, for phenylene diacrylates the activity
is higher than for amino ester. Of amino esters, the m-isomer is the most active, then o- and
n-isomers. The spectroscopy data (the change of intensity of the absorption band in the region of 990910 cm 1 conforming to the deformation vibrations of hydrogen atoms at the
double bond) showed that n-phenylene diacrylate reaches the maximal extent of conversion
of the double bonds (73%) in 200 s. The kinetic changes of the intensity of the band at the
wave number of 990910 cm 1 obey the second-order equation
1/(a x) = K2ef t + C
or
l/D = K2ef t + C,
where a is the concentration of monomer; x is the amount of monomer, which reacted for
time t; K2ef is the second-order age constant; C is a constant; D is optical density.
The following values were obtained:
3.410 5
1.710 4
1.510 5
610 5
7.510 5.
n-PDMA
n-PDA
n-McAPMA
m-McAPMA
o-McAPMA
The rate of photocrosslinking of epoxyacrylates of the following structure was studied

using the method of IR spectroscopy by the vanishing of the absorption band of C=C vibrations in the region of 1640 cm 1:
CH3
IA. CH2
CHCOO
CH2
CH
CH2
OH
CH2
OCOCH
CH2
CH3
CH
OH
CH2
Molecular mass: calc. 809, found 871; 25C = 12,400 poise.

CH2
CHCOO
CH2
CH
OH
CH2
CH3
CH3
IIA.
OCOCH
CH2
CH2
(O
CH2
CH)n
CH2
CH
CH2
CH
OH
CHAPTER 12
417
Molecular mass: calc. 692, found 749; = 13 poise.

IIIA. CH2
CHCOO
CH2
CH
CH2
(OCO COO
CH2
OH
CH
OH
CH2)n
OCO COO
CH2
CH
CH2
OCOCH
CH2
OH
Molecular mass: calc. 662, found 573; = 1367 poise.

It was shown that at the stage of initiation (photoinitiator, 1 wt. % benzoin ethyl ester)
the rate of photocrosslinking is controlled by molecular mobility. The rate of photopolymerization for epoxyacrylates with low viscosity is higher than the same rates of photocrosslinking for epoxyacrylates with high viscosity. The rates of photocrosslinking for
epoxyacrylates at the last stage are more dependent on the glass transition of epoxyacrylates. Epoxyacrylate IIA, which has a lower viscosity, in 40 s of irradiation is characterized
by an almost 100% degree of conversion; epoxyacrylate IIIA, 9293% conversion; epoxyacrylate IA, 70% conversion. The molecular mobility of epoxyacrylates at the stage of initiation and the stage of glass transition is determined by the structure of epoxyacrylates. A
decrease of the viscosity of epoxyacrylate IA by dilution with styrene at a styrene to epoxyacrylate IA ratio of 10:90 decreased the rate of photocrosslinking at the stage of initiation,
but increased at the glass-transition stage. The maximal conversion (95%) is achieved by
the system in 90 s of irradiation by a 500-Wt high-pressure mercuryquartz lamp (model
USH-500D) at a distance of 30 cm from the source of the light.
The effect of the structure on the rate of photopolymerization of epoxyacrylates in a
solution of methyl methacrylate and butyl methacrylate, and the extent of conversion of the
double bonds was determined by the method of IR spectroscopy by the disappearance of
the absorption band of CH2=C valence vibrations in the region of 16601640 cm 1.
The data obtained are well consistent with the results of the gel fraction studies. It was
shown that the process of photocrosslinking is extremal, depends on the thickness of coatings and is limited by the etherification of free epoxy groups in the catalytic effect of the
photoreducer benzophenone-2-diethylaminoethanol. Kinetic studies of the joint photopolymerization of OUA-200 OT with tri-(oxyethylene)-,-dimethacrylate (TGM-3) and
methacrylic acid (MAA) by the method of dilatometry, during the irradiation by a
LUF-80-04 lamp with an illumination intensity of 0.410 3 Wt/(cm2 C) showed that, irrespective of the type of photosensitizer [benzophenone (BP), benzaldehyde (BA)], or photoinitiator [benzoin (BN), benzoin methyl ester (BME)], the maximal extent of conversion
does not exceed 7076%.
The dependences of consumption of monomeroligomer mass per unit of irradiated
surface / on the irradiation time t show that, using initiating compounds of various nature
and concentration in this system, the reaction in all cases is of accelerated autocatalytic
character. The process proceeds with auto-acceleration at the early stages ( = 3555%)
followed by the auto-slowdown at the more advanced stages of conversion ( = 7076%).
The authors explain this character of polymerization by an increment of the structural
viscosity of the system, which is accompanied by the gel effect. A particular feature of the
three-dimensional structuring of the system in photopolymerization is the layer-by-layer
418
advancement of the process, which is characterized by a constant frontal (relative to the

light flux) displacement of the polymerized three-dimensional layer (solid phase) and the
oligomer layer (liquid phase). As the result of this heterogeneity of the system, as well as
the redistribution between the chain termination constant and chain growth constant, the
photopolymerization of the systems studied is of auto-catalytic character. Based on the results of the kinetic studies, the authors arranged all initiating compounds by the photoactivity in the sequence: BA, BP < BN < BME. Printing plates produced based on the systems
studied, owing to the low extent of conversion of photopolymerized compositions, were
characterized by insufficiently high physicomechanical characteristics, an increased swelling in solvents and aged rapidly. Using the heat treatment at 75C after photoinitiation of
the BME system, the degree of conversion was increased up to 9092%, which, in all probability, is due to the increase of the mobility of reaction groups and a further structuring of
polymer material.
Additional introduction of the initiator azo-,bis-isobutyric acid dinitryl (ADN) increases the extent of conversion up to 9698%. In the opinion of the authors, this is due to
the formation of a complex between the carbonyl group of BME in a triplet state and azo
groups of ADN, which accelerates the photopolymerization process, under the action of UV
irradiation.
D.S. Phillips with coworkers, studying the photopolymerization of N,N-4,4-sulfonyl
diphenylene dimaleimide, found using electron spectra that the mechanism of photopolymerization proceeds via the formation of a donoracceptor complex of the sensitizer with
monomer.
Processes in photohardening of oligodienes of copolymer of divinyl with isoprene, oligobutadiene SKD-0 and oligobutadiene diol ORD were studied. Using the method of infrared spectroscopy, it was shown that in irradiation with UV light there occurs first
photooxidation and decomposition of carbon chains at single CC bonds and then
crosslinking of macromolecules via oxygen-containing bridges.
The studies showed that the rate and mechanism of photopolymerization and structural
transformations in irradiation has a crucial effect on the formation of the structure of coatings, whose character determines their physicomechanical properties durability.
The mechanism of photohardening of a composition based on hydroxyl-containing
methacrylates and products of interaction of oligodiethylene glycol adipinates with
2,6-toluylene diisocyanate in solutions of methyl methacrylate, methyl methacrylate in a
mixture with methacrylic acid, as well as in a solution of oligoester acrylate TGM-3 (20%),
was investigated.
Using the method of IR spectroscopy, it was shown that in irradiation of films on hermetically sealed glasses from KBr by ultraviolet light of a DRT-220 mercuryquartz lamp
for 1520 min practically all unsaturated compounds are copolymerized. The absorption
band in the region of 1630 cm 1, which characterizes the CH2=C valence vibrations, disappears. The authors found that the physicomechanical properties of coatings are also controlled by the reaction of isocyanate groups with hydroxides, which continues after
irradiation. The greatest breaking strength (15.030.0 MPa) of coatings is obtained at a ratio NCO/OH = 2.5. Using macrodiisocyanates with a smaller molecular mass (800), the dependence of strength on the NCO/OH ratio is of extremal character, and films with
NCO/OH = 1.5 achieve the highest strength of 370 kg/cm2. In the opinion of the authors,
additional hardening of the film due to the condensation by isocyanate groups and hydroxyl
groups makes it possible to obtain coatings with high elasticity (bending strength, 1 mm by
the ShG scale) and impact resistance (50 kgf/cm). A disadvantage of these coatings is their
CHAPTER 12
419
small hardness 0.20.4 (pendulum M-5) and tackiness, which disappears during the holding of the coating in the air for 12 h after irradiation. To eliminate the inhibitory effect of
oxygen of the air, moist coatings were covered by a polypropylene film and irradiated
through it.
Due to the inhibitory effect of oxygen of the air, without introduction of a paraffin
floating additive it is impossible to achieve the photohardening of oligoester maleinates.
Modification of oligoester maleinates by polyisocyanates makes it possible to avoid the inhibitory effect of oxygen.
Using infrared spectroscopy, it was found that the structuring of unsaturated oligoester
maleinate urethanes in styrene under the influence of UV irradiation includes three
processes:
copolymerization of unsaturated oligoester maleinate urethanes with styrene via C=C
bonds (disappearance of the absorption band in the region of 1645 cm 1);
copolymerization of monomer with isocyanate groups via vinyl bonds (disappearance of the absorption band of valence vibrations ofN=C=O groups at 2270 cm 1);
addition polymerization due to side reactions of free isocyanate groups.
The authors revealed the effect of the chemical structure, its regularity, density of
crosslinks and concentration of polar groups (the ratio NCO/OH) on the physicomechanical
properties of the polymer coating. The use of aromatic isocyanate 2,4-toluylene diisocyanate in the synthesis of oligoester maleinate urethane yielded a coating with larger values of
hardness (0.45 using M-5) and tensile strength (22 MPa) than for coatings based on oligoester maleinate and hexamethylene diisocyanate. With increased excess of the diisocyanate component, the tensile strength increases to reach the maximal values at a molar ratio
of NCO/OH = 1.51.75. At an increase of the molecular mass of macrodiisocyanate, the
hardness and strength of coatings decrease. All coatings are characterized by a high yield
of the gel fraction, 9296%.
Our works showed that an increase of the formation rate of the polyester coating under
the action of ultraviolet radiation increases the rate of relaxation processes, which provides
for a higher strength (15 MPa) and decreases internal stresses in the coating down to 0.6
MPa. Internal stresses in the same coatings at the radiant-heat hardening are 3.3 MPa, and
the strength of coating is 10.3 MPa. In the opinion of the authors, the efficiency of UV irradiation is stipulated by uniform initiation of copolymerization in the entire bulk, which
provides for the formation of a more homogeneous and ordered structure. Kinetic electronmicroscopy and IR-spectroscopy studies of the structure of photohardened coatings based
on epoxyacrylic oligomers showed that the coating formation process is multistage. At the
first stage, we observe the formation of chemical bonds within the limits of a small number
of molecules and initial adsorption blanks; at the second stage, formation of the threedimensional network by forming local bonds between supramolecular structures, which is
accompanied by a sharp increment of the physicomechanical properties. As the result of the
high rate of the relaxation processes, the formation of the three-dimensional network homogeneous ordered structure is observed in photopolymerization. At a 60-m thickness of
the coating, optimal physicomechanical properties could be obtained by UV irradiation by
a PRK-7 mercuryquartz lamp 1000 Wt power from a distance of 10 cm for 3 min. The
coatings obtained are characterized by high adhesion (2.83.2 MPa) and insignificant internal stresses (1.21.6 MPa).
Depending on the number of conjugated and unsaturated bonds formed in ultraviolet
radiation and treatment with an acetylenenitrogen mixture in an alkaline medium of
oil AS-8 based on hydrocarbon and naphthene fractions, the forces of adhesion of photo-
420
hardened coatings were observed to be different. It was shown that the adhesion force of
coatings is proportional to the intensity and duration of irradiation.
It was found that a bonding adhesive containing more than two conjugated bonds, for
instance, CH2=CHOOCRCH2 COOCH=CH2, is capable of hardening under the action of UV irradiation in 0.53.0 min to form a glossy coating. With the amount of unsaturated bonds in the product decreasing to 1%, there was practically no polymerization and
the value of the force of adhesion was zero.
The effect of the nature of crosslinking monomers on the content of the three-dimensional polymer and the resistance to breaking loads in photohardening of oligodiethyl maleinate adipinate have been shown in a number of works. The authors found that during the
introduction of styrene and methyl methacrylate at a ratio of 2:1 with respect to the bonding
adhesive, the photopolymerization rate is optimal, and the coatings thus obtained (in irradiation by LUF-80 for 7 min) are characterized by a high resistance to swelling in cyclohexanone and a resistance to stretching and abrasion.
Thus, analysis of the literature data shows that, despite a great diversity of studies and
commercial designs of photohardened coatings, formation of coatings from oligomer systems under the action of ultraviolet light has been studied insufficiently. The data of patents
on the physicomechanical and anticorrosion properties mainly represent the results of visual studies. The issues of photohardening of coatings from oligomer systems have been
studied insufficiently both on the molecular and supramolecular level. Experiments did not
always show the dependence of the rate of photocrosslinking on intensity of irradiation,
thickness of the coating, concentration of sensitizers and photoreducer. The mechanism of
sensitization in the presence of photoreducers and oligomers has not been sufficiently studied. Such parameters as the density of the three-dimensional network and interaction with
solvents have not been investigated, and their dependence on the structure of oligomer and
their effect on the physicomechanical, stress strain and relaxation characteristics of coatings has not been revealed. The relationship between the corrosion resistance of photohardened coatings and the density of the three-dimensional network and structural
transformations in the process of photocrosslinking has not been studied.
Studies of these characteristics and dependences is not only of scientific interest, but
is a must in practice for finding optimal variants of photocrosslinking coatings.
Analysis of Western and domestic experience of protecting metal from corrosion
showed that one of the promising directions for producing quick-drying primers for rolled
steel on production lines is the method ultraviolet hardening.
As the result of theoretical discussion and experimental studies, it was found that the
system based on unsaturated epoxyesters in a solution of esters of unsaturated acids and
monobasic and polybasic alcohols quickly hardens under the action of ultraviolet radiation
at a wavelength from 250 up to 400 nm; from the radical polymerization mechanism, conditions of etherification of epoxy resins ED-16 and EIS-1 by methacrylic acid were determined; the constants of the etherification rates at various temperatures (70, 80, 9394C)
were calculated and the etherification activation energies were found (EED-16 = 1.745109,
EEIS-1 = 1.604106).
Using the method of extraction, the optimal amount of photosensitizer benzophenone
in the systems studied was found to be 2% of the weight of polymerized components.
The inverse dependence of the time of photohardening on the extent of etherification
of the bonding adhesive was determined using the methods of IR spectroscopy and extraction. It was found that the optimal time of photohardening (i) for compositions based on
epoxyester ED-16 with etherification of 6075% at the thickness of a coating of 40 m is
CHAPTER 12
421
2.50.5 min; (ii) for compositions based on epoxyester EIS-1 with the same extent of etherification at a thickness of 40 m, 30.5 min. These data correspond to the results of studies
of adhesion, internal stresses and impact strength of coatings depending on the time of photohardening and the extent of etherification of the bonding adhesive. At an optimal time of
photohardening, coatings are characterized by the highest adhesion, optimal internal stresses and impact strength.
Higher values of the physicomechanical characteristics correspond to compositions
with a 60% etherification of the bonding adhesive. This is a consequence of the formation
of additional adhesion bonds due to the interaction of free epoxy groups with the metal substrate. It was found that for high-adhesion coatings to be produced it is sufficient to perform
etherification up to 75% at a bonding adhesive to solvent ratio of 70:30 and up to 60% at a
bonding adhesive to solvent ratio of 50:50.
As the result of studies of the physicomechanical and protective properties of coatings
based on the developed photopolymerized compositions, it was determined that coatings
based on epoxyester of resin ED-16 possess the best parameters.
It was found that introduction of oligoester acrylate MGF-9 -,-bis-methacrylate
triethylene glycol phthalate into photopolymerized epoxyester compositions increases
the elastodeformation properties of coatings and their resistance to atmospheric action, water, acids and salt fog.
As the result of a series of studies, we revealed the optimal compositions of photopolymerized compositions (conditionally designated as foton-4 and foton-1) and their process
parameters. Photohardening primers foton-4 and foton-1 are recommended for protection
of rolled steel and rolled metal on conveyor production lines.
Using the method of IR spectroscopy, it was confirmed that photopolymerized compositions based on unsaturated epoxyesters and oligoester acrylates do not practically
evolve volatile components into the environment in photohardening.
Technical-and-economic calculations of the efficiency of proposed photopolymerized
coatings for protection of rolled steel were performed.
The economic effect in the introduction of foton-1 and foton-4 in terms of 1 m2 protection with respect to reduced expenditures as compared with primer KhO-068 is much
larger as the result of better protective properties.
The cost of the loss of metal from corrosion in six months in the absence of protection
of rolled steel was determined. With consideration of this cost, it was found that, depending
on the thickness of rolled metal (15 mm), there is an additional economic effect at the
phasing-in of photopolymerized primers foton-1 and foton-4.
12.7 Properties of epoxy acrylate coatings for transport containers

An optimal time of irradiation is 23 min for all compositions. The characteristics studied
are maximal for this time. Compositions based on bonding adhesives with 60% etherification are characterized by slightly higher parameters of adhesion and of internal stresses,
which can, apparently, be explained by the formation of additional bonds of free epoxy
groups with metal of the support. Therefore, it is expedient to perform the etherification of
the bonding adhesive only for 60%. An increase of the adhesion bond with metal can also
be done by increasing the content of free epoxy groups in the composition by changing the
ratio of the bonding adhesive and solvent to 70:30. Herewith, the optimal time of hardening
(3 min) remains the same.
Based on the kinetic studies, it can be concluded that the best composition with
Resistance coefficient, k
422
1.5
1.0
4
1
5
2
3
0.5
0
0
30
60
90
Time of effect of the medium on primer coatings, days
Figure 12.1 Dependence of the resistance coefficient of primer coatings on the impact time of an
aggressive medium (water) (1, foton-1; 2, foton-2; 3, KhS-068; 4, foton-4; 5, foton-5).
consideration of the physicomechanical properties and photohardening rate is the composition based on epoxyester ED-16 with the etherification of 60% at a bonding adhesive to
solvent ratio of (7050%): (3050%) and the amount of photoinitiator of 2% (of the total
mass of polymerized components).
Studies of the photopolymerization kinetics of unsaturated epoxyesters in a medium
of unsaturated solvents showed that the main process of photohardening occurs due to the
opening of double bonds and polymerization by the free radical mechanism. The disappearance of the absorption band of CH2=C valence vibrations in the region of 16601640 cm 1
in the infrared spectra of photohardened coatings is an indicator of completion of the polymerization process.
Studies of adhesion of photohardened coatings after the impact of aggressive media
on them showed that they significantly exceed KhS-068 by their resistance to water, 20%
NaOH solution, 1 and 0.1 n HCl solutions (Fig. 12.1). It should be noted that coatings based
on primer foton-4 are the most resistant to the action of water and acidic solutions; and coatings on foton-1, to the action of alkali. Coatings based on foton-2 proved close to KhS-068
by their resistance. But introduction of MGF-9 had a positive effect. The resistance of the
coating foton-5 is much higher than that of foton-2.
The results of studies of the resistance of foton coating to the action of aggressive media were supported by tests in a salt-fog cabinet at a temperature of 40C for 150 h.
The resistance coefficients of coatings were calculated by the formula:
k = A1/A0,
where A0 and A1 are the average adhesion values determined, respectively, before and after
the impact of an aggressive medium.
Figure 12.2 presents the curves of the change of the resistance coefficient of foton and
KhS-068 primers depending on the impact time of an aggressive medium.
As the studies showed, coatings based on epoxyesters with addition of MGF-9 are
more elastic, shock-resistant and resistant to the action of water, though the yield of the gel
fraction is slightly lower than in compositions without oligoester acrylate. Herewith, it
should be noted that the composition based on epoxyester ED-16 is distinguished with higher parameters. To enable the final conclusion on the comparison of compositions based on
epoxyesters ED-16 (No 38) and EIS (No 39) and with addition of MGF-9 (Nos 41 and 45),
we studied the protective properties of coatings.
CHAPTER 12
423
1.5
1.0
0.5
1
4
5
2
0
30
60
90
aggressive medium (1 n solution of HCl) (1, foton-1; 2, foton-2; 3, KhS-068; 4, foton-4; 5, foton-5).
1.5
1.0
0.5
4
1
5
2
3
0
30
60
90
aggressive medium (1 n solution of HCl) (1, foton-1; 2, foton-2; 3, KhS-068; 4, foton-4; 5, foton-5).
The protective properties of coatings based on photopolymerized compositions Nos

38, 39, 41 and 45, which were conditionally designated as foton-1, 2, 4 and 5, were assessed
by the results of tests of the coatings in the atmosphere, in a salt-fog cabinet and under laboratory conditions. The laboratory studies provided for the determination of the resistance
to aggressive media using local elements. Adhesion of coatings to metals was determined
after the impact of aggressive media: 1 n solution of HCl, 0.1 n solution of HCl, 20% solution of NaOH and water for three months (Figs. 12.3 and 12.4). The results obtained were
processed by the statistical method of least squares at a confidence coefficient P = 0.95 and
the number of degrees of freedom f = 6. Table 12.4 presents the data of the statistical treatment of the results of determining the adhesion of photopolymerized compositions and
primer KhS-068 after the impact of aggressive media for 7, 14, 28, 60 and 90 days.
Coatings based on KhS-068 were intumescent, cracked, often completely destroyed;
active corrosion of metal was observed. Coatings on foton-2 proved to be permeable, and
underfilm corrosion was observed over a 20% area of the coating; the film was disrupted
in places. Specimens based on foton-5 looked much better after the tests. Underfilm point
corrosion is observed only on an area of 25% of the total surface; herewith, the continuity
of the film is preserved. Coatings based on foton-4 totally preserved their initial form. Coatings based on foton-1 slightly changed. For them, we observed the appearance of underfilm
point corrosion on an area of 0.10.4% of the total surface.
424
1.5
1.0
1
4
2
5
3
0.5
0
0
30
60
90
aggressive medium (20% solution of NaOH) (1, foton-1; 2, foton-2; 3, KhS-068; 4, foton-4; 5,
foton-5).
Thus, the results of tests of primers protective properties enabled their arrangement
in the following sequence by their resistance: foton-4 > foton-1 > foton-5 > foton-2 >
KhS-068.
Table 12.4 Atmospheric constancy of coatings based on primers Foton and KhS-068 (according to
State Standard GOST 6992 68).
Primer
Test duration, months

1
Assessment of properties, points

decorative protective decorative protective decorative protective decorative protective
Foton-4
Foton-1
Foton-5
Foton-2
KhS-068
5
5
5
4
3
8
8
8
8
6
5
5
5
3
3
8
8
8
7
4
5
5
4*
2
2
8
8
8
4
3
5
5
4*
2
2
8
8
8
4
3
*Browning in some points of the surface.
Studies of the weatherability of coatings based on photopolymerized primers supported this conclusion. The physicomechanical properties of coatings are in Figs. 12.5 and 12.6.
A reduced resistance of coatings based on foton-5 and foton-2 is explained by the inhomogeneity of resin EIS-1, containing free phenols. Introduction of MGF-9 into this composition significantly increased the chemical endurance and weatherability of the coating;
so for coatings based on foton-5 the parameters were observed to be higher.
Analysis of the obtained results shows that foton-4 and foton-1 are the best primers
with high protective properties. Advantages of the latter are their insignificant volatility under the action of UV irradiation. This is supported by the data of IR spectroscopy.
As the main volatile components of compositions are -,-unsaturated acid and esters
(methacrylic acid, methyl methacrylate, butyl methacrylate, MGF-9), the occurrence of
1.0
2.0
IIb
II
I
1.0
Ia
IIa
0
425
5.0
4.0
3.0
2.0
Impact strength, Nm
Ib
2.0
Adhesion, MPa
CHAPTER 12
1.0
0
1
2
3
Figure 12.5 Dependences of the physicomechanical properties of coatings foton-1 and foton-2 (I,
II, adhesion; Ia, IIa, internal stresses; Ib, IIb, dynamic strength) on irradiation time and extent of etherification of the bonding adhesive.
2.0
Ia
II
I
IIa
1.0
5.0
4.0
3.0
2.0
IIb
0
0
2
3
Impact strength, Nm
1.0
Ib
Adhesion, MPa
2.0
1.0
0
Figure 12.6 Dependences of the physicomechanical properties of coating foton-4, foton-5 (I, adhesion; Ia, internal stresses; Ib, dynamic strength; II, adhesion; IIa, internal stresses; IIb, dynamic
strength) on irradiation time and extent of etherification of the bonding adhesive.
these compounds in a hardened coating can be determined from the characteristic frequency
of vibrations of the carbonyl group in IR spectra.
12.8 Biocidal coatings based on styromal

Synthesis and the physicomechanical properties of organic and organotin styromal derivatives and coatings on their basis were described. The peculiar feature of these coatings is
426
that, along with the high physicomechanical properties, they possess bactericidal, antimicrobial and antifouling activities.
Styromal exhibits characteristic reactions peculiar of organic anhydrides and readily
enters into etherification reactions with organic hydroxyl-containing compounds.
Copolymers based on styromal were obtained at the interaction of trialkyl stannanols
or hexaalkyl distannoxanes with styromal or copolymerization of maleic anhydride, styrene
and organic or organotin maleates:
1.
CH
CH
CO
CO
CH
R3MOH
CH2
CH
CH
CO
COOH
CH
CH2
MR3
CH
CH
CO
CO
CH
CH2
SnR3 SnR 3
2. CH
CH + CH
CO
CH2 + CH
CH
CO
CO
CO
SnR3 SnR3
CH
CH
CO
CO
CH
CH2
CH
CH
CH
CH2
COOSnR3 COOSnR3
O
x
where M = C1Sn, R = H1CH3, C2H5.

The physicomechanical properties of coatings based on organic and organotin styromal derivatives (SMA) were studied. The study of the thermomechanical properties of organic and organotin styromal derivatives was done on a Tsetlin instrument at a load of 100 g
on a punch of 4 mm in diameter.
At the introduction of organotin groups into styromal, we observed a sharp shift of the
softening temperature to the region of higher values, by approximately 100C. The thermomechanical properties of tert-butyl styromal esters with varying degrees of etherification*
and triethyl stannyl styromal derivatives were studied.
At the same extent of conversion of carboxyl groups to ester groups in the case of
*The percentage of etherified carboxyl groups in copolymer was calculated based on the data of
elemental analysis and potentiometric titration.
427
CHAPTER 12
butanol or triethyl stannol as etherifying agents, the properties of copolymer are observed
to change sharply.
The emergence of a significant deformation of the copolymer containing a di-triethylstannyl substituent in the anhydride group
CH
CH
COOSnR 3 COOSnR3
is, probably, due to the weakening of intermolecular interaction owing to the absence of free
carboxyl groups.
The composition of produced copolymers was determined from the results of the elemental analysis and potentiometric titration. Table 12.5 presents some physicochemical
characteristics of produced copolymers.
Table 12.5
Physicochemical constants of synthesized copolymers.
Copolymer
Tsoft, Capacity of
In
C COOH groups DMF
in mgeq/h
Elemental analysis, %
C
found
SMA 1:1
H
calc.
found calc. found
calc.
205
217
0.52
71.26 71.28
71.34
5.15
5.12
4.95
8.50
SMA with tert-butyl

ester
201
215
2.65
70.25 70.03
70.10
6.35
6.17
6.27
2.50
SMA with triethyl

stannanol
300
2.42
2.80
57.95 57.47
57.03
5.53
5.76
5.74
18.11
18.66
SMA with hexaethyl

distannanol
300
1.87
64.25 64.13
63.90
5.64
5.15
4.34
11.01 10.50
10.95
18.9
Film formers based on styromal modified by organotin compounds form brittle coatings, which break down and peel off in the formation process at a comparatively low value
of internal stresses.
A dependence of internal stresses on the content of triethyl stannanol in the copolymer
was given. It is seen that with the increase of the extent of etherification of anhydride groups
by triethyl stannanol the internal stresses sharply drop down. This is, probably, due to the
weakening of intermolecular interaction of copolymer chains with the decrease of the content of free hydroxyl groups. At a styromal/triethyl stannanol molar ratio smaller than 1:0.04
we observed a spontaneous destruction of coatings in the process of formation and ageing.
Modification of styromal by butanol improves the physicomechanical properties of
coatings.
Table 12.6 presents the data on the effect of the percentage of tert-butanol and triethyl
stannanol on internal stresses and strength properties of coatings. It is seen that modification
of styromal by R3COH and R3SnOH (where R = CH3, C2H5) affects the physicomechanical
properties of coatings in different ways.
A sharp increment of internal stresses is observed in the system at a small content of
etherifying agents; herewith, the breaking strength of coatings changes insignificantly as
compared with the strength of the copolymer.
428
Table 12.6 Dependence of internal stresses (in) and strength (p) (in kgs/cm2) on the ratio of
initial components for coatings based on styromal modified by butanol and triethyl stannanol.
(CH3)3COH
Molar ratio of components
1:0
1:7.02
1:0.04
1:0.06
1:0.1
1:0.2
(C2H5)3SnOH
1.5
3.5
3.0
2.6
2.2
1.9
18.0
21.6
22.8
27.4
30.7
21.9
1.5
3.6
3.0
2.5
2.3
2.3
18.0
16.4
16.8
15.5
11.5
10.8
As the content of these components in the system increases, internal stresses go down,
and the strength of coatings increases in the modification by tert-butanol and drops down
in the modification by triethyl stannanol. A sharp increase of internal stresses in coatings
formed from the mentioned systems is probably due to the reaction of tert-butanol or triethyl stannanol with anhydride groups of copolymer in the process of film formation.
Coatings based on triethylstannyl styromal ester spontaneously break down in the process of formation.
To improve the physicomechanical properties of coatings based on styromal and its
organic and organotin derivatives, their copolycondensation with glycols at 80100C in
an organic solvent was carried out.
Data on the effect of the content of triethyl stannanol or diethylene glycol on internal
stresses and strength properties of coatings based on styromal and diethylene glycol or styromal and triethyl stannanol were given. It is seen that this dependence is nonmonotonic.
Introduction of triethyl stannanol into the styromal diethylene glycol system within the
limits of 0.10.15 wt. % induces an increment of internal stresses, herewith, the strength
of the coating drops down. The further increase of the content of triethyl stannanol leads to
a decrease of internal stresses and a considerable increment of strength.
A significant increment of internal stresses at a certain ratio of the initial components
is, probably, due to the formation of a three-dimensional structure by crosslinking styromal
by diethylene glycol, as well as to the coordinating effect of electron-deficient organotin
groups of the type of R3Sn.
The largest effect of the increase of strength and of the decrease of internal stresses is
observed in modification of the styromal diethylene glycol system by triethyl stannanol
as compared with the styromal triethyl stannanol system modified by diethylene glycol.
Coatings from three-component systems based on styromal diethylene glycol and triethyl stannanol are more resistant to ultraviolet ageing as compared with coatings from oneand two-component systems; data on the change of internal stresses in ageing of coatings
based on styromal and its derivatives under the action of ultraviolet irradiation by a PRK-2
lamp were given. It is seen that the sharpest decrease of internal stresses indicative of the
decomposition of polymer is observed in coatings from styromal. Modification of styromal
by organotin compounds increases the resistance of coatings to ageing.
Preliminary copolycondensation of these components by heating at 80100C for 30
min prior to the application of the solution to the support makes it possible to improve the
physicomechanical properties of coatings as the result of decreasing internal stresses in
them more than threefold (Table 12.7).
CHAPTER 12
429
Table 12.7 Dependence of internal stresses (b) of coatings based on the triethyl stannyl derivative
of styromal modified by diethylene glycol (DEG) on the ratios of the initial components and
formation conditions.
b, MPa
SMA: :DEG molar ratio*
1:0:1
1:0:5
1:0.08:5
1:0.13:5
1:0.2:5
1:0.44:5
1:0.1:0
1:0.1:1
1:0.1:3
1:0.1:5
1:0.1:10
with preheating
without preheating
0.30
0.50
0.70
0.48
0.30
0.21
0.28
0.42
0.35
0.30
0.28
1.2
1.5
1.7
1.8
1.3
1.0
1.3
1.5
1.6
1.2
1.0
*Percentage of diethylene glycol.
The low-molecular-mass copolymer of styrene and maleic anhydride (styromal) and

its organic and organotin derivatives were synthesized and characterized.
The thermomechanical, adhesion and strength properties of copolymers were studied.
It was found that introduction of organotin groups R3Sn into the copolymer by etherification or copolymerization leads to a sharp shift of the softening temperature to the region
of higher values by about 100C.
Modification of organic or organotin styromal esters by diethylene glycol makes it
possible to produce new film formers with higher physicomechanical properties.
Copolymers containing organotin groups R3Sn possess a resistance to ultraviolet light
and good bactericidal properties. They were found to have a high bactericidal activity with
respect to the aurococcus; coliform, hay and brucella bacteria and some others, as well as
to plankton organisms, which inhabit the water of industrial reservoirs. Copolymers containing groups (CH3)Sn, (C2H5)3Sn, (n-C4H9)3Sn and (C6H5CH2)3Sn possess higher bactericidal properties.
430
13
Technology of the
Protection of Large-tonnage
Foodstuff Containers
13.1.1 Methods of protecting storage tanks for potable 96% ethyl alcohol
The basic task of storage tank facilities in storage of a product is to provide for its qualitative
and quantitative preservation in long-term storage.
Most enterprises store products in cylindrical steel tanks made from steel grade 3.
Examination of the corrosion state of the internal surface of tanks for storage of ethyl
alcohol showed metal of these tanks to be in satisfactory state fissures on the bottom are
no more than 0.5 mm deep after a one-year operation.
According to reference data [Vorobyeva, G.Ya., Corrosion Resistance of Materials to
Aggressive Media of Chemical Productions, Moscow: Khimiya Publishers, 1975 (in Russian)] alcohol is a weak corrosion medium, characterized by an average rate of corrosion
no more than 0.001 mm/year at its action on steel grade 3.
Nevertheless, the quality of alcohol after its contact with rust, which catalyzes oxidative processes, changes to a certain extent towards the formation of such products as acetic
acid (Table 13.1).
Thus, the storage of alcohol in steel tanks renders an unsatisfactory effect on the quality of the product.
Studies of the issue revealed that steel grade 3 is not in the list of metals allowed for
contact with alcohol, and in the world practice it is stored in tanks from stainless steel.
Therefore, for tanks from steel grade 3, in which alcohol is stored, it is obligatory to use
protection of the product from metal of the tanks.
Two methods of protection are usually used for protection of the inner surface of steel
tanks from steel grade 3:
inhibition of the protective surface under the action of the medium;
polymer coatings based on lacquers and paints.
The first method of protection from corrosion is applicable mainly for airtight volumes
(pipelines, pressure vessels, etc.). For RVS-3000 intended for storage of food products this
method is difficult to use for a number of reasons:
volatile inhibitors contain amines, which are poisonous and for this reason are not
used in food industry in pure form;
solutions of inhibitory substances should be only aqueous, so their use is impossible
in winter time.
432
Table 13.1 Results of chromato-mass-spectrometric analysis of alcohol after accelerated tests in

contact with polymer coatings.
Compound
Concentration, mg/l
Initial specimen
Methyl acetate
Ethyl acetate
Diethoxy ethane
Methanol
Toluene
Ethyl butyrate
Propanol-1
Butyl acetate
2-Methyl propanol-1
Butanol-1
Xylol
1,3-Dimethoxy propanol-2
3-Methyl butanol-1
1,2,4-Trimethyl benzene
Cyclohexanone
Acetic acid
Propylene glycol
Ethyl ester of hexanoic acid
4.32
0.36
0.15
75.0
0.04
0.20
3.82
0.01
0.56
0.08
0.02
0.25
0.14
0.06
0.02
0.01
After contact with After contact with

Baryer-1P
rust
4.75
0.57
0.20
74.0
0.05
0.23
4.78
0.03
0.62
0.04
0.01
0.16
0.15
0.03
0.06
0.01
0.01
4.68
0.55
0.20
75.0
0.04
0.24
4.75
0.01
0.60
0.05
0.01
0.22
0.14
0.01
0.15
0.29
0.01
0.01
Besides, if the inhibitor would be totally removed which, in fact, is not real in practice the stored product would be in contact with metal of the tank, thus leading to the deterioration of its quality in long-term storage.
In this situation, protection should be of the barrier type to exclude the contact of the
product with metal. In full measure, this requirement is satisfied by lacquer-and-paint protective systems.
13.1.2 Objects and methods of studies
The total of 30 grades of coatings based on water-borne and organic epoxy resins, polyurethane and latex elastomers, chlorosulfonated polyethylene, copolymer epoxy organosilicon
and inorganic compositions were studied.
Standard free films of 30 grades of coatings were prepared and tested in contact with
alcohol by the gravimetric method.
The following methods were used in the work.
Study of the resistance of the coating by the gravimetric method
Free films of 30 grades of coatings were placed into a solution of alcohol at a ratio of
1:1 as compared with the ratio of the inner surface to the volume of the product (0.214 ml
to 1 cm2 coating). The film of the coating was weighed on a daily basis till a dynamic equilibrium was established in the product with respect to the leachability of the components of
the coating and the swelling of the film in the product, which is reflected in the stability of
CHAPTER 13
433
the weight of the tested coating. Usually, the dynamic equilibrium of such a system is established over the period of 7 to 14 days.
If the leachability of the coatings components predominates, the weight of the film
decreases daily. In this case, the coating is unsuitable for use in the tested medium.
If the swelling of the film of the coating predominates, then the film of the coating is
considered to be resistant in the tested medium in the case, when the increase of the weight
does not exceed 3%.
Method of accelerated tests
Accelerated oxidation of the product was performed in an ST-80M-2 thermostat for 4
months at a temperature of 45C in airtight glass vessels without access of oxygen of the
air in contact with chosen coatings.
Quality of the coating after accelerated tests was checked by the following parameters: weight of the specimen film, adhesion to the support, appearance.
Quality of the product was determined by the following parameters: physicochemical
and organoleptic characteristics of quality; chromato-mass-spectrometric analysis of the
depletion of the coatings components; safety parameter of alcohol.
13.1.3 Results of studies
Preliminary tests of 30 grades of coatings in contact with alcohol indicated that most of the
recommended coatings used in food industry did not endure a prolonged contact (up to 14
days) with ethyl alcohol of 96% concentration.
Characteristics of the leachability of epoxy, urethane and copolymer coatings are given in Table 13.2.
Table 13.2 Leachability of components of coatings in medium.
Group of coatings
Epoxide
Urethane
Copolymer
Leachability. wt. %
from 4.66 to 31.93
from 10.45 to 16.99
from 0.11 to 11.64
Out of 30 grades of coatings, 5 specimens passed preliminary tests. They include:

1. Epoxy organosilicon lacquer
2. Fluoroplastic coating
3. Inorganic coating
4. Copolymer modified coating
5. Epoxy coating for food containers.
These grades of coatings were recommended for accelerated tests in contact with
alcohol.
After accelerated tests, specimens of coatings were analysed to assess their appearance, adhesion and change of weight.
The appearance of all five specimens remained without visible changes as compared
with the initial specimens without contact with alcohol.
Adhesion increased from 1 point up to 2 points, except for the inorganic coating.
The change of weight of the coating specimens towards the decrease was characteristic
of four grades of coatings. An exception was the inorganic coating, in which the weight of
specimens remained unchanged after the accelerated tests in the medium.
434
Analysis of the quality of alcohol

Five types of coating were tested in contact with alcohol. After contact with the product, a satisfactory result was shown by one composition, whose characteristics are presented
in Table 13.3.
Table 13.3 Quality indices of alcohol-resistant coating.
Index
Base
Colour and appearance
Density, g/cm3
Silica modulus
Composition
Appearance and colour
Value
Clear liquid with yellowish tint
1.18 1.19
3.6 4.5
Even mat coating of gray colour without

drips or inclusions
Mass fraction of nonvolatiles, %, no less than
80
Time of drying to degree 3 at 20C, hours, no more than
2
Viability at 20C, hours, no less than
10
Relative viscosity by VZ-246 (nozzle 4), s, no more than
21 30
Coating
1.0 (10)
Impact strength of film on a U-1 instrument, J (kgf/cm2),
no more than
Adhesion of film, points, no more than
2
Bending elasticity, mm, no more than
20
Pendulum hardness, arb. units, no less than
0.6
The inorganic alcohol-resistant coating is a two-component system. The base is highmodulus liquid glass; the filler, zinc powder.
The parameters of quality of the base and of the ready-to-use coating are presented in
Table 13.3.
We tested initial alcohol, alcohol after contact with polymer coatings and alcohol after
contact with rust of the inner surface of the tank.
The results of the tests are represented by the following characteristics of the objects
of study.
1. Ethyl alcohol:
physicochemical and organoleptic characteristics of quality,
chromato-mass-spectrometric analysis of the leachability of coatings components,
safety parameters correspond to the norm.
2. Polymer coatings: the list of component parts of the formulations.
physicochemical and organoleptic parameters are given in Table 13.4.
Organoleptic parameters
the appearance: colourless liquid without foreign inclusions and residue,
colour: colourless liquid,
taste and aroma: characteristic of food-grade first-quality rectified alcohol without
taste and smell of foreign substances.
Analysis of the content of trace elements
Elemental analysis was performed on a Liberty-200 inductively coupled plasma
emission spectrometer (Varian).
435
CHAPTER 13
The chosen analytical lines, nm:

Cu 324.754
Hg 184.950
Cd 214.438
Zn 2206.200
Pb 220.353
Fe 259.940
As 188.979
Si 251.611
Table 13.4 Physicomechanical and organoleptic parameters of quality of alcohol.

Parameter
Volume fraction of ethyl alcohol, no less than

Purity test with sulfuric acid
Oxidizability test at 20C, no less than
Mass concentration of aldehydes in terms of acetic
aldehyde per 1 dm3 of anhydrous alcohol, no more than
Mass concentration of fuel oil in terms of isoamyl and
isobutyl alcohols (1:3) per 1 dm3 of anhydrous alcohol,
no more than
Mass concentration of esters in terms of acetic ethyl
ester per 1 dm3 of anhydrous alcohol, no more than
Volume fraction of methyl alcohol in terms of
anhydrous alcohol, no more than
Mass concentration of free acids (without carbonic
acid) in anhydrous alcohol per 1 dm3, no more than
Content of furfurol
Unit
measure
Quality indices
Regulatory
norm
Real value
initial
specimen
after
contact
%
ml
min
mg
96
passed
10.0
10.0
96.0
passed
12.0
6.8
96.0
passed
11.0
8.2
mg
10.0
7.3
9.0
mg
50.0
46.0
45.0
0.05
0.009
0.009
mg
15.0
0.07
0.07
nd
nd
nd
nd, not determined
The content of silicon was determined because it is present in the components of the
coatings:
Conditions of recording the spectra:
power 1.5 kWt,
consumption of argon in plasma 15.0 l/min,
consumption of argon for blowing off the burner 2.25 l/min,
consumption of analyzed solution 1.5 ml/min,
pressure on the atomizer 100 kPa,
viewpoint optimized by the signal/noise ratio,
integration time 5 s,
replication number 5.
The calibration was carried out using Merck standards.
The results are presented in Table 13.5.
From the data presented in the table, it follows that:
1. By the content of toxic metals Cu, Zn, Pb, Cd, As, Hg, Fe all investigated ethyl
alcohol specimens correspond to the safety criteria of the medico-biological requirements
MBT 5061-89 of the Ministry of Health of the Russian Federation.
2. The concentration of Si and Zn present in the component of anticorrosion coatings
does not increase in specimens of ethyl alcohol.
436
Table 13.5 Content of trace elements in alcohol.

Index
Unit
measure
Regulatory
norm
Initial
specimen
Specimen after
contact with coating
Mass concentration of lead

Mass concentration of cadmium
Mass concentration of arsenic
Mass concentration of mercury
Mass concentration of copper
Mass concentration of zinc
Mass concentration of iron
Mass concentration of silicon
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
0.10
0.05
0.10
0.03
0.50
5.00
5.00
nd
<0.01
<0.01
0.02
<0.001
0.23
0.48
0.06
5.3
<0.01
<0.01
0.02
<0.001
0.24
0.46
0.05
5.3
Study of ethyl alcohol specimens by the method of chromato-mass-spectrometry

Chromatographic parameters:
quartz capillary column DBWAX (analogue of Carhowax), length 30 m, inner diameter 0.25 mm, film thickness of immobile phase 0.25 m;
temperature regime: stage 1, 2.5 min at 35C; stage 2, temperature increase up to
180C at a rate of 5C/min;
injector with flow divider (1:10), temperature 220C;
linear rate of carrier gas 5 ml/min.
Mass-spectrometric parameters:
range of masses 41450;
type of ionization by electron impact;
scanning rate 1 spectrum/s;
ionization time setting automatic.
From the data presented in the table, it follows that the investigated specimens are totally identical, which indicates that there is no leaching of volatile organic components from
anticorrosion coatings in their contact with ethyl alcohol.
Thus, the inorganic coating rendered no negative effect on the product and itself did
not undergo significant changes under the influence of alcohol.
13.1.4 Technology of anticorrosion protection of the inner surface of ethyl alcohol
storage tanks
The technology of protecting the internal surface of VRS-3000 from corrosion includes the
following operations:
quality check of lacquer-and-paint material
preparation of the surface of metal
sealing of welded seams of the internal surface
application of the protective layers of the coating
post-operation process control
commissioning of the protected surface for operation.
1. Quality check of lacquer-and-paint material
The supplied materials should satisfy the requirements of respective technical specifications:
CHAPTER 13
437
the composition of the coating. In this case, for food purposes the composition is supplied without the hardener. The applied coating is not subjected to the carbon dioxide treatment,
the solvent in the recommended process is a mixture of ethyl alcohol and acetone at
a ratio of the weight fractions 1:1.
The characteristics of the composition and coating on its basis are presented in Table
13.6.
Table 13.6 Quality indices of composition and coating on its basis.
Quality indices of material
Drying time at 202C up to degree 3, hours, no more than
Viability at 202C, hours, no less than
Relative viscosity by VZ-246 with nozzle 4 at 202C, hours,
no more than
Mass fraction of volatiles, % no less than
Coating
Impact strength by U-1A instrument, J (kgf/cm2), no less than
Bending elasticity, mm, no more than
Initial equilibrium potential, mV
Adhesion, points, no more than
Pendulum hardness, arb. units, no less than
Norm per
technical specifications
Upon drying, the film is even, of
matte gray colour, without drips or
mechanical inclusions
2
10
36
80
1(10)
20
980
2
0.6
2. Preparation of the surface of metal

Preparation of the metal surface of the tank consists in its purification from rust, scale,
dust, grease and other contamination.
Purification should be done by pneumatic metal brushes, whose characteristics are presented in Appendix.
An industrial vacuum cleaner is used for dusting the purified surface.
In cases of grease pollution, the surface is cleaned by wiping cloth soaked in a solvent.
An alcohol-acetone mixture prepared at a component ratio (w/w) of 1:1 is used as the solvent. Degreasing of the prepared surface is also carried out by this solvent. Consumption
of the solvent is 0.15 g/m2.
After degreasing, the surface is held for no less than 1 h in a premise with exhaust ventilation.
The prepared surface should be clean, even; the presence of a dense residual rust of no
more than 40 m thick is allowed.
3. Sealing of welded seams of the internal surface
Welded seams should be thoroughly dusted and degreased in accordance with the process as per p. 2 above.
The prepared surface of welded seams is wiped by wiping cloth soaked in the base of
the composition.
In 1 h, one layer of the composition is applied to the surface of treated welded seams
and in the weld proximity of 10 cm on both sides of the seam.
438
The composition is diluted to working viscosity of 2325 s according to VZ-246 with

nozzle 4 with distilled water.
Application of the ready-to-use composition is done by any of the traditional methods:
by a brush, roll or spraying.
4. Application of the protective layers of the coating
Prior to the application of the coating, all the surface is treated with the base of the
composition. In 24 h after the application of the coating to the welded seams, the treated
internal surface is protected by two layers of the coating. The formulation of the first and
second layer is the same as in p. 3. The consumption of the composition for one layer of the
coating is 250 g/m2. The interlayer drying of the coating is 3 h at the application temperature
of no less than 5C. The composition is not used at negative temperatures of the surface, as
the solvent for it is water.
Painting workers move from top to bottom: roofage upper parts lower parts bottom.
In three days after the last layer of the coating is applied, it should be treated with carbon dioxide to finalize the formation of a strong film of the coating. For this purpose, use
is made of pressure vessels with carbon dioxide, dry ice or carbon-dioxide fire extinguishers.
The thickness of the ready coating on seams is no less than 350 m; and on the other
surface of the tank, no less than 300 m.
5. Post-operation quality control
When performing the work on the application of the composition, the quality control
is provided for at all stages of its execution; this is be reflected in the documents for the
preparation of the surface and application of the composition.
The quality of the coating is assessed by its appearance, extent of drying and adhesion.
The appearance of the coating is assessed according to the State Standards.
The extent of drying of the coating is controlled in accordance with the State Standards.
Adhesion of the coatings is checked by the method of lattice notches.
The thickness of the coating is controlled by any thickness gauge.
6. Commissioning of the protected surface for operation
After all process operations, the coating is ready for performance in contact with a food
product in 5 days of holding at a temperature of the environment no less than 5C. The coating is not electrically conductive, which solves the problem of the electrostatic sparking
safety inside a filled tank. At a prolonged holding of the empty tank, the coating performs
the protective functions and withholds temperatures from minus 30C to plus 50C of the
ambient air. The service life of the coating is no less than 15 years.
Requirements to the safety of works, industrial sanitary and fire safety
Works on the protection of tanks from corrosion should be performed with the observation of safety rules in accordance with the State Standards and preventive fire-fighting
rules for industrial enterprises, as well as sanitary rules approved by the Ministry of Health.
Anticorrosion works should be maximally mechanized; means should be provided to
ensure the elimination of hazardous factors and the reduction of harmful industrial factors
for the workers. The level of hazardous and harmful industrial factors should not exceed
admissible values.
Anticorrosion works should be carried out in accordance with the requirements of the
State Standards.
CHAPTER 13
439
When performing works on open sites or in facilities equipped with forced (local and
general induced draft) ventilation, it is necessary to have fire-fighting means. Ventilation
should satisfy the requirements of the State Standards. Work with faulty ventilation is forbidden.
The content of harmful substances in the air should not exceed the maximally permissible concentrations.
Organization of production premises, utility rooms and work places should correspond
to the requirements of the construction and sanitary norms and design regulations approved
by the Russian Federation Construction Committee and the Ministry of Health.
The level of noise and vibration on work places should not exceed the norms.
Work places should be organized with consideration for the ergonomic requirements
and convenience of workers movements and actions.
Anticorrosion works are allowed to be carried out by persons not younger than 18
years, who passed a medical examination, received training and instructions. Workers
should be regularly checked for their knowledge of instructions and pass regular medical
examinations.
Production personnel should not be allowed to perform anticorrosion works without
personal protective equipment. Kinds of personal protective means are determined by normative documents for the technological process, for materials and equipment used. The
working order of the personal protective means should be checked before work.
Workers should have knowledge of:
hazardous, harmful production factors associated with works performed; harmful
substances occurring in applied materials and present in the air of the working area; the
character of their action on the human organism;
instruction for the sequence of work and the maintenance of the workbench;
instruction on the safety rules, fire-fighting regulations and industrial sanitary;
first-aid techniques to casualties;
rules of personal hygiene;
rules of using personal protective means.
Personnel working with fire- and explosion-dangerous harmful substances and their
mixtures should be granted periodic 10-min work breaks each hour during the working
shift.
Personnel working at a height of more than 3 metres should use safety belts.
When preparing and painting the surfaces of tanks, no less than two technicians should
be on permanent duty at the entrance. Personnel working inside the tank and those on duty
should always communicate (by means of sound or light signals or by means of a rope, one
end of which should be taken outside and tied to a support and the other to the safety belt
of the painting worker). Personnel on duty should be equipped with the same means as the
painting workers.
Electrical equipment for painting works should correspond to classes of fire and explosion safety for premises, as determined by the rules for electrical equipment installation
approved by Gosenergonadzor (State Power Supply Inspectorate). Electrical equipment
should be installed and operated in accordance with the rules for technical maintenance of
electrical installations. Equipment and articles to be painted should be grounded.
Rules for the Design and Safe Operation of Vessels Working under Pressure
approved by Gosenergonadzor bodies should be observed when using equipment operated
under pressure (spraying compressors, shotblasting units, etc.)
Placement of the equipment should take into account the convenience of its
440
maintenance and safe evacuation of workers in emergency. Equipment used for anticorrosion works should correspond to the requirements of the State Standards.
At working sites, it is forbidden to smoke, keep and take food, use sources of open fire
and tools causing spark formation.
Before the start and after the end of works, the production area and protected objects
should be ventilated.
Metal components or assembly units in places of possible spark formation upon impact
or shift should be isolated one from another.
Polymer material, solvents, thinners and hardeners should be kept in storage facilities
equipped with a forced air supply and fire-fighting means in accordance with the requirements of the State Standards (GOST) and in intact sealed containers with appropriate identification information.
Dirty wiping cloths, working cans, painting tools and production wastes should be put
to specially allotted places and degreased.
13.2 Bactericidal wear-resistant coatings for storage and processing of grain

and grain products
The development of highly efficient preserving technologies for storage of grain and its
products using bactericidal coatings, which provide for a significant decrease of contamination of grain and its products by spore bacteria (B. subtilis, B. mesentericus), fungi and
molds, causing the microbial damage of grain fibrin and potato disease of grain, is a topical scientific and applied problem.
Its solution is associated with the development of ecologically pure technologies for
production and processing of agricultural raw materials and functional polymer materials
with special properties. The so called bread diseases, which are caused by the fact that up
to 80% of harvested grain in some regions are affected by pests, pose a serious problem for
bread-baking industry. Even if the food-making technology provides for the subsequent
high-temperature processing of raw materials, it is preceded by low- and mid-temperature
stages, where in the absence of bactericidal protective materials biodeterioration processes
of raw materials with increased autolytic activity (of especially valuable part of grain, gluten) can develop further. This leads to a decrease of safety and native value of grain and its
products, as well as initiates and intensifies the biodegradability of basic stock.
Microorganisms get to flour mainly from the surface of grain during its growth and
grinding, as well in transportation within a flour-grinding plants. For this reason, both the
species composition and amount of microorganisms depend on the conditions and time of
grain storage and pretreatment before grinding, as well as on the content of hull particles
(i.e., on the grade of flour).
The actual contamination of flour by various bacterial species varies within very wide
limits and depends on the content of hull particles in the product and on the thorough preparation of grain for grinding. Examination of various flour samples showed that the general
content of bacteria in them can vary from 1,300 up to 20,000 per 1 g. The bacterial content
in high-grade flour is, as a rule, 23 times lower than in first- or second-grade flour.
Bread-baking plants receive up to 6065% of the general volume of flour with reduced
bread-baking properties. Usually, the reduced quality of flour, especially from injured
grain, is accompanied by an increased contamination with spore bacteria (B. subtilis, B. mesentericus), which cause the potato disease of bread. Bread with signs of potato disease
causes acute gastrointestinal disorders.
CHAPTER 13
441
Various measures are worked out to reduce the negative consequences of this phenomenon, including the processes of producing safe baked goods from flour contaminated with
spore-forming bacteria.
The most topical and efficient solution of the problem is the active (but safe for the
human organism) inhibition of pathogenic microflora using bactericidal coatings at the early stages of the grainflourbread chain. The proposed approach enabled storage, treatment and processing of grain with the lowest losses of its most valuable part gluten, made
it possible to prevent the significant damage to health, as well as to increase the cost efficiency of elevator, flour-grinding and bread-baking plants. The known developments in this
field are based on the use of coatings with low-molecular-mass bactericidal additives. In
operation, the latter easily migrate from the coating, which leads to the rapid loss of bactericidal properties and contamination of food raw materials. With this in mind, technologies
were worked out for storage of grain and its products using bactericidal coatings containing
high-molecular-mass (oligomer and polymer) additives, chemically bound to the polymer
base of the coating and not subject to migration. These bactericidal coatings will provide
for a stable bactericidal effect, microbial preservation and safety of food products throughout the entire service life of the coating.
The obligatory stage of the process of producing high-quality baked goods is maturation of flour in special bunkers for several months. This biochemical process proceeds much
faster, for 4560 days, if the flour is constantly aerated. In this connection, along with bactericidal properties coatings should possess a high wear resistance to granular products.
Maturation is the process of improving bread-baking properties of freshly baked flour
in its storage. Such a flour from new-harvest grain is characterized by a low water-absorbing capability, increased enzyme activity, relatively weak gluten. Bread from immature
flour has the dense and sticky crumb, insufficient volume and porosity. The essence of flour
maturation is to increase its strength as the result of the oxidative action of oxygen of the
air and peroxides on protein substances and enzymes.
Together with the Joint Stock Company Krasky BEP, we developed and introduced
enamel of grade BEP for coatings with high bactericidal properties and abrasion resistance.
Enamel is produced in cream and light-gray colours. Other colours are possible on request (using nontoxic iron-oxide pigments).
Parameters of quality of the enamel base, hardener and ready-to-use enamel should
correspond to the requirements given in Table 13.2.1.
Table 13.2.1
Parameter
Value
Testing method
40
According to GOST and

per p. 2 of these technical
specifications
BASE
Extent of grind, m, no
more than
HARDENER
ENAMEL
of film
Homogeneous liquid of yellow-brown

colour without foreign inclusions. Tint is
not rated.
Per p. 3 of these technical

specifications
Upon drying, enamel should form an even

semi-glossy film of respective colour

per pp. 4 and 5 of these
442
Table 13.2.1
(continued)
Parameter
Value
without foreign inclusions. Brush marks

are admissible. Tint is not rated.
Mass fraction of volatiles,
5
%, no more than
Thickness of non-dripping
wet layer, mm, no less
than
Time of drying t up to
degree 3 at 20 2C,
hours, no more than
Impact strength of film by
U-1 instrument, cm,
no less than
Bending elasticity of film,
mm, no more than
0.5
Adhesion of film, points,

no more than
Resistance of film to static

action of water at
(1002)C, hours,
no less than
Abrasion resistance,
kgf/m
24
40
3
10.5
Testing method
specifications
Per pp. 4 and 7 of these
specifications
specifications
specifications
According to GOST,
Section 2 and per p. 4 of
these technical
specifications
According to GOST,
Method A and per pp. 4
and 8 of these technical
specifications
GOST, international
standard ISO 77 84
Note: Resistance of film to static action of water is checked by samplings, no less than twice a year.
Methods of tests
1. Taking samples according to the State Standard.
Before conducting tests, samples of hardener and enamel base are held for not less than
24 h at a temperature of 202C, and then are thoroughly mixed. It is admissible to warm
or cool the sample to this temperature on a water bath during the mixing.
2. The degree of grinding of the enamel base is determined in accordance with the State
Standard (GOST) by the boundary of the beginning of the lines, by the place of the appearance of the third uninterrupted line, with its depth reaching the metal. A separate uninterrupted line, beginning at a distance of more than 15 mm from the other lines, is not taken
into account.
3. Determination of the colour and appearance of the hardener are performed visually.
The hardener is poured into a test tube and viewed in transmitted light. The absence of inclusions is checked by pouring onto a glass, which is viewed in reflected and transmitted
light.
4. Preparation of enamel for the test.
4.1. Before conducting the test, the enamel base is thoroughly mixed with the hardener
for 35 min.
4.2. To determine the colour and appearance of the film, it drying time, impact
CHAPTER 13
443
strength, adhesion and resistance to the static effect of liquids, enamel is applied to plates
from steel, grades 08 kp or 08 ps, 7050 mm in size and 0.81.0 mm thick, prepared according to GOST. To determine the bending elasticity of the film, the primer and enamel
are applied to tin plates 20100 mm in size and 0.2528 mm thick, prepared according to
GOST.
4.3. To determine the colour and appearance, drying time, impact strength and adhesion of the film, enamel is applied to the plates in one layer on one side. To determine the
resistance to the static effect of water, enamel is applied to the plates in one layer on both
sides, protecting the edges by the tested material. Enamel is applied by a brush. The thickness of the one-layer enamel film after drying should be 150200 m. The thickness of the
film is measured by any thickness gauge, which provides for the measurement within the
given range with an error margin of no more than 8 m.
4.4. To determine the thickness of the nondrip wet layer, enamel is applied to steel
plates not less than 150150 mm in size by means of an applicator.
4.5. To determine the abrasion resistance, enamel is applied in one layer on one side
of glass plates made from special-purpose glass 9060 mm in size and 1.2 mm thick. Enamel is applied by an applicator with the height of the slit 200 m.
4.6. Before the determination of the colour and appearance, impact strength, bending
strength and adhesion of the film, specimens are dried at a temperature of 202C for 24 h.
4.7. Before determining the resistance to water and abrasion resistance, specimens
dried at a temperature of 202C for 24 h are held for complete hardening at a temperature
of 802C for 1 h or at a temperature of 202C for 6 days. Prior to the test, the specimens
hardened at the increased temperature are held at room temperature for no less than 1 h.
5. The colour and appearance of the enamel film are determined visually at natural
light or artificial diffuse daylight.
6. The weight fraction of volatiles is determined in ready-to-use enamel according to
GOST at a temperature of 802C for 2 h.
7. Determination of the thickness of the nondrip wet layer.
7.1. Devices and materials:
applicator as per GOST with the slit height of 0.5 mm; 0.3 mm;
spatula or glass rod.
7.2. Carrying out the test.
Ready-to-use enamel is applied by an applicator from the centre to the edge of the plate
such that the length of the trail of paint be no less than 100 mm. Then the plate is installed
vertically, the painted part up, and the dripping is observed for 1 h. The temperature of the
air during the test should be within the limits of 202C. The thickness of the nondrip wet
layer is no less than the value set by the applicator, if the dripping is not observed during
the examination. A displacement of the layer of material relative to the support is considered to be a dripping. A sag (of up to 1 mm) on the lower boundary of the layer of the material is admissible.
8. The resistance of the film to the static effect of water is determined according to
GOST.
Tested specimens are held in distilled water at a temperature of 1002C.
After holding in liquid media, specimens are wiped with a soft wiping cloth, held at a
temperature of 202C for 1 h and examined visually.
Regularities of grain contamination with toxins secreted by fungi at various stages of
grain growth and processing, as well as the effect of mycotoxins on the ecological safety of
food for man and animals, have been established based on the works performed at the
444
All-Russian Institute of Grain Research (VNIIZerna) and its branches for over 30 years on
problems of microbial pollution of grain and it its products.
Domestic grain is subject most often to accumulation of aflatoxins B1 and G1. The
most hazardous regions from the ecological point of view are the southern regions of European part of Russia, Ukraine, Moldova and Kazakhstan.
An increased-risk crop is maize. In some regions, aflatoxin B1 was found to affect up
to 40% of maize lots; in Southern Caucasus, 14%.
Small-grain cereals (rye, wheat) are more resistant to the damage by the fungi Aspergillus flavus and contamination by aflatoxins.
The routes of pollution by mycotoxins were fount to be as follows:
Unfavourable conditions of storing grain mass due to the violation of the temperature-moisture regime. This leads to mold development and spontaneous heating. The localization zone of mycotoxins is the surface layer of the grain;
Mycotoxins affect the head and grain in ripening in the field. In some years, products
of their vital activities affect wheat grain batches of up to 4 million tons;
The degree of contamination of grain depends on the anatomic features of a crop, the
character of development of producing fungi, the chemical properties of mycotoxins, as
well as on the technology of storage and processing.
Mycotoxins concentrate mainly in bran and feed wastes, which is predominantly
caused by the surface growth of saprophyte species of fungi.
The content of aflatoxins B1 in bran exceeds that in initial grain 34-fold, whereas in
flour it was 14 times smaller.
As the fungus and mycotoxins penetrate deep into the grain kernel, processing of affected wheat only leads to a weak decontamination of the product. All sorts of flour
(4954% of the grain content) are contaminated uniformly.
The same high concentrations of mycotoxins are observed in bread, which makes affected grain hazardous.
In chaffy crops (rice, barley), considerable part of mycotoxins is removed with husk;
an insignificant part of mycotoxins get into grits.
13.3.1 Modified coatings of tanks for storage of vegetable oil
Storage of vegetable oils is accompanied with changes, which affect their food value and
biological value.
The quality of vegetable oil is determined to a large extent by its stability with respect
to spontaneous oxidation by atmospheric air.
Oxidized oil has a reduced biological value of fats and decreased organoleptic properties (taste, smell, colour, consistence), the most characteristic of which is rancidification.
In storage, all oils are subject to oxidative and autooxidative rancidification, i.e., the
emergence of specific unpleasant flavour and smells.
The mechanism of oxidation and major processes, occurring in vegetable oil and other
fats in storage, have been fundamentally studied.
The extent of oxidative changes of oil in long-time storage depends on a number of
factors: particular features of the chemical composition of raw materials; production process, catalytic action of transition metals and secondary oxidation products on oxidation,
storage temperature, packaging materials or materials of the storage tank, etc.
The authors have shown that one of the factors initiating the autooxidation processes
of vegetable oil are ions of heavy transition metals (Me), such as Ni, Co, Fe, Mn etc.
445
CHAPTER 13
During the storage of vegetable oil in vertical steel unprotected tanks made from steel
grade 3, the initial content of iron ions increases in 1218 months more than 2 times, which
is seen in Table 13.7.
Table 13.7 Content of iron ions in vegetable oil samples.
Iron content in an average sample, mg/kg
Initial data in an average
sample
0.210
0.295
0.488
0.500
0.700
0.507
0.450
0.550
0.500
0.620
After 12 months
of storage
0.310
0.443
0.570
0.665
0.765
0.818
0.665
0.825
0.742
0.882
After 18 20 months
of storage
0.405
0.487
0.586
0.700
0.825
0.700
0.885
0.825
1.107
0.557
0.578
0.785
0.850
0.800
1.107
0.945
0.887
1.200
1.100
0.565
0.500
0.785
0.975
1.050
1.130
0.990
0.995
1.230
1.150
Iron present in oil in the amount of 0.250.28 mg/kg increases the intensity of forming
peroxides of organic compounds of oil 1.52-fold. An even greater oxidation intensity
should be expected from the presence of iron in an average oil sample in the amount of
0.8821.100 mg/kg.
At the same time, iron was noted to concentrate in the lower layer of oil in the residue,
which is explained by the interaction of metal with proteins and phospholipids sedimenting
to the bottom of the tank. The increase of iron content in oil is noted to directly depend on
the amount of free fatty acids in it.
Earlier studies have shown that the mineral part of vegetable oil is represented by alkaline and alkaline-earth metals, as well as variable-valence metals.
The unprotected inner metal surface made from steel grade 3 is leached under the influence of vegetable oil. This leads to an increase of the content of iron compounds in oil,
which is seen in Table 13.8 presenting the dynamics of change of the iron content along the
height of oil during its storage in a tank (average climatic zone).
Table 13.8 Dynamics of the change of iron content in vegetable oil during storage.
Storage time,
months
0
6
12
18
24
30
36
Mass fraction of iron, mg/kg

Upper layer
Mid layer
Lower layer
2.39
1.47
0.68
0.39
0.44
0.36
2.42
2.56
1.75
0.88
0.76
0.47
2.44
3.68
5.26
7.13
7.07
7.39
446
From the data presented, it follows that the initial period of oil storage is characterized
a rather uniform distribution of iron ions in the bulk of oil. Further on, the content of iron
in the upper and mid layers was gradually observed to decrease (by 75%) at a simultaneous
increase (2.5 times) in the bottom layers.
This indicates the migration of iron from top to bottom, probably, in the form of organomineral compounds (salts, complexes) formed as the result of interaction with free fatty
acids of oil. Unfortunately, the form of organomineral compounds in oil is not yet clear.
The classical scheme of hydrocarbon oxidation requires the presence of Me in its highest valence:
Me + RH --- Me + R + H
Me + O --- Me + O
propagation of the chain reaction
The high catalytic activity of transition metals can be seen by example of Fe+3, which
accelerates the oxidation of linolic acid C17H29COOH or its methyl esters at the addition
of 1 part of ironporphyrin complexes per 100 mln parts of acid. The similar catalytic properties are exhibited by solutions of iron salts in oxidation of fats.
It is commonly recognized that copper and iron are the most efficient catalysts of the
oxidation of edible fats.
It was shown that if Me occurs in fats in small concentrations (1 mg/g fat), then by
their catalytic activity they are arranged in the sequence:
Cu > Fe > Ni > Zn > Co > Mn,
and at large concentrations of Me in fats (10 mg/g) this sequence looks as follows:
Fe > Cu > Co > Mn > Ni > Zn.
Metal catalysts can have various effects on the rancidification process of vegetable oil:
affect the initiation rate of the autooxidation chain process by a direct reaction between the catalyst and the oxidized vegetable oil molecule;
at the stage of development of the oxidation chain reaction, they can catalyze the degradation of hydroperoxides to free radicals and accelerate the autooxidation reaction:
Me + ROOH - - - Me + RO +
Me + ROOH - - - Me +RO +
can stipulate the termination of the oxidation chain reaction, for instance, for an aqueous solution of hydrogen peroxide:
Fe + - - - Fe + +
Fe + - - - F +
Fe + - - - Fe +
Analysis of the already published works on long-term storage of vegetable oil and the
classical views of the oxidation of organic compounds in the presence of variable-valence
metals indicate that a required measure for stabilization of the quality of oil in its storage
in tanks is protection from oxidation initiators, i.e., from the direct contact of metal with the
food product.
CHAPTER 13
447
The most convenient method of protection is the anticorrosion coating based on oilresistant lacquer-and-paint material, which should conform the following requirements:
the coating should not contain toxic impurities and additives, which impart vegetable
oil with off-flavour and taste;
the coating should be resistant to oil within a certain temperature range;
the coating should have satisfactory adhesion and physicomechanical properties
(elasticity, hardness, impact strength etc.).
Companies in the West widely use epoxy coatings for palm oil storage tanks, as well
as reinforced polyester coatings, lining with thin stainless-steel sheets, deposition of a thin
layer of titanium.
The aim of the study was to issue recommendations on the anticorrosion protection of
the internal surface of steel tanks intended for long-term storage of oil. The tasks of the work
were as follows:
choice of protective coating;
accelerated tests of chosen materials in contact with oil;
analysis of the quality of oil after the accelerated tests;
by the results of the test, preparation of technical documents for the Moscow City
Centre of the Russian Sanitary Epidemiological Control Committee;
procurement of the hygienic certificate for the recommended coating.
Food-grade compositions were chosen for contact with vegetable oil. A total of 12
types of coatings were tested; after contact with vegetable oil, satisfactory results were
shown by three compositions, whose characteristics are presented below.
1. Food-grade epoxy composition EP-1M.
Quality parameters of the base and ready-to-use enamel are given in Table 13.9.
Table 13.9
Index
BASE
Colour
Appearance
Degree of grind, m, no more than
Value
White, brown, rose
Homogeneous viscous mass without foreign
inclusions
40
ENAMEL
Appearance and colour of film
Upon drying, film is smooth and

homogeneous
Mass fraction of volatiles, %, no more than
5
Thickness of non-dripping wet layer, mm, no more
0.5
than
Time of drying to degree 3 at 20C, hours, no more
24
than
Impact strength of film by U-1 instrument, cm (g),
30 (0.3)
no more than
Adhesion of film, points
1
Solvent
Alcohol acetone mixture
The composition is permitted to be used in contact with many food products: sugar
molasses, wheat, 20% ethyl alcohol, meat products, etc.
448
2. Food-grade polyurethane, permitted for contact with potable water.

The physicomechanical properties are given in Table 13.10 (certificate No 000412 of
12/04/1995 for contact with food products).
Table 13.10
Index
Colour
Relative elongation, %
Breaking strength, MPa
Shore hardness A, arb. units
Impact resilience, %
Tearing strength, kN/m
Brittleness temperature, C
Shrinkage, %
Value
Milky white without inclusions
400 500
18 22
65 75
25 30
60 65
minus 65
not available
3. Food-grade epoxy enamel EP-2M. The physicomechanical properties are given in

Table 13.11.
Table 13.11
Index
Viscosity by VZ-246, sec, no less than
Content of nonvolatiles, wt. %, no less than
Impact strength, N/m, no less than
Adhesion, points
Viability at 20C, no less than
Solvent
Value
Homogeneous viscous mass of gray colour
30
90
5
1
6
Alcohol acetone mixture
Crude sunflower oil, quality category 2, was chosen as the object of study in contact
with polymer coatings.
Sunflower oil has parameters of quality, presented in the quality certificate.
Method of accelerated tests of vegetable oil in contact with polymer coatings
Accelerated oxidation of vegetable oil with specimens of coatings and a control without a coating was carried out in a ST-80-2 thermostat for 60 h (6 h per day) at a temperature
of 40C in sealed glass vessels without access of oxygen of the air, which corresponds to
18 months of the storage of this product in a steel tank.
Vegetable oil was taken in terms of one litre per one sample in contact with 5 cm2 of
each type of coating, which corresponds to the stringency of the test with respect to fullscale investigations as 1.5:1 for RVS-700 and 2:1 for RVS-400.
13.3.2 Results of tests
The results of the tests are represented by the following characteristics of the objects of
study.
449
CHAPTER 13
1. Vegetable oil:
physicochemical and organoleptic characteristics of quality,
composition of the volatile part of oil,
parameters of safety of oil in accordance with safety regulations MVT 506189.
2. Polymer coatings: the list of component parts of formulations.
The physicochemical and organoleptic characteristics of quality after accelerated tests
in contact with polymer coatings are given in Table 13.12.
Table 13.12 Characteristics of quality after accelerated tests.
Quality index
Moisture and volatiles, %,

no more than
Content of phosphatides,
wt. % in terms of
phosphorus pentoxide, no
more than
Acid number, mg KOH, no
more than
Norm
Initial
specimen
After accelerated tests

Specimen Specimen Specimen
6
7
8
Control
0.30
0.15
0.075
0.080
0.084
0.078
0.070
0.021
0.021
0.022
0.020
0.020
6.0
3.52
2.97
3.03
3.00
3.05
Organoleptic indices
Transparency: specimens are transparent without residue.
Smell and taste: peculiar of sunflower oil without foreign smell, off-flavour and bitter taste.
Analysis of the content of trace elements

Weights of specimens of vegetable oil Nos 6, 7, 8, 10 (control sample) were subjected
to wet cineration according to the standard method in an MSD-2000 microwave oven. Three
parallel samples of each specimen were taken for the analysis.
Elemental analysis was carried out on a Liberty-200 inductively coupled plasmaemission spectrometer (Varian).
The chosen analytical lines, nm:
Cu 324.754
Cd 214.438
Pb 220.353
As 188.979
Hg 184.950
Zn 206.200
Fe 259.940
P 178.284
Ca 317.933
Ba 493.409
Sr 421.552
Si 251.611
Ti 334.941
The contents of calcium, barium, strontium, silicon and titanium were determined
because they are present in the components of the coatings.
Conditions of recording the spectra:
power 1.5 kWt,
consumption of argon in plasma 15.0 l/min,
consumption of argon for blowing off the burner 2.25 l/min,
consumption of analyzed solution 1.5 ml/min,
pressure on the atomizer 100 kPa,
viewpoint optimized by the signal/noise ratio,
integration time 5 s,
replication number 5.
The calibration was carried out by the Merck standards.
450

Table 13.13 Elemental analysis of specimens after accelerated tests.
Index
Mass concentration of lead

Mass concentration of cadmium
Mass concentration of arsenic
Mass concentration of mercury
Mass concentration of copper
Mass concentration of zinc
Mass concentration of iron
Mass concentration of calcium
Mass concentration of barium
Mass concentration of strontium
Mass concentration of titanium
Mass concentration of silicon
Mass concentration of
phosphorus in terms of
phosphorus pentoxide
Unit
measure
Norm
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
0.10
0.05
0.10
0.03
0.50
5.00
5.00
below norm
below norm
below norm
below norm
below norm
350
Specimen
6
10
<0.01
<0.01
0.02
<0.001
<0.10
3.20
1.90
48.0
0.63
0.26
absent
absent
205
<0.01
<0.01
0.02
<0.001
<0.10
2.90
1.80
51.0
0.57
0.26
absent
absent
216
<0.01
<0.01
0.015
<0.001
<0.10
3.20
1.70
46.0
0.54
0.24
absent
absent
196
<0.01
<0.01
0.02
<0.001
<0.10
3.10
1.80
51.3
0.62
0.25
absent
absent
203
From the data presented in the table, it follows that:

by the content of toxic metals Cu, Zn, Pb, Cd, As, Hg, Fe all investigated samples of vegetable oil correspond to the safety criteria,
the concentration of Ca, Ba, Sr, Ti and Si, present in anticorrosion coatings components, is not increased in samples of vegetable oil,
the concentration of phosphorus-containing substances is within admissible limits.
Study of specimens of vegetable oil by the method of chromato-mass-spectrometry
Volatile components occurring in vegetable oil were isolated using a Kuznetsov concentrator by transferring them into the phase of normal hexane.
The concentrates obtained were analyzed by the method of chromato-mass-spectrometry on a Saturn-3 instrument (Varian).
Chromatographic parameters:
DB-5 quartz capillary column (analogue of SE-54), length 30 m, internal diameter
0.25 mm, thickness of the film of the immobile phase 1 m;
temperature regime: stage 1, 0.1 min at 40C; stage 2, temperature increase up to
100C at a rate of 20C/min and holding for 3 min at 100C; stage 3, temperature increase
up to 200C at a rate of 5C/min and holding for 20 min at 200C;
SPI-type injector (direct input) with temperature programming: initial temperature
60C, then heating at a rate of 225C/min up to 250C;
input pressure: 0.6 atm.
Mass-spectrometric parameters:
range of masses: 41450,
type of ionization: by electron impact,
scanning rate: 1 spectrum/s,
451
CHAPTER 13
ionization time setting: automatic.

Investigated samples are totally identical, which indicates the absence of the leaching
of volatile organic components of anticorrosion coatings in their contact with vegetable oil.
Analysis of the content of chloroorganic pesticides
Vegetable oil (12 ml) was placed into a 200-ml conical flask, 1015 ml of n-hexane
was added, and the contents were subjected to extraction for 1520 min on a shaker. The
extracts were purified in flat-bottomed flasks on a slide by shaking for 57 min with 510
ml saturated solution of anhydrous sodium sulfate in concentrated sulfuric acid. After settling, the extract was decanted into another flask. The contents of the flask with acid after
the primary purification was rinsed with 12 ml hexane, which was added to the main extract. Purification was done several times until the layer of acid after mixing was colourless.
The purified extract was transferred into a separating funnel, 25 ml of 0.5 n sodium
bicarbonate solution was added, the contents were shaken for 12 min, the aqueous part
was discarded, then the extract was washed with distilled water to the neutral reaction of
the washing waters. The final extract was filtered through anhydrous sodium sulfate into a
flask for distillation of the solvent.
The solvent was evaporated on a rotary unit to a small volume (57 ml), then in a
nitrogen flow to a volume of 0.51.0 ml and was analysed by the method of gas-liquid chromatography on a Star 3400 CX instrument (Varian).
Two samples were arbitrarily chosen and analysed: No 10 (control) and No 6.
Chromatographic conditions:
DEZ electron capture detector;
DB-5 quartz capillary column, length 30 m, internal diameter 0.25 mm, thickness of
the film of the immobile phase 1 m;
temperature regime: stage 1, 1 min at 90C; stage 2, heating up to 180C at a rate of
25C/min and holding for 10 min at 180C; stage 3, heating up to 240C at a rate of 2C/min
and holding for 20 min at 240C;
SPI-type injector (direct input) with temperature programming.
Qualitative analysis was performed by the retention times of standard compounds;
quantitative analysis, by the internal standard.
Table 13.14 Assay of the content of chloroorganic pesticides.
Index
Unit
measure
Regulatory
norm
Specimen 6
Specimen 10
Mass concentration of GHCG, sum of

isomers
Mass concentration of heptachlor
Mass conc. of DDT and its metabolites
Mass concentration of epoxy heptachlor
Mass concentration of endosulfon 1
Mass concentration of dieldrin
Mass concentration of endrin
Mass concentration of endosulfan 2
Mass concentration of endrin aldehyde
Mass concentration of endosulfan sulfate
mg/kg
0.05
0.012
0.013
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
mg/kg
not admissible
0.10
below norm
below norm
below norm
below norm
below norm
below norm
below norm
absent
0.005
absent
0.006
absent
absent
absent
absent
absent
absent
0.0042
absent
0.008
absent
absent
absent
absent
absent
452
From the data presented, it follows that by the content of chloroorganic pesticides the
investigated samples of vegetable oil correspond to the safety requirements.
The constituent parts of the formulations of coatings: enamel EP-1M, food-grade polyurethane, enamel EP-2M.
Conclusion
The results of the tests of quality and the technical documents for the coating EP-1M
were handed over to the Moscow City Centre of the Russian Sanitary Epidemiological Control Committee. Based on this, we received a certificate for the safety of use of the coating
EP-2M in contact with oil, and developed the process of its application to the internal surfaces of steel tanks with the guarantee period of 15 years.
13.4 Food-grade coatings resistant to the action of sign-variable

temperatures
We developed compositions for food- and technical-purpose coatings, resistant to the action
of various reagents and sign-variable temperatures, as well as process documents for their
production and applications.
Enamel is intended for protection of the inner surfaces of steel and concrete tanks for
storage and processing of 96% alcohol, alcohol-containing products, including beer, malt,
cognac, vodka, wine; cold potable water, juices, lemonades, other cold drinks, oil-containing products, including vegetable oil. It is admissible to be used for protection of highcapacity reservoirs operated in contact with granular food products (sugar, flour, grits,
grain, etc.). The operation temperature range, from 25 up to +40C. It is permitted to be
used for protection of sewage systems, as well as for painting of walls and ceilings in public
baths and pools.
Peculiar features of coatings:
the coating possesses high anticorrosion properties, resistance to organic media,
fresh and sea water, oils, petrol, detergents; admits steaming. The durability of the coating:
57 years;
thixotropic materials; enable application of a required thickness of coatings in two
layers;
low content of volatile substances, 5%.
Main characteristics:
two-package materials based on epoxy resins and amine-type hardeners; hardener :
base ratio, 20 g / 100 g;
colour: creme, brown; tints not rated;
appearance of the coating: homogeneous semiglossy;
methods of application: by airless spraying, brush or roller;
spreadable life of materials at temperatures from 5 up to 30C: from 2 to 0.5 hours;
a layer of coating dries at a temperature of 20C for 24 hours;
consumption of materials per layer: 250350 g/m2;
recommended number of layers, 2; total thickness of coating, 400 mm;
guaranteed storage time of the base, 12 months; of the hardener, 6 months.
Recommendations on use:
Preparatory work
The metal surface should be cleared of rust, scale, metal oxides etc. to grade 2 according to GOST (the surface should have a uniform roughness, metal gloss; a darker hue of
CHAPTER 13
453
metal is admitted on areas cleared of scales) and degreased to grade 1 according to GOST
(no traces of grease on filter paper after wiping the surface). Cleaning should be done by
sand-blasting or shot-blasting treatment; it is permitted to use cord brushes. For degreasing,
the surface of metal is cleaned by wiping cloth soaked in white spirit and by dry wiping
cloth; use of easily volatile solvents is not permitted. If painting is to be done immediately
after the sand-blasting (shot-blasting) treatment, degreasing could be not carried out; herewith, it is recommended to degrease too dirty areas preliminarily. If it is necessary to paint
components of vessels fabricated from alloy steels, aluminium, titanium or copper alloys,
the metal surface should be painted with a very thin (not more than 20 m) layer of phosphatized primer VL-02 or VL-023 to provide for adhesion.
The surface of concrete should be completely cleared of dirt and the old coating. The
fresh concrete surface should be matured for no less than 1 month before application of
enamel, slightly scraped to open pores in concrete and dust should be removed.
The test for the determination of the completeness of water removal from concrete: a
segment of the tank of no less than 1 m2 area is covered with a rubber mat or closely fitting
piece of polyethylene film and left for 24 hours. If the covered segment did not become dark
and there are no drops of condensed water, the concrete is ready for application of the
coating.
The maximal interval of time between the preparation of the surface and the application of the coating is 24 hours.
Painting
The temperature of the base and hardener before the application should be within the
range of 1530C. Prior to the beginning of work, the base and hardener are well mixed to
homogeneity over all the volume of the can; dry films should be preliminarily removed
from the surface of the hardener, if they were formed.
Enamel is applied by airless spraying units, by a roller or a brush.
In application by airless spraying units with separate supply of the components, the
base to hardener volume ratio of 3.5:1 is maintained; it is admissible to warm the components up to a temperature of 4060C.
For application by a brush, roller or an airless spraying unit with the supply of the prepared mixture, the material is prepared by adding 20 g of hardener for 100 g of the base and
thoroughly mixing. It is admissible to add ethyl alcohol, a mixture of ethyl alcohol with acetone at a ratio of 1:1 or another solvent in the amount of no more than 10% of the weight
of the ready-to-use material. The composition of the solvent is chosen with consideration
of the sanitary requirements to the coating. The material is prepared by portions of no more
than 20 litres (taking into account the spreadable life). It is recommended to prepare portions for 2030 min of work.
Enamel is applied to metal in two layers. The drying between layers should be up to
grade 3 according to GOST (to the disappearance of tackiness;24 hours at 20C). When preparing enamel for the first (priming) layer for concrete, it is to be diluted with ethyl alcohol,
a mixture of ethyl alcohol with acetone at a ratio of 1:1 or another solvent suitable for dilution of epoxy materials in the amount of about 50% of the mass of enamel. The composition of the solvent is chosen with account for the sanitary requirements to the coating.
The first (priming) layer of diluted enamel on concrete is dried for no less than 24
hours, then two layers of enamel are applied, with intermediate drying up to grade 3 according to the State Standard (GOST). The enamel for application of the subsequent layers is
prepared without dilution or with dilution of no more than 10%.
The maximal interval between the painting of the layers is 3 days after the last layer
454
has dried. If the interval is larger, it is recommended to sandpaper the surface to a matte
finish and to remove dust.
The number of layers is chosen such that the total thickness of the hardened coating
be 350400 m.
Material is applied at an ambient temperature of 10 up to 30C and relative humidity
no more than 80%; the temperature of the painted surface should be higher than the dew
point.
Before operation begins, the tank painted with enamel should be washed according
to the tank-washing instruction in force at the enterprise.
It is preferable to use neutral or alkaline detergents.
The duration of holding a coating after drying the last layer before the washing:
at a temperature of 20C and higher, no less than 10 days,
at a temperature of 1519C, no less than 15 days,
at a temperature of 515C, no less than 30 days.
After washing, the painted tank is filled with tap water, held for 24 h and a sample is
taken to determine the weight fraction of migrating chemical substances, smell and taste. If
the weight fraction of migrating substances, smell and taste do not correspond to the norm,
the washing is repeated.
Safety precautions
Material is highly inflammable! Harmful if inhaled or swallowed. Do not work near
open fires. Work should be done in rubber gloves with good ventilation in the working area.
If material gets onto the skin, wash the skin with warm water and soap. Keep material indoors, excluding direct sunlight and moisture.
14
Ecology and Safety

of Utilization of
Container/Packaging
Materials
14.1 Methods of utilization of packaging materials

Since the time the first polymer materials appeared, much effort has been used to solve the
problem of their stabilization and extension of their service life. This problem has not been
completely solved until now. However, as production and consumption of polymers increased, it became clear that many polymer materials, in particular, those for packaging,
have excessive lifetimes. The most heavy-duty polymers polyolefins, polyvinyl chloride and polystyrene are not subjected to biodegradation and are preserved under natural
conditions for many years.
In countries with developed polymer industry, plastic containers, films and packaging
materials have become one of the major sources of pollution of forests, fields, rivers and
sea coasts.
According to the available data, wastes are and will be in the near future about 30% of
the total output of plastics. A significant part of wastes of polymer materials are films and
packaging materials. These are just the sort of wastes, which are most difficult to collect.
It should be noted that wastes of polymer materials are valuable resources, which can
be recycled and used again both as polymer materials and as raw materials for production
of monomers, oligomers, lubricants, construction materials, and as fuels.
Issues of regulating the degradation rates of polymer material wastes, which do not get
into the collection system and become a source of pollution, have been considered.
Wastes of polymer materials were analyzed in the USA. It turned out that 90% of all
wastes are three polymers: polyethylene, polyvinyl chloride and polystyrene (21%). According to Swiss data, wastes of polyolefins are 55%; polystyrene, 15; and polyvinyl chloride, 13%,; i.e., these polymers make 83% of all wastes. Therefore, it is necessary to
develop methods of increasing the rates of decomposition of namely these polymers.
Polymers degrading under natural conditions at a growing rate are used in the West to
produce not only packaging materials, but also agricultural films for mulching, which degrade over one season. Thus, for instance, the output of such films in Japan is at present
25,000 tons per year.
It is desirable that polymer wastes getting into the environment degrade under the
action of natural conditions: light, oxygen, air, water, microorganisms, fungi. However,
456
studies have shown that polyolefins, polystyrene and polyvinyl chloride are preserved under natural conditions for an extremely long time, for many years. Measures are, therefore,
required to accelerate the degradation processes. Polymers rapidly degrading under natural
conditions should satisfy a number of requirements dictated by the conditions of its applications:
polymers should degrade rapidly, but only after they are discarded, not in processing,
storage and performance of a respective article,
time to degradation should be known beforehand and should be variable,
the consumer should be aware of the time when rapid degradation of polymer begins,
modification of polymer, which leads to an increase of the rate of decomposition under natural conditions, should not significantly change its performance characteristics.
Only polymers degradable under the action of light and biodegradable to a lesser extent satisfy these requirements. Therefore, we shall consider the works on the development
of photodegradable polymers. It is those works that led to the creation of polymer materials,
degradable sufficiently rapidly under natural conditions.
14.2 Accelerated degradation of polymers by biocides

Experiments with aliphatic low-molecular-mass direct-chain hydrocarbons modelling
polyethylene showed that biodegradation proceeds to a molecular mass M < 450 (C32).
Chain branchings prevent the assimilation of hydrocarbons by bacteria. If polyethylene is
subjected to pyrolysis, biodegradation proceeds when the average molecular mass of polyethylene reaches 3,0001,000. For biodegradation of polystyrene to become possible, its
molecular mass should be less than 4,000 (by the number of links, equivalent to polyethylene with a molecular mass of 1,000). Thus, for the biodegradation of these polymers to begin, they should be preliminarily decomposed to low-molecular-mass products.
14.3 Photodegradable polymers

Photodegradable polymers have no drawbacks mentioned above. A given polymer resistant
to the action of light can be converted to a photodegradable polymer either by using additives or by introducing light-sensitive groups or groups with weak bonds into the macromolecule. Only variations of these two principles are discussed and are used in practice. It
should be noted that it is sufficient to bring decomposition of macromolecules under the
action of light to a molecular mass of 5001000, because hydrocarbons with such a molecular mass, as we noted above, can be assimilated by microorganisms and, thus, be included
into the natural biological cycle.
Ketone groups are usually introduced into macromolecules to produce photodegradable polymers. This is due to the fact that these groups are rather resistant to processing conditions, whereas under natural conditions under the action of light they degrade. The light
with the wavelength of more than 350 nm is not absorbed by ketones, especially aliphatic
ones. Therefore, polymers with ketone groups are stable indoors.
Polymers are produced by copolymerization of common monomers styrene, ethylene, vinyl chloride with monomers of the structure
R
C
R1C
CH2
O
CHAPTER 14
457
or carbon oxide. In the former case, polymers with the ketone group in the side chain are
obtained; in the latter, in the main chain. By varying the nature of R and R, as well as the
concentration of the chromophore groups, we can obtain, e.g., based on ethylene, polymer
degradable under natural conditions in the time from several hours up to several months.
Ketone groups can be also introduced into ready-prepared polymer. Thus, interaction
of copolymer of ethylene and vinyl alcohol with diazo acetophenones yields a polymer containing aryl ketone groups in the side chain. The rate of decomposition of this polymer depends on the structure of the substituent in the aromatic nucleus of ketone.
Using the method of copolymerization, it is possible to introduce not only ketone
groups but also aldehyde groups. Thus, for instance, copolymerization of methyl methacrylate or styrene with propiol aldehyde yields a polymer degradable under the action of light
much faster than corresponding homopolymers. However, the decomposition rate of copolymers of styrene or methyl methacrylate with methyl vinyl ketone is much larger under
these conditions.
Studies of polyolefins showed that the processing conditions of polymers render a significant effect on the light permanence of articles. Thus, the heating of high-density polyethylene at 200C decreases the time to cracking of the film prepared from this polymer
with the extent of oxidation increasing under the action of light. Thermooxidation of the
polymer was shown to occur under these conditions. The main oxidation products are polymer carbonyl-containing compounds. Thus, heat treatment leads to the formation of chromophore groups, mainly carbonyl ones, and can be considered as one of the ways of
chemical modification of the polymer.
Chromophore groups can be also introduced by way of a special treatment of a completed article. For instance, a completed polyethylene film can be converted into a photodegradable one under the action of UV radiation in the presence of carbon oxide or a
mixture of methyl acetylene and tetrafluoroethylene. Products of grafted polymerization of
these monomers are degraded in the light and induce the conversion of polyethylene film.
Not only the method of copolymerization but also the method of polycondensation is
applicable for production of photodegradable polymers. Thus, for instance, Japanese
authors obtained from dioximes and diisocyanates polyoxime urethane film-forming polymers of the general formula:
(
ON
NO
NH
R'
NH
(I)
)n
As monomers, they used dimethylglyoxime (II), cyclohexandione dioxime (III) and

benzoquinoglyoxime (IV):
HON
(II)
NOH
CH3 CH3
HON
(III)
NOH
HON
NOH
(IV)
These monomers were polymerized with hexamethylene diisocyanate (V) or diisocyanate of diphenyl ester (VI):
O
(V)
458
(CH2)6
(VI)
A study of the light permanence of polyoxime urethane polymers showed their molecular mass rapidly drop down in irradiation. This is primarily due to the rupture of the weakest NO bond, whose energy is about 53 kcal/mol. The ester group breaks down slightly
slower.
It is known that polyolefins containing side aliphatic groups are oxidized under the action of light much easier than polyethylene. This feature of polymer photodecomposition is
used in production of photodegradable polymers. A method of producing polybutene-1 and
copolymers of butene-1 with ethylene and propylene or cis-butadiene was developed in the
USA. The polybutene-1 film of about 25 m thick decays in 2575 days depending on the
concentration of antioxidants, UV absorbers and other additives.
Double-bond polymers possessing a low light permanence are also used to produce
materials degrading under the action of the sunlight. Japanese investigators developed a
novel process for production of polybutadiene containing more than 90% of 1,2-structures.
Polybutadiene used in production of films possesses a syndiotactic structure and has a crystallinity of 1030%. A packaging from this polybutadiene degrades during the summer
time under the action of light in one week. Light stabilizers can extend the service life up
to several months.
14.4 Modified photodegradable polymers

Production of photodegradable polymers by synthesis of new polymers containing chromophore or reactive groups, as well as by modifying mass-produced polymers, requires the
existing polymer-producing technology to be changed or new processes to be developed.
Apparently, for this reason a major part of works seek to find efficiently acting additives;
what is more, mainly their action on polyolefins and polystyrene is investigated.
By their action, the additives used can be divided into the following groups:
photosensitizers,
additives preventing the crosslinking of macromolecules;
polymer oxidation catalysts;
complex metal compounds, which are stabilizers of polymers, but in the process of
recycling or photochemical decomposition of polymers are converted to oxidation catalysts. As photosensitizers of decomposition of polyolefins, it is proposed to use aromatic
hydrocarbons, aliphatic and aromatic ketones and diketones, quinones and other compounds; in particular, compounds mentioned in patents are aldol-2-naphthyl (VII), aldol-2(VIII) and aldol-1-naphthylamine chromone (IX), flavone (X) and xanthone (XI), 1,4-dialkyl-substituted benzene (XII), benzophenone (XIII) derivatives, p-benzoyl benzophenone (XIV); derivatives of acetophenone (XV), anthraquinone (XVI), benzathrone (XVII),
cumene (XVIII), mercaptobenzothiazole (XIX), acridine (XX), chlorinated aromatic compounds, aliphatic ketones (XXI) and diketones (XXII).
CH2CH(OH)CH2CHO
(VII)
CHCH2CH(OH)CH3
(VIII)
459
CHAPTER 14
(X)
(IX)
O
(XI)
(XII)
R'
(XIII)
C
O
(XIV)
O
C
(XVI)
CH3 (XV)
CH3
(XVII)
(XVIII)
CH
CH3
O
N
XSC
(XIX)
(XX)
N
R'
(XXI)
(XXII)
To accelerate photodegradation of polystyrene, additives were proposed, which are

close by their properties to those used for polyolefins, for instance, 1,4-naphthoquinone
(XXIII), 1-nitronaphthalene (XXIV), aromatic ketones (XXV)
O
NO2
(XXIII)
O
(XXV)
(XXIV)
O
460
and high-molecular-mass additives, for instance, halogenated polystyrene produced by the

action of chlorine or bromine on polystyrene.
The efficiency of sensitizers depends not only on the class they belong to but also on
the nature of substituents. Thus, quinones containing methyl groups or haloid atoms as substituents are more efficient, and amino and oxy groups less efficient, sensitizers of the oxidation of polystyrene than unsubstituted quinones.
Usually sensitizers are proposed to be used at concentrations from 0.01 up to 10%
(most often about 1%). As experience shows, at these concentrations they are consumed
much faster than the required polymer decomposition rate is achieved. However, photodecomposition of polymer does not stop after conversion of sensitizer, because by this time a
sufficient amount of photooxidation products of polymers are formed, which are also sensitizers.
The use of ketones and some derivatives of aromatic compounds as sensitizers is associated primarily with the fact that they initiate the conversion of polymer only under natural conditions, as such compounds are stable under conditions of polymer processing and
in storage of articles indoors, where the light gets through the window glass, which absorbs
a shorter wave component of the sunlight.
The mechanism of action of sensitizers in polymers has been studied insufficiently yet.
The action of compounds containing carboxyl groups, especially ketones, was studied the
most completely. Probably, this is due because the mechanism of photochemical reactions
of ketones in solutions has been studied the most completely. Compounds, containing carbonyl groups, are able in an electron-excited state to break loose H atoms from macromolecules or fall into radicals. Low-molecular-mass radicals formed react with macromolecules, thus initiating the oxidative decomposition of polymer. By analogy with the
known photochemical reactions of compounds containing CHal bonds in liquid and frozen solutions, it could be assumed that chlorinated aromatic compounds and halogenated
polystyrene fall under the action of light into radicals via the CHal bond. This process can
be sensitized, using compounds with sufficiently high levels of electron-excited states.
Probably, for this reason some works, to accelerate the decomposition of polymers under
the action of light, recommend to use mixtures of compounds with CHal bonds with
ketones.
The decomposition mechanisms of polymers sensitized by aromatic hydrocarbons or
heterocyclic compounds has been studied to a lesser extent.
The decomposition rate of polymers can be also increased by introducing substances,
which are photochemically inactive. Thus, additions of small amounts of paraffin or oleic
acid significantly increase the decomposition rate of polyethylene. It was shown that the
presence of these additive reduces the crosslinking of polyethylene, because additives are
added to macromolecules. Formation of the branched polymer in this process, in turn, accelerates decomposition.
Other photochemically active compounds, which can accelerate decomposition of
polymers, are oxidation catalysts. Usually, compounds of transition metals are used as catalysts: iron, copper, manganese, as well as metals in free state. Catalysts are used mainly in
a mixture with sensitizers. They accelerate oxidation of polymer during the action of sensitizer, and when the sensitizer is consumed, they complete the decomposition of polymer.
Sometimes, use is made of metal compounds, for instance, of iron naphthenate, which can
serve simultaneously as sensitizer and catalyst of polymer decomposition. The role of catalysts in polymers filled with carbon black or other pigments is less clear. Probably, films
from such polymers, owing to their opacity, are warmed significantly under the action of
CHAPTER 14
461
the sunlight, and the catalysts strongly accelerate the thermooxidation of the polymer. However, it is possible that the role of catalysts in these compositions is to accelerate the thermodecomposition of polymer mainly in processing, which is known to lead to a strong
decrease of the light permanence of articles. The latter hypothesis seems to be the most suitable to explain the increase of the decomposition rate of double-bond polyolefins and polymers in the presence of metal salts.
One of the most interesting classes of substances used as additives for accelerating the
decomposition of polymers are complex metal compounds, which stabilize polymers
but under the action of light or in the processing are converted to oxidation catalysts. An
example of such compounds are, for instance, dialkyl dithiocarbamates of metals (XXVI):
S
Alk
N
Alk
Me(n)
C
S
(XXVI)
Compounds of iron are the most efficient. The use of such compounds enables issues
important for practical purposes to be solved. The proposed additives protect the polymer
in processing. An additive can be chosen and adjusted in such a way that the polymer will
be also protected under natural conditions for a certain time. In practice, it is exhibited in
the occurrence of the onset of the polymer decomposition process in the presence of the additive. After the decomposition of the complex to form the catalyst, the decomposition rate
increases and the polymer is decomposed faster than the control specimen of the additives.
During the induction period, the coloration of the complex compound vanishes. By the
change of coloration, the consumer can determine the onset of the decomposition of the given article.
Using metal dialkyl dithiocarbamates, it is not possible to produce compositions with
a sufficiently high degradation rate under natural conditions, so the introduction of a photoactivator is proposed, for instance, iron acetyl acetonate. The value of the induction time
of photooxidation of polymer in this case will also depend on the concentration of photoactivator.
Besides the above said, another method of delaying the degradation of polymers is also
proposed. A water-soluble film containing a light stabilizer is applied to the surface of polymer, for instance, polypropylene. The film protects the polymer, but after it is removed the
article is rapidly decomposed.
The effect of additives on the rate of photodecomposition of polyvinyl chloride has
been studied much less. It is only known that polymethyl vinyl ketone does not affect the
rate of decomposition. Stearate and oxide of trivalent iron significantly accelerate the decomposition. Photodecomposition of polyvinyl chloride, in contrast with polyolefins, is little affected by iron dialkyl dithiocarbamates.
The main requirements to which polymer materials rapidly degrading under the action
of light under natural conditions should satisfy were noted above. We should add to them
three more uses of such polymers dictated by the practice:
polymers should be nontoxic, because their major applications are packaging materials;
costs of photodegradable polymers should not significantly exceed those for common polymers;
and finally, it is desirable that conversion of polymer to a photodegradable form does
not exclude the possibility of its recycling.
462
At present, there is no polymer or method of converting known polymers to photodegradable form(s), which would completely satisfy all these requirements.
The main advantage of the methods based on the introduction of chromophore groups,
or groups readily oxidized under natural conditions, into macromolecules is complete nontoxicity. However, if high-molecular-mass compounds are used as additives as, for instance, in the method of converting polystyrene into a photodegradable form at the addition
of halogenated polystyrene, or iron compounds are used, then it is also possible to obtain
photodegradable polymers, which are in practice nontoxic.
A disadvantage of the method of modification is, first of all, the need to change the
existing polymer production process, which would inevitably lead to an increase of the cost
of a polymer. Besides, the signal mechanism, which would indicate the fast degradation of
polymer, has not yet been developed for modified polymers.
Disadvantages of the methods of converting a polymer into a photodegradable form
by introducing additives are, first of all, the slow rate of degradation in the presence of small
concentrations of additives (of the order of several percent). Introduction of large concentrations of additives can lead to a significant change of the mechanical properties of polymer. Introduction of catalysts or substances, which change into oxidation catalysts, hampers
the reprocessing of the polymer.
Probably, for this reason some works make use of both the modification of polymers
and introduction of additives. Thus, organometal compounds salts of mono- and polycarboxylic acids; acetyl acetonates of copper, iron, manganese, chromium and some other
complex compounds of transition metals; also additives of light stabilizers are proposed
to be additionally introduced into copolymer of ethylene and carbon oxide (the content of
CO, 612 wt. %) as a degradation accelerator to produce articles with a preset lifetime from
polybutene-1 and 1,2-polybutadiene, because without stabilizers they degrade under natural
conditions too rapidly.
The extent of photodegradability of packagings largely depends on the place of their
disposal. Time to decomposition of a given article under natural conditions would depend
on the colour, thickness and shape of the article and not only on the properties of the initial
material.
Owing to great interest in photodegradable polymers, the most successful developments are introduced into industry.
Thus, polybutene-1 used for production of mulching films and photodegradable polystyrene are commercially available. Other photodegradable polymers being launched include copolymer of styrene with methyl vinyl ketone (Ecolight S), 1,2-polybutadiene, as
well as polyethylene and polystyrene, which contain additives accelerating their decomposition.
Mainly industrial production of films for agriculture is being developed, because the
requirements to them are more mild as compared with packaging materials, and they are
used within one season only. In the West, the use of such films is considered to be economically advantageous for the consumer. In the future, photodegradable packaging materials
would, probably, be also widely produced. Though it would require some additional expenses, their use would prove profitable for the society as a whole.
14.5 Principles of developing modifiers for biodegradable materials

1. Biodegradation of latex envelopes. Packaging materials are a means of protecting and
decreasing the losses of foodstuff production from the impact of the environmental factors.
CHAPTER 14
463
By protecting a product, the packaging contributes to the contamination of the environment.

To solve the problem of the polymer matrix, it is proposed to introduce polyfunctional
natural substances capable of simultaneously unifying the set of the performance properties
of polymers and to provide for its biodegradation after use.
The effect of a set of dietary supplements on the biodegradability of active latex envelopes was studied. Systems based on vinyl acetate modified by an activated mixture of lactic
bacteria (dietary supplement), rennin, were studied. A combination of polymer matrix and
dietary supplements affects the kinetics of the biodegradation process. Introduction of additives activating the growth of bacteria providing for the biodegradability under natural
conditions accelerates the fragmentary decomposition of the polymer matrix.
The increase of biodegradability of films in time is related to the structure of coatings;
dietary supplements are distributed in the bulk of the film between globules of polymers to
form the fragmentary structure of the film an aggregate of components united on the
supramolecular level.
As biodegradation (utilization) of the dietary-supplement additive by microorganisms
proceeds from the surface layers to deeper layers, the access to dietary supplements of the
deeper layers is facilitated, and biodegradation of the coating continues. The change of
character of the process at the initial stage of biodegradation using the enzyme as a dietary
supplement is related to the structural changes of the coating and the character of distribution of the enzyme in the polymer matrix.
2. Prospects of developing a biodegradable packaging from natural polymers. Ecologically safe containers and packagings can be rapidly degraded under natural conditions
or recycled to enable their use as feed additives.
For this purpose, an advanced method is to use accessible, cheap and rapidly reproduced natural raw materials for packaging materials. High-molecular-mass compounds of
animal and plant origin have a broad range of process and performance compositions for
coatings, film materials and consumer containers.
Thermoplastic compositions based on plasticized triple systems starchcellulose
derivativescollagen partial decomposition product were developed; also, the technology of their processing into container-and-packaging materials with polyfunctional properties conforming with modern requirements was worked out.
3. Promising self-degrading polymers. Coatings based on polyvinyl alcohol and
polysaccharides for protection of meat and fish products. Self-degrading polymers are degraded under the action of the environment much faster than traditional polymers. Their
degradation can occur under the action of bacteria, sunlight or chemically.
In world practice, much attention is given to biodegradable packaging materials, especially to polyolefins with addition of starch from cereal crops.
Biodegradable films based on polyvinyl alcohol with the contents of maize starch as
a biodegradable additive from 30 up to 150% were produced. The effect of the amount of
additive on the technological, thermophysical and stress strain parameters of films was
studied; the biodegradability indices were determined by the method of Shturm. Addition
of up to 30% of starch has no significant effect on all packaging characteristics of films; at
a concentration of starch over 50%, the stress strain properties of films decrease and the
biodegradation index drops down from 80 to 1.
The process parameters of producing biodegradable coatings based on polyvinyl alcohol modified by an optimal amount of starch were developed.
4. Use of reproducible plant raw materials for production of biologically degradable
polymer packaging materials. The use of polymers from natural raw materials or their
464
combination with traditional plastics makes it possible to solve some problems associated
with pollution of the environment, reduction of reserves, energy resources and global warmup of climate owing to the disturbance of the CO2 balance.
A rational approach from the technological point of view is to use natural polysaccharides starch and cellulose, which possess a set of valuable properties.
A method of producing biodegradable polymer materials with a wide range of plasticity and the required set of performance properties was worked out.
The regularities of the rheological behaviour of melts of thermoplastic starches plasticized with water, glycerol and their mixtures were studied.
It was found that tribasic alcohol in the plasticizing system increases the temperature
of the onset of gelatinization; studies of the transitions of the starchplasticizer system by
thermomechanical methods indicate that water and glycerol possess a selective effect on
polysaccharides.
They endow materials with a set of rational properties, such as elasticity, in the case
of plasticizing with water, and rubberlike properties when using glycerol.
Optimal thermoplastic properties are observed at a concentration of the plasticizing
waterglycerol mixture at a ratio of 25:25.
Thermoplastic starch is recommended to be used as a concentrate to endow synthetic
polymers with biodegradable properties.
14.6 Industrial and domestic plastics wastes

14.6.1 Secondary plastic raw materials in the public reproduction process
The raw materials base of the country is the sum total of raw materials available for a certain
period of time from its own stocks and from imports. The raw materials base includes primary and secondary raw materials. Primary raw materials are mineral resources and all mineral and biochemical raw materials mined in nature. Secondary raw materials are
production and consumption wastes, which can be returned into the public production process as a subject of labour, because they still preserved their value to a significant extent.
Industrial wastes are substances which in the process of social reproduction lost totally
or partially their initial consumer properties as a subject of labour or a subject of consumption. In the available form they are useless for a given or any other industrial process, i.e.,
are not consumed in processes of fabrication, conversion or refinement of a material.
Wastes emerging in the consumption sphere are previously used materials and articles.
They are assigned to potential secondary raw materials. As soon as wastes are transferred
by various methods into the form suitable for use, they immediately occupy their place in
the raw materials base of the country.
Primary plastic raw materials are understood to be materials, which are presented in a
suitable form for production of final or semifinished products from them. This, as a rule, is
associated with the formation or conversion of a substance. Secondary plastics raw materials are reprocessed into finished articles (once or many times).
Plastics are used in all branches of the economy, because this saves materials and increases the productivity of labour. Despite the finite resources of the majority of raw materials and increasing costs of their recovery, the consumption of raw materials constantly
increases. Polymer materials are characterized by higher rates of increase as compared with
other groups of materials. The state and volume of modern industrial production, the
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general exchange of industrial products with the environment has reached such a scale that
nature can not do without the conscientious activity of man to protect it. Costly works are
required to be carried out to prevent (or eliminate) the damage inflicted to the environment,
including that due to pollution by chemically resistant polymer materials.
On the other hand, major part of the countrys national income is spent due to the absence of our own sufficient raw materials base for purchasing polymer raw materials, whose
costs are constantly rising owing to the rise of energy expenses for their recovery and processing.
The existing macroeconomic situation makes it necessary to solve two main problems:
the efficient thrifty use of materials by reducing production wastes or using waste-free technologies and economy constructions; the economical efficient preparation of wastes for
processing and using as secondary raw materials.
Approximately 1011% of the demand in plastics should be covered by secondary
plastics raw materials. This necessitates investments into studies and developments in this
field, long-term plans for solving the problems associated with the reduction of the amount
of wastes and their rational use. Scientific research is to be carried out, new technologies
developed, industrial installations worked out, principles of decreasing the materials consumption in designing new plastic articles developed, drawbacks in this field eliminated.
In Germany, for instance, more than 400 various types of industrial wastes are produced at present; about 25% of them are used again. Simultaneously with the commitment
to reduce the amount of production wastes, it is necessary to increase the volumes of their
use, which leads to the decrease of the demand in primary raw materials, the decrease of
the costs of primary and secondary polymer raw materials.
A significant economic effect also arises due to the lower cost of secondary raw materials. The amount of plastics scrap in production and consumption constantly increases
despite the numerous measures to reduce the intensity of use of materials. When performing
scientific and technical measures for the development of small- or no-waste technologies
and respective equipment, it is necessary to take into account the issues of economic efficiency both within the framework of a particular enterprise and the countrys economy.
The complex character of the problem renders its solution difficult, as, for instance, in
the case of using household plastics wastes.
14.6.2 Sources and turnarounds of secondary polymer raw materials
Plastic wastes emerge in industry in production of materials, their processing, fabrication
of semi-finished products and articles, as well as in the consumption sphere as overage
articles.
Production wastes are used in the same production process (this is a closed turnover
of material, it is characterized by the lowest losses of material resources); in another production process after a respective preparation (this is a branched flow of materials); are not
used at all (the turnover of the material flow is theoretically closed via the environment).
One should always aim for closed turnovers, which save the material and yield the greatest
economic effect. The modern level of scientific-and-technical development makes it possible to create closed material turnovers.
Plastics are characterized by all these three forms of material turnovers. If a regenerate
of a thermoplastic is introduced into primary raw materials, and a mixture is produced for
the fabrication of the same articles as previously, we have a closed material turnover relative to production wastes.
466
Material I
Material II
Mining
Extraction
Production
wastes
Preparation
Preparation
of wastes
Processing (stage 1,
semifinished / finished
products)
Processing (stage 1)
Processing (stage 2)
Use
Processing (stage 2,
finished products)
Use
Consumption
wastes
Preparaition
of wastes
Harmless disposal
Scheme 14.6.2 Closed and branching turnarounds in plastics technology.
As multiple processing leads to a change of the structure and properties of material,

the deterioration of the properties being largely uncontrollable, regenerates are as rule used
for fabrication of articles with lower consumer properties. Here we have the case of a
branching material flow, because the regenerate is used in another process. When the regenerate of a thermoplastic is prepared from consumption wastes, prediction of the extent
of deterioration of the properties is the most difficult.
The third variant, i.e., the non-use of wastes, occurs especially frequently in production
of articles from thermosetting materials. Their wastes are subjected to long-time storage and
even disposal (incineration).
Secondary plastics raw materials are classified using various, mainly technological,
criteria, which enable conclusions on their possible applications. The criteria include the
place and sphere of origin (production or consumption wastes), as well as specific features
of appearance: contamination, type and shape. Using these criteria, one can characterize the
turnarounds of secondary plastics raw materials, singling out five different situations,
which require various economic, organizational and specifically technological measures for
their realization (Scheme 14.6.2, Table 14.6.1).
Turnaround I of the secondary plastics raw materials occurs in plastics-producing industry. Wastes include crusts formed on the walls of reactors and filters, off-standard polymers (decreased or increased molecular mass, undesirable isometry, non-standard size of
particles), as well as specimens of materials after physicomechanical tests. About 40% of
such wastes can still be sold as marketable products, and the other 60% are wastes proper.
In copolymerization of vinyl chloride, these are mainly deposits on the walls of reactors; in
production of polypropylene, atactic isomers; in production of polyethylene, low-molecular-mass products; and in production of styrene, too small or excessively large granules, etc.
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Partially, such wastes are used by producers of plastics themselves (by means of depolymerization, for instance, using the method of low-temperature pyrolysis or oxidative degradation). According to some estimates, in production of polyolefins the share of wastes is
about 1.2%, and on average in the plastics-manufacturing industry lower than 1% in different countries.
Table 14.6.1 Characteristics of turnarounds of secondary plastic materials.
Turnaround
of secondary
plastic raw
materials
Sources of secondary
raw materials
Industries producing
plastics
Industries reprocessing
plastics
Industries processing
articles from plastics
Single-type
Used plastics from

production and consumer spheres
Plastics from the sphere
of individual and public
consumption
Damaged
single-type
and combined
Damaged
mixed and
combined
II
III
IV
V
Type of raw
materials
Single-type
Single-type
and combined
Extent of
pollution
Appearance and shape
Not polluted Powder, granulate,

agglomerate
Not polluted Pieces of different size
Not polluted Pieces of different size,
film, canvas, bands, fibres,
pieces of foamed materials
Polluted
Articles, films, pieces of
foamed materials
Polluted
Articles, films
Turnaround II of secondary plastics raw materials is attributed to plastics-processing

industry (wastes are used at the same plants where they emerge). The procedures of using
wastes strongly differ from plant to plant. At present, the predominant method is collection
of same-type cast-gate wastes, rejects, other wastes emerging at the start-up of the processing machine. These wastes are usually comminuted in the cutting mill and then passed
through the single-screw extruder for homogenization, stabilization, dyeing and granulation. There are examples of automatic separation of manufactured articles and cast gates,
their automatic preparation and return to the same process. This method provides for the
highest purity and uniformity of type of material. There are no data on in-plant recovery of
wastes; the number varies from 3.1 up to 3.6%. According to German experts, the share of
turnover plastics material is about 5%.
The estimate of the total wastes of plastics-processing industries is 8.3%. In the USA,
the share of wastes in primary processing of plastics is assessed to be within the limits of
5.66.9%; from 1.9 up to 2.5% is not used subsequently. However, with introduction of
new processing technologies these estimates are constantly decreasing. Also, the share of
plastics scrap strongly depends on the type of material and method of processing. It is especially high in processing of polytetrafluoroethylene, polyurethane and epoxy resins, and
also foamed polymer materials.
Turnaround III of secondary plastics raw materials embraces thermoplastic production wastes occurring in the subsequent processing of semifinished products and articles.
Thermoplastic semifinished products pass further treatment (vacuforming, pressing, cutting, shaping) at a large number of plants, often very small (and even in craft workshops),
so the storage, preparation and re-use of emerging wastes requires the solution of many
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problems. Selection of one-type secondary raw materials is also complicated by the fact that
wastes mix with other materials, and in sites where they emerge personnel often has no sufficient knowledge of the processed materials to be able to collect them in a correct way.
Some important industries in Germany, oriented on the consumption of thermoplastic
secondary raw materials inside the country, were analyzed. The minimal calculated share
of thermoplastic wastes was 1.4% without the data for plants manufacturing packaging
means and fancy goods from artificial leather. With account for these plants, where the
amount of wastes is 9,000 tons, the total minimal share of wastes increases up to 1.6%.
In industry processing plastic semifinished products and components, the share of
wastes is 360 thousand tons a year or 6.55%. The use of these wastes is even more complicated, as their preparation and use can only in rare cases be done at the same plants where
they emerged.
Many technical problems also occur in connection with wastes of combined materials,
for instance, combinations of plastics with textiles. In Germany, such wastes make 17.6%
of thermoplastic wastes.
Turnaround IV of secondary plastics raw materials involves thermoplastic wastes,
which emerge in the production and consumption spheres as used products. These, for instance, are film materials in agriculture and packaging materials in trade. Such wastes are
usually strongly soiled, contain foreign bodies, are distinguished by increased moisture
content. Often over the years of operation the structure of materials has strongly deteriorated, as the result of which they should be subjected to additional preparatory operations on
special process equipment before being used as wastes. Of this group of wastes, the most
important are films from low density polyethylene, polypropylene bands and containers
from high density polyethylene. Available literature data on plastic packaging for chemical
industry are rather contradictory.
Turnaround V of secondary plastics raw materials covers plastics wastes of individual
and partially public consumption. A major part of such wastes is from households. They
are not of one type, are as a rule soiled and contain foreign bodies. Until recently, these thermoplastic wastes were considered unsuitable for use; however, interest in them constantly
increases in many countries. Special installations for their preparation and processing are
now being developed and phased in on the pilot scale. Due to the problems associated with
the control of the extent of deterioration, because of the variation of composition, wastes
are not separated by the type of plastics. Secondary plastics raw materials are produced with
relatively low mechanical properties.
Significant expenses for the collection of these wastes, as well as for their sorting and
cleaning are the main obstacles for their wide use.
14.6.3 Economic assessment of secondary plastic raw materials
The economic effect in the procurement, preparation and use of secondary plastics secondary raw materials should be calculated in the national aspect. This also concerns the technical solutions on the level of enterprises, which should be acted upon only taking into
account the interests of the economy.
The national economic effect is a complex value affected by a multitude of economic
and non-economic factors. The quantitative assessment of the economic effect of using secondary raw materials requires a system of absolute and relative characteristics, which reflect as closely as possible all expenses and positive results received by the economy.
Herewith, the criteria should be specified with respect to expenses and results:
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With respect to expenses:

One-time expenses
capital investment
training
Current expenses
prime cost
intensity of use of material
purchase prices
consumption of energy
Expenses for import
requirement in work force
pollution of the environment
With respect to results:
Profit, production volume, payback time
Economy of labour time, productivity of work, less work force is required
Economy of material
Quality of products, export potential
Economy of energy
Reduction of imports
Ecological characteristics, economy on the storage of wastes, less facilities are required, lower expenses for environment protection measures.
The purchase price for thermoplastic wastes should be stimulating and cover the expenses. It is known from experience that plants where wastes emerge do not want to give
them away free of charge or at a price just covering the expenses, if it becomes known that
secondary raw materials would be used further. Logically, this contradicts the fact that insignificant expenses for the harmless disposal of these wastes are compensated for by the
state.
There are various opinions on the collection of used plastics, and a certain experience
was accumulated in this field, based on which in Germany collection of household thermoplastic wastes was decided to be expedient.
The active use of secondary plastics secondary raw materials naturally requires significant capital investment. Available capacities are insufficient, and the required technological level has not been achieved to enable using previously used combined plastic materials.
Special production facilities are required, as well as transport means, packaging materials,
installations for compaction or grinding, additional personnel, which should be specially
trained.
Criteria with respect to the results can only partially be expressed quantitatively. One
of the possible characteristics is the ratio of the costs of secondary and primary raw materials; one should also take into account the level of properties of the regenerate. Material
and energy values present in wastes and relatively small expenses for recycling predetermine a significant economic effect, which is even greater due to the economy of primary
resources. It is known that production of 1 ton of polyethylene and 1 ton of PVC requires
the processing of, respectively, 32 and 16 tons of petroleum (the initial product can be specific petrol fractions of petroleum). Together with petroleum required for production of energy for processing of raw materials and for synthesis, it is required to use 1.9 tons of
petroleum to produce 1 ton of ethylene the monomer for polyethylene synthesis. With the
most advanced methods of synthesis, if we exclude the energy expenses, the petroleum
equivalent would be:
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1.6 ton of petroleum 1 ton of PE and 1.2 ton of petroleum 1 ton of PVC.
Production of primary plastic raw materials is extremely energy-intensive. The data of
Table 14.6.3 can give an idea of the total energy consumed and separately of the energy
used for polymerization for some widespread bulk plastics. These data form grounds in deciding upon the preparation of plastic wastes for use as secondary raw materials.
Table 14.6.3 Consumption of energy in production of plastics.
Plastics
HDPE
LDPE
PP
PVC
PS
Polyamide P-6
Polymethylene oxide
Total energy,
kWh/t
13.670
8.187
8.240
9.490
18.905
8.840
6.830
8.070
9.180
10.840
38.170
28.410
Energy for
polymerization,
kWh/t
Energy
equivalent*,
kWh/t
Enthalpy of
combustion**,
kWh/t
10.100
4.600
4.700
2.300
10.500
20.850
18.900
20.020
14.180
21.960
46.150
12.010
12.070
11.950
5.000
11.120
7.980
4.390
*Energy equivalent also includes the energy consumed for the cracking of raw petroleum, auxiliary
technological processes and additional substances, transport expenses and the energy required for
polymerization.
**Enthalpy of combustion expresses the content of energy in a substance.
The difference between the values of the energy equivalent and enthalpy of combustion can be understood as materialized labour, which is expressed in the use value of products (this is approximately equal to the total consumption of energy). If plastic materials are
subjected to further processing to obtain semifinished products or articles, the energy equivalent increases from 800 up to 3,500 kWth/t depending on the processing method.
When thermoplastic wastes are used, the earlier materialized labour is used again to a significant extent. Preparation of secondary raw materials from these wastes requires an insignificant consumption of energy for many process methods. If, however, the energy of
plastic wastes as well as pyrolysis products is used for production of heavy-duty plastics,
then we can obtain only 35 to 65% of the energy equivalent. On the other hand, a significant
economy can also give a decrease of the cost of storing wastes and freeing storage facilities
(for instance, about 4000 m3 of storage space is required for storing 100 tons of plastic bottles); what is more, it is altogether impossible to express the effect from the point of view
of protection of the environment. Thus, a big problem in storage of phenol-containing plastic wastes is pollution of ground waters.
On the whole, the use of thermoplastic secondary raw materials, including plastic regenerates with the low level of properties, which replace better-quality regenerates and materials, improves the provision of polymer materials; in turn, this makes it possible to reduce
primary raw material imports, and to increase exports of domestic thermoplastics.
14.6.4 Collection and use of thermoplastic wastes from domestic consumption sphere
Wastes of this category are characterized by inhomogeneity and considerable extent of
damage. This determines two major methods of their preparation: selective collection of
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plastic wastes via procurement organizations and isolation of plastic wastes from domestic
wastes. The latter approach requires large investment expenses and has a number of drawbacks, though makes it possible to isolate and use other valuable components (iron, nonferrous metals, glass, paper).
For territories with a large concentration of industries, it could be expedient to have
the selective collection. Herewith, (as for all the other kinds of secondary raw materials occurring in the consumption sphere), the share of plastics returned to production depends on
the limitations (for technical and hygienic reasons) on the procured kinds of wastes, on the
range of coverage, method of actions and reliability of the procurement system, as well on
the preparedness of the general public to cooperate. Proceeding from the experience of procuring other types of secondary raw materials from the public, the return rate of 20% could
be taken at the initial phase of procurement. This enables an estimate of the reserves of this
kind of raw materials in Germany of approximately 10,000 tons a year (which is about 1.5%
per capita). The accepted low rate of return makes it possible to account for the complex
conditions of procurement. With the improvement of the arrangement, the rate of return can
be made higher.
Rational organization of the procurement of municipal thermoplastic wastes should
satisfy the following requirements: clear-cut limitations on the range of procured wastes (at
a simultaneous provision of small soiling, low amount of inclusions of foreign bodies and
observance of health, occupational safety and fire-fighting requirements), a strict regulation
of amenability, rights and responsibilities of all participants of the procurement process
organization where wastes emerge, collectors, procurement bodies, enterprises preparing
and processing plastic wastes; regulation of the required economic parameters minimal
economic and material expenses of enterprises where wastes emerge, and the procurement
process itself; the stable and valid organization of procurement intended for work under various conditions and making it possible to reach a high rate of return of wastes.
At present, there are various variants of procurement systems. For instance, in Funasabi (Japan) (400,000 population and about 30,00 households) household plastic wastes are
collected from domestic garbage. About 300 workers are involved. Preparation for procurements was done by way of a written appeal to the public. Plastic wastes are collected into
weekly issued light plastic bags, which are collected once a week. This system of collection
is expensive, but its advantage is that the share of plastics is 90% on average [foreign substances include metals (up to 5%), as well as glass, textiles, paper and other materials].
Most diverse one-time experiments are known. Thus, in one of the districts in the USA
28 thousand polyethylene bottles were collected and recycled to drainage pumps. A similar
experiment was carried out in Halle-Neustadt. Information is available on broad experiments on the collection of plastic wastes in Great Britain, Austria and Germany. However,
they can not be a substitute for procurement systems on a permanent basis.
In France, manufacturers of PVC established a special society with the view of recycling bottles, because more than one quarter of all drinks and liquid food products there are
sold in PVC bottles, which makes 20% (or 130 thousand tons per year) of the total consumption of PVC. The aim of the society is to provide for the return and regeneration of
40 thousand tons of material per year. In collection sites, bottles are pressed into packs of
about 90 kg, which makes expedient the transportation of material to distances of up to 500
km. In Havre and Lyons, two installations for preparation of polymer raw materials for use
were operated; the regenerate is used mainly for fabrication of drainage and cable pipes. It
is known that individual procurements are carried out in France and Belgium also for other
kinds of used plastic materials.
472
In agricultural regions of Austria, procurements of used polyethylene (LDPE) bags for

fertilizers, films for hothouses etc. are dealt with by volunteer fire brigades (an insignificant
money reward makes it possible to stimulate this activity).
Of special significance is the storage of procured raw materials under conditions preventing it from pollution and moisture. This requires large storage facilities and sites. Films
are pressed and processed predominantly in special enterprises. Water after washing bags
for fertilizers is used for watering plants, which simultaneously makes unnecessary the construction of expensive waste disposal facilities. The regenerate is used for fabrication of
thick films, construction pipes and components.
The most favourable variant from the point of view of the considered criteria is procurement via the system of trade for secondary raw materials. Its disadvantage are high purchase prices, which are set due to the necessity of approaching the conditions of purchase
of the other kinds of household secondary raw materials. At a purchase price of plastic bottles (predominant articles) equal to 0.05 DM per piece, the purchase cost of 1 ton is 1500
DM. The lowest limit rendering a stimulating effect on the procurement process is the purchase price of 1.00 DM per 1 kg for mixed plastic wastes. At such conditions of purchase,
an economically advantageous use of secondary raw materials is possible only in special
cases. The advantage of procurement via the secondary raw materials trade is the observance of the stringent requirements to the purity of procured plastic wastes, the absence of
inclusions of foreign materials.
Another acceptable variant of procuring secondary raw materials, similar to that accepted in Funabasi (Japan) is collection into polyethylene bags. In new building areas, it
should be combined with the installation of special containers for collection of only plastic
household wastes in allocated places. The purpose of the containers should be identified by
the signs on them. From hygienic considerations, such containers should have self-closing
covers. Collection of these containers could be done by municipal bodies, organizations
dealing with purchase of secondary raw materials, enterprises processing the collected
wastes into the regenerate.
This variant has two drawbacks. The first is the absence of material incentives. However, the experience of Japan shows that this approach can be realized by raising public
awareness, but with a relatively low return rate (for instance, due to the availability of garbage disposers in multistorey block of flats). The second drawback is that other municipal
wastes would also get into these bags, so the contamination of secondary plastics raw materials would be higher and, respectively, expenses for its sorting and cleaning would rise.
Other presented variants require a number of additional organizational measures to be
taken: expansion of the network of trade by secondary raw materials for purchasing plastic
wastes for fixed prices with account for the quality of raw materials, charge-free procurement of raw materials by processing enterprises etc.
The success in the organization of procuring household thermoplastic wastes depends
on the conscientious support by the general public. Though most citizens are in principle
prepared to participate in procurements, it is necessary to constantly and purposefully raise
the public awareness and provide information on this subject, using radio, TV, newspapers,
posters and postcards. It is necessary to attract public organisations, which already had an
experience of procuring other kinds of secondary raw materials. Economic stimulation,
though playing a supporting role, can not become the dominating motif of procurements.
Procurement of plastic wastes can be done in two stages. First, it is expedient to
procure plastic bottles: in Germany they make about 30% of the total amount of household
wastes; material of bottles is of relatively one type, the risk of foreign inclusions not high.
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From the point of view of hygiene, it is necessary to demand the thorough cleaning and rinsing of submitted bottles. The same-type composition of procured wasters significantly facilitates their regeneration. Subsequently, with the development of processing facilities and
and the increased demand for the regenerate, procurements should change to mixtures of
plastic articles, but still excluding combined articles (for instance, plastics with metals), as
well as, if possible, articles from thermosetting materials.
When accepting household wastes in a trade of secondary raw materials, the purity of
the accepted material is controlled visually, it is weighed. Soiled packagings of food products are returned, foreign bodies and thermosetting materials are separated. The procured
plastic raw materials are kept in special vessels (boxes, bags, mesh containers etc.), which
could be used not only for storage but also for transportation. Transportation from procurement centres to places of intermediate storage is carried out by traders of secondary raw
materials. Intermediate storage, as a rule, is required to accumulate the amount of secondary
raw materials, expedient to be supplied to processing plants. The rational use of transport
is a serious problem. Secondary raw materials should be compacted in intermediate storage.
Processing enterprises can be at distances of several hundred kilometres from procurement
centres. To efficiently use transport means, it is necessary to comminute thermoplastic
wastes or press them into rolls. For this purpose, procurement enterprises should be
equipped with special devices (impeller breaker mills, presses, etc.).
Collection and delivery of plastic wastes in polymer bags does not make possible the
control of wastes contents. It could be expected that in delivery of bags once a week only
preliminarily washed plastic wastes would be submitted. The demand in work force for the
organization of such a variant of procurement is smaller than in equipping special pick-up
centres. Issue and collection of bags for plastic wastes can be done by local communal enterprises. Before transportation, the collected raw materials in this case should also be compacted (comminuted or pressed) and well as liberated from non-plastic component parts.
Wastes collected in containers placed in allocated sites can be soiled very much. Delivery of containers can be performed by communal enterprises and processing plants. Separation of non-plastic component parts, considering the high degree of contamination of the
wastes collected, requires additional work force.
14.6.5 Separation of plastic wastes from domestic garbage
This variant can be economical only when all components of garbage are subsequently used
as secondary raw materials. Earlier developments on garbage separation focused primarily
on scrap metal and waste paper. Utilization of old glass, nonferrous metals and plastics significantly increases the economic efficiency of the separation method. The composition of
domestic wastes varies depending on the season and locality. Below we present the composition of domestic wastes collected in Holland and Sweden and separated in RRR-type
installations, %:
Paper, paperboard
Iron
Nonferrous metals
Organic products
23 50
2.5 5
0.3 0.5
20 37
Glass
Plastics
Wood, textiles, leather
Sand, ceramics
8 12
5.5 8
up to 5
up to 20
To separate garbage, it is necessary to perform processes of comminution and separation. Separation can be wet and dry.
474
The wet method is characterized by a high consumption of water and energy (especially for the subsequent drying), significant expenses for the purification of water, and separated products are of relatively low quality. If garbage is supplied in polymer bags, the
process of its preparation begins with the cutting of bags. For coarse comminution of garbage, hammer swing mills and one- and two-roll impeller breaker mills are used; and for
fine comminution, impeller mills. For inorganic components of garbage (stones, bricks,
etc.) use is also made of grooved rolls. Fractionation is performed using drum and vibrations
sieves.
Separation of wastes by the wet method can be carried out in flotation chambers or
counterflow separators. The operation of flotation chambers is based on the flotation of
some and sedimentation of other components of the separated mixture. In counterflow separators, the separation into the floating and sedimenting fractions is performed in accordance with the set flow rate. To separate ferromagnetic component parts of garbage, use is
made of electromagnetic drum or band separators. In the wet method, heavy nonmagnetic
fractions are separated using liquid media of high density. Especially great technical problems occur in separation of paper, polymer films and combined polymer textile films. A
high-voltage separator was designed for separation of paper and polymer films. In the wet
method, paper is dissolved and is thus separated from insoluble plastic and textile component parts. A known variant of the wet method is the BlackClawson method. An installation in Franklin (Ohio, USA; capacity 150 thousand per year) operates according to this
method.
Separation units for automobile scrap, operated by the wet method, were designed by
the firm Bureau of Mines. In flotation chambers, plastics of various types are separated; and
in aqueous counterflow separators, floating (for instance, porous materials), precipitated
(heavy metals) and flotated (light metal, glass, rubber, heavy plastics) fractions. The further
separation of nonferrous metals is performed in separators with heavy media (for instance,
with barite).
The wet method of separation should be used when the component parts of garbage
are presented in an already enriched form; purification and fine separation occur in the process of preparation. Thus, the process developed by the firm Bureau of Mines makes it possible to obtain the paper fraction of 99.8% purity. The firms Recycling B.V. and Esmil B.V.
(Holland) make use of the wet method only to separate the light fraction; the yield of polymer films is from 70 to 80% at a purity of 99%.
Most processes developed for separation of domestic wastes use the dry method at the
first stage. The equipment used are air separators and classifiers; classifiers are predominantly with the zigzag air ducts. In the process developed by the firm Kraus-Maffei (Germany) the dry method predominates. Only for separation of paper and plastic fractions a
hydroseparator is used, in which the component parts are comminuted even more, and the
paper fraction is turbulized and isolated by means of water. Plastics together with textiles
form an easily removed upper layer. The method is intended for recovery of paper, but can
be also used for utilization of plastics.
A combined method of processing domestic wastes was developed in Aachen (Germany). After the magnetic separation of iron and sieving of fine garbage, large components
are comminuted and separated. The light fraction, which consists predominantly of paper
and plastics, is separated by the wet method; moreover, the paper fraction, in water. The
further processing of the heavy fraction is performed in a counterflow classifier or a separator with heavy media. This method can prove to be economically advantageous at an annual volume of recycled material of 250 thousand tons.
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A significant advantage of the last three processes is that comminution is carried out
after the separation of the larger part of the metal fraction (mainly preserve cans).
In Rome, a completely automated unit for separation of garbage is operated. Garbage
is first roughly sorted, then, after magnetic separation, comminution, air separation and
sieving, light fractions containing paper and polymer films are isolated. Separation of polymer films and cardboard, as well as heavy paper, is performed by means of compressed air.
Light paper is separated from polymer films by means of mechanical clamp shells. Due to
the high content of polyethylene (LDPE) film in garbage, the unit is intended to yield just
these plastic raw materials. Then PVC and polystyrene are isolated by the wet method, as
well as glued paperaluminium films. Polyethylene films are washed, dried, subjected to a
special treatment to eliminate the smell and are pressed into rolls 25 kg each. They also contain 5% of other plastics, 4% paper and paperboard, 2% inorganic components and 0.12%
wood, rags, feathers and porous materials. Using various methods of purification and separation, it is possible to reduce the content of foreign materials to 0.12%, so that in the end
a high-quality regenerate is obtained, which can be used for production of films by the blow
method. The yield of the regenerate reaches 3040%. Two such installations in Rome annually process 1.8 thousand tons of garbage. The efficiency of these installations is higher
than that of garbage incineration units.
The process developed at the Franklin Institute (USA) makes use of exceptionally dry
separation. Garbage is comminuted in a hammer swing mill, then separated using air and
magnetic separators and air classifiers. Additional comminution is provided for certain intermediate fractions. Separation of paper and plastics is carried out in a high-voltage trap.
The RRR process is similar. The plastic fraction is pressed into a roll. In Stockholm, a unit
of 120 thousand tons per year capacity is operated, which supplies 6 thousand tons of separated plastics per year. The Holland units have a lower productivity.
The recovery of secondary plastics from domestic wastes is considered differently.
Foaming agents, as well as other auxiliary substances, change the density so strongly that
the floatingsedimentation processes do not make it possible to obtain pure fractions. A
significant role in the separation process is played by the geometric shape of wastes and the
soiling of the surfaces with fats, oils and surfactants. As the result, the separation of only
97 to 99% can be achieved, and impurities can have a significant effect on the process properties of material. Therefore, methods of separating plastic wastes from domestic wastes realized in practice are mainly restricted to the recovery of used LDPE films.
14.6.6 Application of plastic wastes as fillers and additives
Wastes of thermosetting materials after comminution can in certain amounts be added to
formation masses without any significant change of properties of the latter. This approach
is justified if the cost of preparing the material does not exceed 50% of its new cost.
Installations for preparing and mixing thermosetting plastic wastes, developed by the
companies Hull (USA) and Meiki (Japan) do not differ in principle. The installations are
mobile, their output is about 50 kg/h.
Ground wastes of thermosetting materials are used as inert fillers whose particles
should be of the same size as particles of the filler in the new material. Before the formation,
the primary material and the used secondary raw material should be well mixed. Mixtures
with wastes of thermosetting materials are reprocessed by pressure die casting and injection
molding; these methods make possible a good homogenization of the melt.
Addition of wastes as a filler slightly reduces the yield of the mass. Thus, introduction
476
of up to 15% filler insignificantly changes impact viscosity, tensile strength and bending
strength, electric and chemical properties, thermal resistance under load also increases. Addition of such a filler in the amount of higher than 20% is used only for nonessential articles.
An efficient method is comminution of thermosetting material wastes at low temperatures the size of almost 95% of particles becomes less than 0.4 mm. Addition of 1520%
of this powder to the formation masses does not worsen the properties of the material.
Comminuted wastes of thermosetting materials can be also added to thermoplastics as
fillers. The filler often has to be dried before use. No technological problems arise in processing of powders of filler and thermoplastic. Chips of synthetic-resin bonded paper laminate and fabric-based laminate, formed in machining of pressed laminated materials, can
be added to polyamide. Materials containing up to 30% fillers from wastes of thermosetting
materials can be processed by injection molding. The surface of articles produced is of satisfactory quality. With the content of the filler increased, an insignificant decrease of the
strength of articles at a simultaneous increase of their rigidity is observed.
Addition of industrial wastes of LDPE to concrete the major construction material
yields concrete with increased thermal insulation properties. Milled packaging articles
from foam polystyrene are used as sound absorbents under the seamless floor. Addition of
flocs to concrete yields foam concrete, which is distinguished with good sound and heat insulation properties.
Additions of comminuted rubber wastes in the amount of 0.51 wt. % improve the
performance properties of hollow concrete blocks. Large additions of rubber wastes are not
used, which is due to the problems with comminution of wastes. This approach can be also
used for filling gypsum walls. Household plastic wastes were used in production of body
brick 16 wt. % of comminuted plastic wastes was added to the brick mass. After burning,
the density of bricks decreases by approximately the same value (16 wt. %); the thermal
insulation properties of the brick are significantly improved.
In road construction, thermoplastic wastes are used for modification of bitumens, the
requirements to which are sufficiently high softening temperature and small brittleness at
low temperatures. These contradictory requirements are partially fulfilled for bitumens
based on petroleum with a large content of paraffins. Studies were carried out with the view
of achieving required structural changes in the complex colloidal system of bitumen by its
modification by wastes of LDPE, HDPE and SEVA. These polymers were introduced as
granulates into liquid bitumen at a temperature of 160180C. This process requires about
2 hours, which restricts its use for production of casting asphalt. Additions of polymers
(57%) lead to the formation of typical casting asphalt mixtures with increased strength in
compression and bending within the temperature range of 040C. Herewith, the yield does
not change significantly as compared with nonmodified material, and in tests for long-term
strength under dynamic loads the material exhibits itself as a stronger substance. The material passed long-term tests on the roads. A similar use of wastes of polyethylene as additives to bitumen is known to be used also in Austria. Polypropylene and ABS resins match
with bitumen much worse. Addition of 7 up to 8% polypropylene considerably widens the
temperature region of applications of bitumen asphalt. It is expedient to introduce comminuted wastes of PVC to asphalt mixtures in repairs of road pavement, as this contributes to
the increase of its low-temperature and heat resistance. A positive experience of using PVC
as an additive is known to exist in Japan. Wastes of polystyrene are also applicable for this
purpose.
Plastic wastes granulates are used in underground excavations for pipeline placement;
flocs of foamed polystyrene, as an intermediate layer to increase water impermeability.
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In agriculture, wastes of foamed polystyrene (flocs) are used for soil amelioration.
This increases the air and water permeability of loamy soils in the long term, because these
wastes are not degradable. Flocs of wastes are mixed with soil, and this mixture replaces
peat or pine needles. For better drainage, they are placed into a package. This approach facilitates the treatment of soil and saves on other materials used for soil reclamation, heating
of soil is faster (in comparison with pine needles, the temperature of soil is 2C higher); the
soil structure becomes better and the capillary effect smaller, which is important for sensitive seed buds. In Germany, over 100 thousand m3 of wastes was used for this purpose.
14.6.7 Mechanism of degradation
Photochemical degradation is a manifestation of the ageing of polymer materials under the
action of UV radiation with the wavelength of 330 nm. At the action of common lighting
equipment, a material placed behind the glass should preserve its properties for a time corresponding to the requirements, with account for the climatic conditions and season in the
degradation period. A special indicator, for instance, a stained substance added into the material, indicates the acceleration of the degradation process. To perform both photolytic and
accelerated photooxidative degradation, the following can be used: introduction of photosensitizing links into the polymer chains (destruction of chains occurs predominantly at
these sites); introduction of photosensitizing catalysts, which enhance the natural process
of ageing; new specially synthesized sensitizing polymers. Photodegradable polymers are
obtained by introduction of ketocarbonyl groups, which under the action of UV radiation
cause the degradation of organic compounds. Vinyl ketones are introduced into polymerization polymers; bifunctional monomers, into polycondensation polymers. For mixed
polymers, use can be made of dibasic acids, diamines or glycols:
R'
HOOC
(CH2)n
(CH2)n
COOH,
R'
H2N
(CH2)m
(CH2)n
NH2,
R'
HO
(CH2)m
(CH2)n
OH.
where R is alkyl, aryl, alkaryl or alkenyl C1VC2; R is H or alkyl C1 C6; m, n = 2, 4.

Degradation is faster if the ketone group is not part of the main chain but is directly
adjacent to it. Sensitization assumes the mobility of segments, so that polymers should have
the glass-transition temperature not higher than 30C.
The method is used in production of packaging films and films for agriculture from
polystyrene. Sensitized copolymers are added to usual commercial materials, so that, for
instance, for polystyrene the content of carbonyl groups is from 1.4 up to 0.08%. Decom-
478
position time in this case is from 6 up to 60 sunny days. A significant advantage of the method is that materials are in the end decomposed to give H2O and CO2. Materials pose no
hazard for ground waters and are quite suitable for packaging food products. As additives,
a large number of aromatic carbonyl-containing unsaturated ketones and dienic monomers
are proposed to be used.
A method developed by Scott is an example of using photooxidative catalysts. Organic
complex compounds, for instance, iron diethyl dithiocarbamate, serve as additives. Under
the action of UV radiation, these compounds form a radical possessing a catalytic action.
If, after a certain induction period, radicals are formed, the further decomposition of polymers occurs without the action of light. The induction period depends on the amount of
compounds added. The decomposition products are then degraded by microorganisms. In
recycling, additives act as heat stabilizers.
Organic salts of polyvalent transition metals are recommended to be used as degradation catalysts, predominantly of Fe, Mn, Zn or Co, as well as chelates with these metals of
the general formula CH3COCH2COOR. A combination of both these mechanisms are offered. Similar organic ferrous compounds were developed by the Swedish company Akerlund and Rausing.
Peroxides and hydroperoxides are also light adsorption centres in polymers and induce
chain growth reactions.
Initiation reactions are caused by multivalent transition metals under the action of
light:
Fe3+OH
Fe2+OH
OH + RH
Fe3+OH ,
Fe2++ OH ,
H2O + R .
To perform this function, compounds of heavy metals should be soluble in polymers.

Compounds of the form X Fe Y have a good solubility in polyethylene; besides, X can
be a hydroxyl group, and Y are stearates or oleates, which contribute to the solubility. Many
derivatives of ferrocene have been proposed.
Polyisobutylene oxide belongs to polymers, which have a relatively weak photostability. It is recycled mainly to produce packaging films. To provide for a certain degradation
time, it is also necessary to introduce photosensitizers into polyisobutylene oxide, though
at lower concentrations than in the case of heavy-duty plastics.
After a certain time, the mechanical properties of the material change owing to decomposition. This is especially manifested in a decrease of relative breaking elongation. Films
become rigid and brittle, first break into pieces and then finally turn to powder.
An example of biodegradable polymers is bioplastic filled with 1040% starch, developed by Coloroll (UK). A special treatment can enhance adhesion between polymer and
particles of starch. This enables producing films by the method of blown extrusion. These
films are used as a packaging material.
During the storage of old films starch is an ideal object for the attack of a multitude of
microorganisms, which, by excreting enzymes, transfer it into soluble amylase. These processes also proceed in sea water. Only the sunlight without the involvement of microorganisms does not cause accelerated decomposition. Products of decomposition are absolutely
harmless.
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Separation of water-soluble films, for instance, from hydroxypropyl cellulose or polyvinyl alcohol, combined with oiled paper, aluminium foil, polyvinyl chloride or polyethylene, causes no problems, because cellulose is easily and harmlessly degraded by means of
microorganisms. Naturally, the potential for the introduction of such films is limited.
14.6.8 Energy efficiency of incineration of plastic wastes
Plastics and elastomers are high-quality combustible materials, which yield a high combustion temperature. Combustion of polyolefins, for instance, makes it possible to save an approximately equal amount of black-oil fuel. Combustion of wastes produces energy
converted to steam, which can be used for heating, or to electricity. If wastes of elastomers
and plastics are burned together with domestic wastes, they are energetically the most energy-rich part of this fuel. According to estimates of British experts, about 2% of energy
requirements in Europe can be met if a significant part of municipal wastes are burned in
centralized installations and the energy carrier is produced in the form of steam.
In contrast with goal-oriented production of energy, the aim of common incineration
of garbage is to produce a hygienically admissible residue in the form of slag, whose volume is much smaller than that of incinerated garbage. The produced heat can be used for
maintaining the incineration process or for heating purposes.
The heat of combustion of common domestic wastes is 29008400 kJ/kg; the combustion heat of plastics is more than twice higher. In incineration of garbage, it is expedient
to separate it or enrich with particular components. Higher combustion temperatures are
achieved in the presence of plastic components in garbage. For the content of plastics of
5% in garbage, its incineration presents no problems; at a more than 10% of plastics, it is
recommended to separate them and perform incineration in special furnaces.
Characteristics of production units for garbage incineration were compared. The productivity of the units reaches 27 tons/day. Material should be loaded in a ground state. Furnaces with the travelling-chain grate and fire feeding by means of black-oil fuel or gas are
used. The technological problems in connection with the lining of furnaces occur at high
temperatures from 900 up to 1200C and the presence of aggressive gases. Excessive formation of soot occurs. Combustible waste gases via the air blower are supplied for incineration; herewith, waste gases with a temperature of about 1000C are formed, which are used
for heating the air supplied to the incineration furnace.
According to the environment protection requirements, glue gases, which may contain
toxic components (ammonia, chlorine, hydrogen chloride, hydrogen cyanide, nitrous gases,
sulfur dioxide), should be purified before being discharged into the atmosphere. There are
a wet and dry methods of purifying flue gases. In the wet method, alkali liquors or suspensions are injected into the evaporative reactor; in the dry method, alkaline dust, for instance,
NaOH. Both methods need tissue and electric filters for dust separation to be installed.
A unit for incineration of wastes of plastics and elastomers has been developed in
Czech Republic; the installation incinerates 1 m3 of wastes per hour with addition of 20 kg
of diesel fuel, light petroleum product or heating gas. There is no pollution of the environment in this case.
A pilot plant in Germany recycles 400 kg/h of plastic wastes (rubber, plastic films and
articles, packaging materials, nonwoven materials). In the first stage, wastes pass a thermal
preparation; in the second, they are incinerated. Modern production methods of pyrolysis
and gasification of plastic wastes give significant results. For instance, their incineration in
the deficit of oxygen yields heating gases with the heat value of up to 12,600 kJ/kg.
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14.7 Secondary raw materials based on packaging material wastes

Of all raw materials used for economic activities, only 12% become products, the rest goes
for wastes, the great bulk of which cause harm to nature. Enterprises of meat-and-dairy industry massively use polyethylene, polypropylene, saran films; cellophane, aluminium foil,
multilayer films, paper with paraffin and polymer backing.
Many of them can last for several hundred years. However, when unsuitable for useful
applications, they are converted to wastes, which are incinerated or utilized.
An ecologically efficient method of protecting the environment from pollution with
wastes of polymer packaging materials is to develop polymers with the regulated service
life. These are biodegradable polymers capable of being degraded to low-molecular-mass
products under the action of heat, light, air oxygen and soil microorganisms. An efficient
approach is the development of edible packagings for food products.
Many materials can be used as secondary raw materials in fabrication of light sandwich-type materials. They include large-size tilt-up layered wall sections, whose mass is 50
kg per 1 m2 with foam-plastic filler.
Such constructions are suitable for small enterprises, as well as in constructing auxiliary building and refrigeration storages of 250100 ton capacity.
14.8 Use of secondary energy resources

Food industry enterprises are large consumers of heat energy resources. The problem of fuel
economy in food industry is especially acute. The most energy-intensive is sugar production, where about 40% of the total fuel is consumed; the next in the range are fat-and-oil,
distillary, vegetable-dehydration productions etc.
Of great importance in the solution of these tasks is the use of secondary energy resources, which are up to 10% in the fuel-and-energy balance of the country. The issue of
using secondary energy resources is also important because the discharge of thermal wastes
into the environment, especially into natural reservoirs, leads to thermal pollution and the
disturbance of ecological equilibrium.
Theoretical calculations and experience of operating thermal schemes testify to the
significant potential of fuel economy by using secondary energy resources. Systematic
measures on the use of secondary energy resources require certain efforts on the development of special devices and energy technology combination.
There are considerable losses of thermal energy in food industry owing to the improper
organization of heat economy, so it is necessary to introduce measures to decrease unproductive losses of energy and the most complete use of secondary energy resources. Secondary energy resources represent a potential of a certain kind of energy (thermal, chemical,
mechanical, electric) contained in wastes, intermediate or ready-prepared products.
The secondary energy resources of food industry enterprises can be divided into four
main groups:
the heat of waste gases and liquids (flue gases from boilers and furnaces, as well as
the heat contained in barometric water, distillary stillage, etc.);
the heat of waste steam of steam-power units and secondary steam, heat-consuming
units (evaporation units, rectification apparatuses, driers, self-evaporating vapours);
the heat of combustible wastes (for instance, the husk in oil-extracting plants is used
as fuel in steam boilers);
the heat contained in products and production wastes (this group includes the heat
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contained in slags of boilers, bagasse of sugar plants, hot bread, sugar, etc.; and also the
heated air of hot production shops).
Of the groups listed, the role of the first two groups is the most significant; that of the
fourth group is less significant. The heat of the secondary energy resources is used in three
directions: for processes proceeding in the main process installations inside the shop or enterprise (closed schemes); for external purposes not related to processes proceeding in the
main process units, which are the sources of the secondary energy resources, for instance,
the use of secondary energy resources for district heat supply and hot water supply of residential buildings (open schemes); for internal and external purposes with respect to the process in a technological unit (combined schemes).
Each branch of food industry has its own sources of secondary energy resources. Various principles of the technology determine their qualitative composition (temperature level
and properties of the heat carrier) and quantitative composition. Consider the most energy-intensive branches.
Sugar industry. By its volume, complexity and the costs of the heat energy facilities,
by the inseparability of links between the heat energy processes, as well by the possibility
of using secondary energy resources, sugar production occupies a leading position among
the food industry branches.
The main constituent parts of secondary energy resources are the heat of steam from
vacuum apparatuses, self-evaporating vapours (boiler deaerator, saturators and sulfiters,
collectors of condensates and process solutions), waste gases from boilers, condensates,
barometric water, blowdown water of boilers, pulp press water, enthalpy of pulp, heated air
of production facilities.
Distillation industry. As secondary energy resources, the heat of stillage from the distillation column is used; of secondary stillage; production products (alcohol, fusel oil,
yeasts, ether-aldehyde fraction, etc.); the heat of condensers, distillation water, secondary
steam from yeast driers, cooling water from condensers and refrigerators, heated air of production facilities, waste gases from blowdown-water boilers.
Distilleries equipped with installations for evaporation of secondary stillage, additionally as secondary energy resources have the heat of secondary steam, condensate of evaporation apparatuses, barometric water from the condenser.
Brewing industry. Secondary energy resources include the heat of secondary steam of
boiling vessels, condensates, cooling water, effluent gases of driers and boilers.
Baking, confectionary and starch industries. Elements of secondary energy resources
are the heat of condensates, secondary steam of vacuum apparatuses, coiled columns, barometric water, secondary steam of evaporation units, production products, waste gases of
furnaces, driers and boilers.
Fat-and-oil industry. As secondary energy resources, use is made of condensates and
cooling water, production products, heat of incineration of wastes, heat of waste gases of
driers and boilers.
Canning industry. Secondary energy resources of canning production include the heat
of secondary steam of evaporation units and vacuum apparatuses, barometric and cooling
waters, condensates, semifinished products and ready-prepared products, the heat of waste
gases of dryers and boilers. Consumption of thermal energy for the main products by the
fields of food industry are (in mln GJ/year):
Sugar industry 127
Brewing industry 16.5 Distillation industry 50
Baking and confectionary industry 60
Fat-and-oil industry 15
Starch industry 8
Canning industry 1.05
482
Estimates of experts relative to the possibilities of using secondary energy resources

vary, which can be explained by the absence of a unified method of determining and accounting for the secondary energy resources.
Analyzing the heat balance of an enterprise, one should pay attention to large heat losses with production wastes (cooling or recirculating water, unused process products, excess
condensors, heated air, hot gases, blowdown water, etc.), accompanied with the tapping of
the heat carrier (liquid, solid, gaseous). A simple and widespread way of decreasing heat
losses is to return the tapped heat carrier to the process flow again; in this case, the returned
working medium and heat are saved.
The problem of using secondary energy resources and protection of the environment
in food industry are closely connected. Many enterprises are forced to put out of operation
a significant amount of wastes, including those that have elevated temperature, which leads
to large heat losses, pollution of the environment and disruption of the ecological balance.
The wastes that have a sufficiently high temperature are sources of secondary energy
resources (unexpended heated waters, flue gases, exhaust from drying installations,
self-evaporating vapours, hot air, etc.). To date, sufficient experience of using low-potential
heat has been accumulated:
development of heat exchangers (recuperative and contact-type, operated at a small
temperature difference);
return of heated waste waters to the process cycle;
use of flue gases for drying processes;
maximum use of condensates for feeding steam boilers;
use of excess condensate for process purposes;
introduction of surface condensers;
use of secondary steams of vacuum apparatuses and vacuum evaporators;
use of self-evaporating vapours for heating liquids;
use of heated air for heating production facilities;
use of secondary steam for district heat supply;
recovery of cooling water to the process cycle;
elaboration of condensate traps and condensate schemes;
replacement of steam heating by water heating;
multivariant calculation of heat schemes and search for optimal solutions with the
view of saving fuel, electric energy, materials;
recirculation of the drying agent;
improvement of heat application schemes with the maximal use of secondary energy
resources;
compression of secondary steam in jet and mechanical compressors;
use of thermal wastes for cold production, etc.
14.9 Economic and ecological aspects of utilization of secondary raw

materials
High growth rates of production and consumption of plastics, characteristic of industrially
developed countries, stipulated the emergence of a relatively new problem disposal and
utilization of plastic scrap. This problem is of special significance both because the packaging industry is one of the largest consumers of polymer materials and due to short service
life of containers and packagings.
On the whole, the content of plastics in solid wastes is at present in the Western Euro-
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483
pean countries 34%, in Japan, 8%; in the USA, 5% and increases up to 68, 1215 and
710%, respectively.
The growing volume of plastic scrap leads to the necessity of preventing the pollution
of the environment, which is associated with considerable expenses. Expenses for controlling the pollution of the environment in chemical industry of industrially developed countries reach 610% of all capital investment. A significant part of expenses (up to 25%) is
related to the prevention of the pollution with solid wastes.
According to the data available, the costs of processing and disposing plastic scrap exceed approximately eightfold the expenses for processing most industrial wastes and almost
threefold for disposal of household wastes. As plastics do not decay and do not decompose,
their wastes could not be compacted during the disposal; as the result, plots of land required
for the disposal should be four times as large as those for the disposal of household wastes.
In incineration, plastics usually evolve toxic and corroding substances; the required incineration temperature is approximately 600700C higher, and the volume of evolved incineration products 35 times larger than in incineration of household wastes; all these
factors make the process more expensive.
One of the waste disposal methods developed specially for polymer containers is introduction (during the synthesis or recycling) of additives, which initiate bio-, photo- or
water degradation of containers used. Containers from decomposing plastics are produced
mainly in Japan, Germany, the UK and the USA.
The practice of using decomposable plastics revealed a restricted potential of this
method for solving the pollution problem: wastes of containers, when getting into the general mass of household or industrial wastes, cease to be subjected to the action of factors
that cause their decomposition. If decomposition does occur, its products can also cause the
secondary pollution of soil and water. Besides, there is a possibility of contaminating a
packaged product with substances formed in decomposition.
Recent studies by the sanitary services of Germany, Great Britain and the USA indicate a negative effect of decomposing plastics also on the environment. All these make one
to assess the prospects of using decomposing materials with caution, though does not rule
out the possibility of their use in a number of fields, for instance, in agriculture.
Thus, a brief consideration of the main waste-disposal methods for polymer containers
shows that they require considerable expenses and in many cases can not efficiently solve
the problem of pollution of the environment.
In the recent years, methods of utilizing wastes of polymer containers have been developed, primarily the following: recycling of plastics based on wastes of structural materials, thermal and catalytic cracking, pyrolysis of wastes of polymer containers.
Recycling is the most expedient method of utilizing wastes formed in production of
containers. Economy of the expenses for processing packaging wastes can reach 70% of
the cots of fresh raw materials.
Wastes of polyethylene film widely used for packaging various products can be recycled to produce either secondary granulate or be mixed with fresh raw material to produce
films.
In connection with the rapid development of producing multilayer packaging films and
combined materials with layers of foil, paper and tissue, much attention is given to the methods for the regeneration of these materials.
Consumption of containers from plastic foam high expands at a high rate. Wastes the
weight of which reaches 30% of the weight of produced containers can either be used again
in production of foamed articles, or be recycled into granulate after their degassing. Wastes
484
of foam plastics are also used as one of the layers in production of combined packaging materials, where base layers (paper, tissue, foil, polymer films) are alternated with layers of
comminuted plastic foam. Containers from thermosetting materials are used on a much
smaller scale than containers from thermoplastics; however, their absolute volume of consumption are still high. An important condition of increasing the efficiency of these containers is recycling of wastes produced. Installations for the fine comminution of wastes of
thermosetting materials are operated in the USA and Japan. Regenerate is used an additive
(up to 20%) to fresh raw materials; herewith, the properties of the initial composition are
not worsened considerably.
Reprocessing of used polymer containers is more complex as it is associated with the
need to collect, sort and clean them. Nevertheless, this problem is successfully solved in a
number of countries. Thus, the experience of work of German firms for reprocessing of
packaging wastes indicates the economic feasibility of these measures and shows that the
rational organization of the collection of packaging wastes makes it possible to reduce the
amount of household and industrial wastes by no less than 40%.
In the USA, a number of large dairy enterprises perform recycling of polymer containers for milk products; a specialized enterprise Seajay Plastic Bottles Center provides service to companies producing polymer containers. Used containers are recycled into
secondary granulate, which is then used for fabrication of agricultural-purpose articles. The
cost of granulate is 2.53 times as low as that of the initial raw material. Recycling of packaging wastes for food products is, as a rule, preceded by the stage of purification from the
residues of the product.
In Japan, household plastics wastes, which are mainly various kinds of packagings, are
collected. Collected wastes in the form of a mixture are processed on units of various capacity (50 up to 700 kg/h) into secondary granulate. The cost of obtained material does not
exceed 25% of the cost of the cheapest primary polymer. The secondary material obtained
is mainly used as heat and sound insulation in construction and agriculture. However, it can
also be used for packaging purposes. Thus, in Japan, cups and other containers from polystyrene are recycled to fabricate packaging materials used to produce, for instance, packaging boxes. In Germany, polyethylene bags used for packaging chemical fertilizers and peat
are recycled. The secondary granulate obtained is again used for fabrication of bags, which
meet the requirements and, besides, as compared with bags from primary raw materials, are
less slippery when stacked.
One of the economic methods of utilization of polymer packaging wastes is production
on their basis of structural materials, in which the wastes play the role of a polymer bonding
adhesive. In this case, there is no need to purify and screen wastes; it is also possible to utilize packaging wastes together with other components of household and industrial wastes.
The properties of such materials are largely determined by the properties of the filler; they
can be used in municipal and road construction, in production of furniture, as heat and sound
insulation materials. Their cost is 23 times lower than that of replaced traditional materials
and articles. This method is especially widely used in Japan, where it is realized in a number
of semi-industrial installations. It is envisaged to expand the existing facilities and to construct new installations of 46 tons per hour capacity.
A promising method of utilizing polymer material wastes is their depolymerization to
oligomer or initial monomer products. Of the depolymerization techniques, of greatest significance are pyrolysis, thermal and catalytic cracking. The conditions of the process and
the nature of reprocessed wastes are determined from the ratio of the products obtained: hydrocarbons for the synthesis of plastics, gas oil, kerosene, fuel oils, activated carbon etc.
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The energy crisis due to the deficit of oil-and-gas raw materials, created prerequisites
for the development of this method of utilization.
Works are underway to include pyrolysis installations into production of plastics fro
oil-and-gas raw materials. There is experience of using obtained gases for production of
electrical energy.
Below, we present a technical-and-economic comparison of the methods of thermal
treatment of wastes: incineration as the main method of disposal, on the one hand, and pypolysis, cracking, on the other hand. Capital operational expenses for installations operated
by the thermal cracking method are, respectively, 5 and 1.52 times as low as similar parameters for units of comparable capacity (3 tons/h), operated by the incineration method.
One should also take into account an additional economy from the use of products obtained.
Thus, fuel oils whose yield in the pyrolysis of discarded polyethylene containers is 94.7%,
contain no sulfur, which is an advantage with respect to raw petroleum products and common types of fuel.
On the whole, the technical-and-economic parameters of the methods of utilization of
polymer packaging wastes do not exceed the expenses for their disposal, and in some cases
are even lower. Besides, wastes utilization methods, in contrast with disposal methods provide for the rational use of raw material resources. They are also the most efficient from the
point of view of preventing the pollution of the environment by production wastes and container consumption wastes.
The development of photo-, bio- and water-degradable plastics is caused by environment protection requirements. Overage articles from such plastics are degraded harmlessly.
Degradation of plastics occurs due to photolytic, photooxidative and biological reactions.
The use of these plastics contributes to the decrease of environmental pollution and
labour costs, especially in agriculture, where polymer films reach such an extent of degradation after the vegetation period of agricultural crops, that they do not prevent soil treatment; to a sharp reduction in the amount of plastics scrap in refuse dumps. On the other
hand, degradable plastics are not involved further in material and energy turnarounds. It
should also be noted that there is still no clear understanding as to the action of plastic degradation products on soil and on ground waters.
The effect of decomposition is achieved mainly due to the introduction of additives or
addition of initiating groups to polymer chains. In any variant, this makes the material more
expensive. Herewith, the exact economic assessment is impossible due to the complexity
of accounting for the expenses for protection of the environment. If plastic wastes are kept
unexposed in storage facilities, their degradation can be only biochemical. There is also
some negative psychological effect of using articles from degradable plastics due to the
awareness that self-degradation of plastic articles probably contributes to the contamination
of the environment.
14.10 Self-degrading polymer materials

Most polymer materials manufactured at present are distinguished by an exceptionally high
resistance to microbial action. This is one of the major reasons of their wide use. However,
this advantage turns to be a serious drawback for waste polymers. Under natural conditions,
polymer wastes are degraded extremely slowly, are practically not subjected to the action
of soil and air microorganisms, and are, thus, a source of environmental pollution. In recent
years, great attention has been given to the development of self-degrading polymer materials. These materials are divided into three major groups: biodegradable, degradable under
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the action of light and chemically degradable.

Biodegradable materials. Biodegradable polymers are photodegradable compositions, which, being for a certain time under atmospheric conditions, are degraded so strongly that are easily assimilated by microorganisms present in the soil and in the atmosphere.
Therefore, photodegradable polymers are called biodegradable.
The company ICI (Great Britain) developed a technology of producing a new packaging material in bioreactors biopol the use of which for packaging food, pharmaceutical
and cosmetic products would make it possible to solve problems associated with utilization
of traditional plastic packagings.
Biopol is the first biodegradable thermoplast in the world. It is produced by fermentation of such agricultural raw materials as sugar and starch. Used packagings from biopol
can be freely dumped on acting waste disposal sites without disturbing the ecological balance. Biopol completely degrades in soil under the action of fungi and bacteria. The degradation rate of used packagings depends on their thickness and type of surface treatment.
Rough films degrade faster than bottles with smooth surface fabricated from the same material.
Biopol is a thermoplastic aliphatic polyester (polyhydroxybutylate). The physical
properties of this material (melting point, crystallinity, etc.) are the same as in prolypropylene, though its rigidity and brittleness parameters are slightly higher. Biopol is processed
as traditional thermoplastics. Technical and economic prerequisites for the re-use of biopol
in industry were established.
In the opinion of ICI specialists, the use of sugar or starch for production of biopol is
justified from the economic and ecological point of view. Economic forecasts suggest that
in the foreseeable future costs for sugar in the Commonwealth countries would go down to
the level of the world market. Besides, the general reduction of costs on agricultural produce
due to the intensification of agriculture is expected. Production and application of biopol in
sugar supplying countries which have no stocks of oil of their own for production of plastics
is economically justified already today.
At present, biopol is produced at a pilot plant at the ICI Biotechnological Centre in the
UK. Its costs are still relatively high, as the process developed by the company enables the
production of the final product with a diverse range of the physical properties. By the estimates of specialists, the mass production of biopol is economically justified at an annual
output of no less than 1,000 tons.
The company Weisstech Edward Weiss (UK) developed three biodegradable polymer
materials having different degradation rates, costs and application areas. One of the materials is based on polyethylene with addition of polyamide links and several other chemical
substances. Depending on the content of stabilizers, its life time can vary within a rather
wide limits from 30 days up to 4 6 months. Another material can be degraded at a temperature of 25C in water for 45 sec. The third material (25 m thick) possesses a light transmission value of 4% and surface smoothness of 78%. The latter material has high protective
properties at the action of alkali and most known solvents, is heat impermeable and
low-temperature-resistant. Apparently, it would find use in packaging chemical additives
of agrotechnical application and aggressive pesticides. Placing a packaging with these substances into slightly warmed water, one immediately obtains a solution of the substance.
The packaging dissolves completely and has no effect on the properties of the fertilizer.
One of the ways of creating polymers degrading under the influence of microorganisms present in the soil and atmosphere is addition of substances, which easily degrade
themselves and are assimilated by microorganisms, into the polymer matrix.
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They include carboxymethyl cellulose, various kinds of starch (rice, potato, wheat,
etc.), mannitol, lactose, casein, yeasts, urea and many other compounds of natural origin.
Material based on grain starch compares favourably to polymers, whose basis are comparatively hard-to-degrade macromolecules. Experts claim that the starch basis can be used
for series production of materials degradable under the action of one of the three degradation factors or their combined effect.
Specialists of Warner-Lampert Co (USA) succeeded in developing a technology of
producing polymer materials capable of complete degradation under the action of the environment conditions. New polymer materials are fabricated based on starch. Until now,
self-degrading polymers were obtained based on compounds isolated from petroleum.
According to reports by specialists of the company, the cost of the new polymers is
quite comparable with known self-degrading materials, because their production will be
based on renewable raw materials potatoes, grain and rice. At present, material known
under the name of biopolymer starch (trade name Novon) started to be used for fabrication
of pharmaceutical capsules, which before then had been produced from gelatin.
The possibility of series production of small self-degrading polymer packagings from
Novon was demonstrated by Warner-Lampert Co. It is expected that in the near future
self-degrading film packagings based on this material will be available.
The company Capsugel AC (Switzerland) together with the Institute of Polymers
(Zurich) also developed a process for production of packaging material from starch. Produced material is absolutely harmless for the environment, its physicochemical properties
are similar to those of traditional thermoplastic materials (polyethylene, polypropylene,
polystyrene), discarded packagings are degraded in the soil without disturbing the ecological balance. It was found experimentally that biopolymers (starch, cellulose, gelatin etc.)
could be subjected to thermal treatment by pressure without changing their properties. The
crucial role in this case is played by the correct choice of temperature and pressure. Experimental studies made use of a machine for casting under pressure, which traditionally is
used for fabrication of disposable cups and tableware. Common powder starch was fed into
the charging funnel to yield in the end a solid shape of required configuration. The company
has begun series production of this material. The first serial product were capsules for medicines.
In agriculture, this material could be used to fabricate long plastic tunnels for protection of vegetable crops from atmospheric forcing. After being used under field conditions
for one or two months, these tunnels are subjected to simple biological degradation in soil.
Besides materials obtained on the basis of grain starch, a polymer based on potato peels
started to be developed; potato peels are first converted to glucose and then to lactic acid
introduced into polymers and copolymers.
At present, when the reprocessing of domestic wastes is oriented not to incineration
but composting, the use of novel packaging material from starch has some advantages; in
particular, there is no need for preliminary sorting of domestic wastes. For instance, carrot
tops or potato peels are composted together with containers (bags from starch film).
Grain starch can be used to produce thermoshrink and stretch film materials widely
applied in packaging, disposable cups for cold drinks, wrapping materials for confections.
Auxiliary components for packaging (for instance, connective rings, clips, etc.) can be also
fabricated from polymers with the degradation time of 3 months up to 2 years.
Materials degraded under the action of light. The main action on light-degradable material is rendered by ultraviolet rays present in the solar spectrum. Usually, to impart polymers with an ability to be degraded under the action of light, use is made of special additives
488
or special light-sensitive groups introduced into the polymer. For such polymers to find
practical application, they should satisfy the following requirements:
as the result of modification, the performance characteristics of the polymer should
not change significantly;
additives introduced should not be toxic, because polymers are primarily intended for
fabrication of containers and packagings;
polymers should be reprocessible by a traditional method and be non-degradable by
the process;
polymer breakdown time should be known and vary within a wide range;
items fabricated from these polymers should be stored and operated for a long time
in the absence of direct ultraviolet radiation;
polymer degradation products should not be toxic.
One of the most known methods of creating photodegradable polymers is introduction
of carbonyl-containing groupings into the polymer chain. Under the action of ultraviolet radiation in natural or artificial conditions, such photodegradable polymers fist crack, then
are covered with a continuous network of cracks, and, finally, break up to pieces of various
sizes, which subsequently turn to powder.
In the USA, a technology was developed for production of ketone-series polymers.
The process is used in the synthesis of polystyrene powders. Ketone branchings from the
main polystyrene chain create favourable conditions for photodestruction under the action
of ultraviolet rays of the solar spectrum. The rate of destruction is directly proportional to
the content of ketone-based copolymer.
Chemically degradable materials. In chemical decomposition, there occur oxidative,
hydrolytic and other reactions with macromolecules of polymer compounds. In Switzerland, a process was developed, which admits both reprocessing of polymer materials, and
their self-degradation. The new technology consists of using polymers based on acrylates,
which totally dissolve in alkaline solutions. Film material, the micromolecular chains of
which have acidic groups, dissolves in solutions with acidity of 9 up to 12. The solubility
of polymer material can be changed by varying the number of acidic groups. Material with
high solubility can be totally degraded in sea water in 4 days.
One of the areas of using new polymer materials is fabrication of labels for returnable
glass containers. The use of such labels was calculated to reduce the duration of washing
containers in caustic soda by one-third. It is also possible to use this material for labelling
dairy packs from high-density polyethylene. After a simple flush, the packaging is completely suitable for reprocessing. Herewith, the possibility of polluting the polymer mass
with other undesirable chemical compounds is excluded.
Increased production of self-degrading polymer materials in the USA is associated
with increased demand for disposable packagings, which should be utilized or destroyed.
American experts on environment protection believe that self-degrading polymer materials
should play in the future the main role in reduction of the amount of solid wastes. Many
packaging materials (paper, cardboard, etc.), getting to waste deposits, degrade very slowly
(no less than 10 years), which presents certain problems in protection of the environment
and makes the authorities to expand waste disposal sites. The use of biodegradable packagings could help to solve this problem, because polymers degrade rapidly under the action
of heat, moisture and light and decompose to form water and carbon dioxide, which do not
disturb the biospheric equilibrium of the ecological system on the planet.
Complete transition to production of bags from self-degrading polymers is an issue under consideration in the USA; these bags would be given to customers in shops. However,
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manufacturers of plastics regard mass production of such packaging materials with great
care. The main reason for this is the non-coordination of actions by manufacturers and consumers. In the opinion of a number of organization, self-degrading polymer materials could
not totally replace the existing polymers, especially in packaging business. Besides, the development and setting-up of series production of such materials requires large capital investment. Opponents of the use of such materials also believe that landfarming of
self-degrading films creates the danger of polluting neighbouring plots of land. Besides, the
film biodegradation rate, depending on the amount of active microorganisms in soil and
photodegradation determined by the intensity of solar radiation, is different for different
areas.
A number of public organizations in the USA argue against the uncontrollable release
of self-degrading polymers, as, in their opinion, aesthetic problems associated with film
degradation products still remain unresolved and the possibility of polluting the environment has not been ruled out. In the near future, research is to be carried out to elucidate the
possible side effects caused by the degradation of polymer packaging materials. In the opinion of specialists, standards for self-degrading packagings and packaging materials should
be worked out. Simple and reliable methods for separation of self-degrading and common
polymers should be developed. The viability of self-degrading polymers in common disposal sites should be assessed in full measure.
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15
Packaging of Meat and

Meat Products
Manufacture of meat and meat products has always been and remains the most labourintensive and expensive industry. Meat goods, especially specialty foods, are high-nutritive
value products, which provide for the requirements of man in animal proteins, vitamins,
mineral substances.
Preservation of the quality of meat and specialty meat products, as well as increase of
their shelf life is a very topical problem. In storage, complex biochemical and microbiological processes occur in meat and meat products. They not only decrease the quality of
products and deteriorate their appearance, but can also produce food poisoning, dysbacteriosis, allergic reactions, metabolic disorders and often make products unsuitable to be used
for food.
The aim in this field is to develop high-quality packagings, capable of not only preserving their properties in transportation, storage and sale of a product, but also of protecting it for the time required.
However, lack of knowledge of packaging materials properties, packaging techniques
and requirements imposed by food products, when the sole criterion of choosing a packaging material is its cost, can not only make achieving the desired result impossible, but also
lead to an adverse effect of the packaging on the quality of the product.
When choosing a packaging for meat and meat products, of great importance are
microbiological and biochemical processes occurring during the storage of fresh meat and
meat products, which can additionally be subjected to culinary and heat treatment. Therefore, the main requirement for packaging of meat products is that polymer material should
not interact with the product, change its quality and create hazardous media. The expiry
date, conditions of storage and transportation of the product should also be taken into
account.
The packaging should ensure, first and foremost, protection from the environment,
namely, should possess the set of optimal properties, which would enable preserving the
original quality of the product. Packaging material should have a sufficient mechanical
strength, air tightness, chemical endurance; should possess optimal barrier properties:
aroma permeability, permeability for gases, water, vapours and fats. Almost all meat
products are fat-containing, so polymer materials intended for their packaging should be
grease-resistant and simultaneously provide for protection from oxygen, which initiates
oxidation of fats.
A broad range of polymer film materials is used at present for packaging meat and
meat products.
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Cellophane, polyethylene, polyvinyl chloride, polyvinylidene chloride, polystyrene

and other films are used as single-layer films. Besides single-layer monofilms, combined
multilayer film materials are widespread. Of special attention are thermoformed combined
materials, including deep draw films, which are characterized by a high strength of heat seal
and a high rupture strength.
Use of materials with a given set of physicomechanical properties for packaging a concrete type of product by a definite method ensures optimal preservation of the product.
15.1 Range of single-layer packaging materials in meat packaging

Cellophane both common and waterproof is produced from regenerated cellulose. The
specific features of cellophane are its low air permeability, resistance to sunlight, fats, oils
and aromatic substances. The film preserves its properties at a change of temperature within
the range of 40C up to +150C. In dry state, cellophane has a high mechanical strength.
Drawbacks of this film include moisture permeability and the dependence of its properties on humidity. The mass of products containing a significant amount of moisture and
packaged into common cellophane film decreases in storage; that of dry products stored in
facilities with increased humidity, increases. Common cellophane is not heat sealable but
can be pasted by dextrine adhesive.
To increase its water resistance, cellophane is lacquered on one or both sides with
various lacquers based on copolymers of vinyl and vinylidene chloride, epoxy resins, nitrocellulose. The lacquer coatings 0.00450.006 mm thick reduce water and vapour permeability of cellophane. Lacquered cellophane yields to heat sealing, which makes it possible
to use it in packaging machines.
The international system of designating individual brands of cellophane:
A and M resistant to atmospheric action, lacquered
H flexible
S heat sealable
T uncoloured
P common nonlacquered.
Widespread materials used for packaging meat products are films from polyolefins:
polyethylene (PE) and polypropylene (PP), which possess valuable physicomechanical and
physicochemical characteristics. Proceeding from the polyethylene production process,
three kinds of polyethylene film are distinguished: low pressure (high density), high pressure (low density) and medium pressure.
High-pressure polyethylene (HPPE) films have no smell, taste, are chemically inert
and nontoxic. Polyethylene belongs to thermoplastic polymers: the film is readily sealable
at a temperature of 110150C by contact and thermopulsed methods. Its high gas permeability for oxygen and carbon dioxide in combination with moisture impermeability and
low hydrophilicity make this film suitable for packaging chilled meat, meat semifinished
products and other products. However, in prolonged contact with fat and oils it swells, its
strength decreases, and fats and oils acquire a specific smell. High-pressure polyethylene
films are insufficiently transparent and have a low heat resistance (90100C).
Low-pressure polyethylene (LPPE) films, as compared with high-pressure films, are
more heat resistant (up to 125C). Besides, they are characterized by a lower moisture permeability and permeability for volatile aromatic substances, a greater resistance to fats and
oils, a higher rupture and puncture strength.
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Low-density linear polyethylene (LDLPE) is structurally similar to HDPE, i.e., it is

based on linear macromolecules, which have longer side chains. This product has excellent
performance properties at high and low temperatures, a good chemical endurance and is
used for production of impermeable stretch films and shrink films.
Thermoshrinkable (oriented) PE films, whose shrinkage under the action of heat is
from 15 up to 65% are used for packaging food products.
The most promising and widespread material for packaging fresh meat on trays is
HDPE (LPPE) the mono- and biaxial oriented thermoshrinkable film. The advantage of
this polymer is an ideal combination of oxygen permeability, because fresh meat needs
oxygen for its colour to be preserved.
Polyethylene films are manufactured under various trade marks: Germany, Suproten,
V-56; USA, Cryovac-U, Irraten, Diotex, Conolex; UK, Rijitex; Japan, Estron-s; etc.
A particular feature of Irraten, along with its enhanced heat resistance (up to 130C)
is its capability of heat setting (about 50%).
V-56 films (Germany) yield to deep drawing, endure high temperatures (120140C),
the action of oxidizers and chemical reagents excluding aromatic and haloid-substituted
hydrocarbons.
Colonex (USA) possesses an increased strength, is stable within the temperature range
from +120C to 70C.
UK-manufactured Rijitex films of up to 0.025 m in thickness have a high gas and water impermeability, low vapour permeability, high chemical endurance, and heat resistance
up to 120C.
In Germany, food products are packaged using new types of polyethylene films. Thus,
low-pressure linear polyethylene (HDPE) has the unbranched molecular structure, which
provides for the required strength at the simultaneous increase of transparency and impact
strength and a decrease of gas permeability.
To protect food products from various undesirable impacts (e.g., ultraviolet radiation)
and to increase the quality of PE films further, copolymerization of ethylene with other olefins is broadly introduced. The known film materials are Marlex-500 based on copolymers
of ethylene with butene; Dutral and Norden, with acrylate; Zetafin, with ethylacrylate;
Elvax, EVA, with vinyl acetate; etc.
Films based on copolymers of ethylene with vinyl acetate (CEVA) became the most
widespread. By their properties, they are close to materials from high-pressure PE, but differ from them by a lower melting temperature, greater transparency, elasticity, high
low-temperature resistance and satisfactory sanitary-hygienic properties. At present, mainly two types of such films are used in packaging practice: deep drawn to 55 mm and
thermoshrinkable oriented.
Formable films, e.g., EVA (USA) have a high strength (20002500 MPa) and rigidity,
as well as increased elasticity at a temperature of minus 3035C, which provides for the
formation of disposable packagings of various sizes.
Thermoshrinkable films from these copolymers are capable of up to a 50% shrinkage
at a temperature of 90100C. The film is strong, possesses an increased grease resistance,
is well heat sealable.
Along with CEVA, products of its saponification are used copolymers of ethylene
with vinyl alcohol (trade mark EVOH), which possess a high transparency, glossy surface
and low gas permeability, in particular, with respect to oxygen and carbon dioxide. These
copolymers are suitable for packaging meat and finished goods.
Ionomers (offered most often under the trade mark of SURLYN-A of the Swiss
494
company Du Pont) are based on polyethylene with carboxyl groups arranged along the
polymer chain, which provides for stable ionic bonding. The cationic bonding is provided
for by metal ions (sodium, potassium, magnesium, zinc). The polymers are processable by
all methods known for thermoplastics. The high strength of the melt enables their use for
extrusion coatings and in skin packagings. Films from ionomers are distinguished by a high
transparency, puncture resistance, grease resistance, tight adhesion to the support, increased
strength of the heat seal in contamination of the film surface with fats, powders, etc.
At present, research is underway to develop films from polyolefins with special propeerties. The film from transparent AFFINITY polyolefin plastomers (POPs) for packaging meat possesses the properties similar to those of surlyn ionomers but costs one third less.
Manufactured according to the INSITE technology developed by Dow Chemical Company,
it is easily heat sealable, is characterized by the strong heat seal for rupture and high barrier
properties. Transparency and gloss of this film promote efficient exposure of packaged
products.
After PE, the most widespread films for packaging meat products are polypropylene
(PP) films. This is a material with good performance properties and relatively established
consumption structure. They are not toxic, are chemically inert, have no taste or smell, are
not subject to mold development. Their vapour impermeability approaches the similar value
for PE films; their moisture and gas impermeability is much higher than these parameters
for PE; their light permeability approaches that of glass.
By their basic properties (inertia to most chemical agents, to acids and alkali), PP and
PE films are similar.
PP films possess a higher heat resistance (120C) and have an increased resistance to
oils and fats, but their heat sealability is inferior to that of PE films. However, the lowtemperature resistance of PP film is only about 20C. It is readily oxidized, as the result
of which its mechanical characteristics deteriorate. The ultimate tensile strength of PP films
is higher than that of polyethylene films, the drawbacks of the film are eliminated by its
orientation in extrusion in two mutually perpendicular directions. Orientation increases the
rigidity of PP film, its resistance to solvents, as well as water and vapour impermeability.
The low water-absorbing value and good resistance of PP films to fats and oils stipulates their use for packaging fat-containing and culinary articles, edible rendered fats etc.,
and the high heat resistance enables sterilization of products in these films at a temperature
of 120130C.
Polypropylene films, as well as polyethylene films, are manufactured under various
trade marks: in the USA, Moplefan-TQ and Moplefan-Q, Profax, Proplin, Cryovac-U; in
Italy, Moplen, Marlen; etc.
According to several estimates, about 10% of the total production of polymer packaging throughout the world is biaxially oriented polypropylene (BOPP).
In Russia, the market for this product is yet at the development stage; nevertheless, the
estimated market potential of this packaging film can reach 100,000 tons. Experts call
BOPP the queen of polymer films. Owing to its crystal-clear transparency, shock resistance,
absence of smell and flavour, high protective properties and pronounced gloss, this film is
used for manufacturing various packagings mainly for food products.
It should be noted that the cost of PP films is higher than that of similar items from
LDPE, so they are used in applications, which require higher barrier properties, transparency and gloss than those provided by LDPE. Besides, PP finds wide use as sheets in forming disposable plastic containers and as blown material to produce various plastic bottles
and cans.
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A new type of PP, Pro-fax SC-204 (Montell North America) is especially suitable for
packaging frozen products. Although this material becomes rigid, it possesses a mechanical
strength to damage and replaces the bilayer composite materials used until now.
Recently, the market of polyolefin-based packaging materials was supplemented by
an advanced development of the Swedish company Ecolean, lean material, a 21st century
packaging product. Manufactured from calcium carbonate in combination with polyolefins,
which are produced from natural gas, it is capable of replacing many materials used nowadays. This is a universal packaging material recommended for a broad range of food
products. Its increased barrier properties to ultraviolet radiation make it possible to use this
film for automatic or manual packaging of chopped meat patties.
Lean materials possess evident advantages over a number of currently used packaging
materials. The technological merits of lean materials demonstrate a considerable economy
at all stages of packaging production. The economy is present already at the stage of production of these materials. This is achieved, first of all, by using generally available resources as raw materials. Besides, the production process requires less energy consumption as
compared with traditional packaging materials with paper, foil and plactics as their components. As lean materials consist of calcium carbonate by 50%, they require no energy for
utilization and completely dissolve in soil in several months. Thus, these materials have
excellent ecological parameters and do not contaminate soils. Lean materials can be
formed, made soft as silk or hard as glass.
Along with polyolefins, film materials from polyvinyl chloride (PVC) are used for
packaging food products.
They can be conditionally divided into two groups: the first group, rigid films based
on nonplasticized PVC and rigid shock-resistant films based on modified PVC; the second,
plasticized films with plasticizer content of over 30%.
Nonplasticized PVC films are rigid films possessing a high mechanical strength and
high chemical endurance; they are characterized by low vapour, water and aroma permeability, resistance to fats, oils, acids, alkali and a number of solvents; are practically devoid
of smell and taste; are resistant to mold development, are physiologically harmless.
One of the valuable properties of rigid PVC films is their capability of molding, which
stipulates their widespread use as consumer containers (tubes, cups, bottles, etc.) for a broad
range of food products, including meat products and fats. A disadvantage of these films is
their low heat resistance, light resistance and poor heat sealability.
Plasticized PVC films are soft packaging films. Application of a plasticizer (diethyl
phthalate, dioctyl phthalate, dibutyl cebacinate, butyl stearate etc.) increases their low temperature resistance, tearing strength, imparts them with elasticity, but decreases heat resistance even more. The strength and chemical endurance of plasticized PVC films are lower
than those of nonplasticized films; and vapour, water and gas permeability are higher.
At an increased temperature and high humidity, the vapour permeability of plasticized
(soft) PVC films increases severalfold. Under these conditions, it is subject to microbial action, which is due to the presence of plasticizers in the film. Plasticized PVC films have high
strength parameters but poor slide.
Soft PVC films have advantages over PE films with respect to resistance to puncture,
but are more permeable for water vapours and change their properties stronger under the
action of temperature.
Plasticized PVC films are used the most for packaging food products. They possess an
increased low temperature resistance (minus 3050C), preserve their elasticity at these
temperatures, are heat sealable on common packaging machines. A characteristic property
496
of such type of films is their capability of heat setting (about 60%). These valuable properties determine their wide use for packaging various food products (meat, fish, vegetable,
fruit etc.).
The most known trade marks of PVC films are as follows: in Italy, Cryovac-XL,
Cryovac-HS; in Germany, Resinit-PC, Vinol, Elaston, Miraplast; in the USA, Vitafilm; in
the UK, Vestolit, Suproterm etc.
Polyvinylidene chloride (PVDC) films are films from copolymers of vinyl chloride
and vinylidene chloride. They are manufactured as hoses and plane-oriented films
0.010.07 mm thick. The films are strong, elastic, transparent; have a low vapour, water,
gas and aroma permeability; are resistant to fats, oils, chemical reagents; are wear-resistant.
The thinnest PVDC film exceeds by its vapour impermeability the thickest films from other
polymers. Thus, the gas permeability of a PVDC film for oxygen and carbon dioxide is
500-fold, and for nitrogen 320-fold lower than that of a twice thicker film from other polymers.
At a temperature below 0C, PVDC films lose their elasticity, become more rigid,
reaching a maximum rigidity at 18C. Therefore, they are not recommended to be used
for packaging long-storage products.
The most known and competitive brands of PVDC films are as follows: the USA and
Italy, Saran, Cryovac-S and S-204; Japan, Kurehalon CA, CB, SB, F; Russia, Poviden.
They are manufactured as strongly oriented films (up to 80%). In orientation, polymer crystallizes, which significantly increases the strength characteristics of film material; besides,
the oriented film is more transparent than the non-oriented one.
Orientation imparts the film with a capability of heat setting, which depends on the fabrication conditions, extent of orientation, temperature and composition of polymer and
varies within the range of 3080%. Setting of the film begins at 5060C, and at heating
up to 95100C it reaches 6080%. At 8090C, the setting stress reaches a maximum
(12.715.6 MPa).
A characteristic property of these films is their ability to carry an electric charge, which
provides for electrostatic adhesion; owing to a combination of these two properties (heat
setting and electrostatic adhesion), a packaging from the film overwraps the product very
well, prevents the development of molds on it, improves the appearance of the packaged
product, etc.
PVDC films are heat sealed at a temperature of 155165C. The most efficient method
of heat sealing is by high frequency.
Russian chemical industry manufactures the Poviden film of grade U (thickness,
0.030.04 mm) and grade VU (thickness, 0.030.051 mm). Along with the main basic
properties characteristic of such type of films, these grades have their own features. Thus,
the extent of heat setting of the film of grade U is 1525%; and of grade VU, 3540%.
The Japanese company Kureha Chemical Industry Co. Ltd manufactures Krehalon
films of grades CA, CB, S8 and F; the Italian company Grace Italiana S.P.A., the film Cryovac of grades S, S-204, O-300, etc.
The Krehalon film of grade CA is characterized by a low vapour and gas permeability;
a good stickiness of the film makes it suitable for manual packaging. The film of grade CB
has an even lower permeability for vapours and gases. Grade CB films are characterized by
a high transparency and increased tearing strength; grade F films have an increased setting
value in heating.
Owing to their physical and protective properties, PVDC films are widely used for
packaging food products. Their gas, water and vapour permeability enables their use for
CHAPTER 15
497
packaging products under vacuum or in a modified gas atmosphere (carbon dioxide, nitrogen or a mixture of gases). This kind of packaging increases the shelf life of products.
Another widespread method of packaging food products is called Cryovac (with
second skin appeal), based on the capability of the film for heat setting. It is applied, as a
rule, simultaneously with vacuumizing the product and makes possible long-term storage
of products, because the film adheres to the product as tightly as the skin leaving almost no
air in the packaging, and thus preventing the development of aerobic microorganisms. Low
temperature storage at minus 1820C of products packaged by the Cryovac method provides for the preservation of their high quality for 610 months.
Polyamides are obtained by condensation of dibasic acids with diamines and are
characterized by the number of carbon atoms in each of the monomers. Of commercial
significance for production of films are polyamides PA-12, PA-6 and PA-66. Besides
monofilms obtained by blow extrusion, a great number of laminates with them are manufactured (e.g., polyamidepolyethylene) and coextrusion films (e.g., PAadhesivePO,
POadhesivePAadhesivePO).
Polyamides are a rigid material with a high breaking strength and high abrasion hardness. They withstand sterilization up to 140C by steam and up to 180C by dry air. PA
films possess a high vapour permeability and low gas permeability. Nonoriented and littleoriented PA films in combination with heat sealable layers are widely used for thermovacuum packaging by automatic machines. They are aroma-impermeable, require no additional treatment for overprinting. These films are resistant to organic solvents, oils, fats. The
transparency and gloss of PA films are not too high, but are improved by addition of modifiers and by biaxial orientation, which improves their mechanical properties, rigidity;
vapour and gas permeability.
Nonoriented PA films preserve their strength properties within the temperature range
from 20 up to +150C; and oriented films, from 60 up to +150200C. The films are
resistant to alkali, organic solvents and oils. However, they are little resistant to oxidants.
The vapour permeability of these films depends on temperature; e.g., at 205C, this parameter increases 2.5-fold as compared with usual temperature (2022C).
The currently used PA films for packaging food products in the West are Rilsan
(France) based on polyamide 11; Silon Nylon-film (USA); Supronyl, Suprotex (Germany),
etc.
PA films are used for packaging meat articles, semifinished products, ready-to-eat
meals under vacuum or in an inert gas medium. They are used when oil resistance is
required, as well as if products are subjected to low temperatures, because films remain
flexible even under these conditions.
Polyester films are mainly polyethylene terephthalate (PET) films.
The structure of PET imparts material with truly unique properties: a high transparency in amorphous state, low gas permeability, and, therefore, excellent barrier properties;
resistance to fats and mineral acids; high shock resistance (90 kJ/m2) within a wide temperature range; low moisture absorption coefficient; easy coloration in the bulk; excellent
colour overprinting; good processibility by extrusion, injection casting, thermoforming.
This set of properties stipulates a wide use of PET in packaging industry.
These films are distinguished by an increased rupture and impact strength. Possessing
a high endurance to surface inflections, they withhold over 20,000 deformations before failure. The films have a high heat resistance; herewith, the strength properties are preserved
within the temperature range from 60 up to +150C. However, prolonged heating for
1.52 h at a temperature of 150C insignificantly decreases the mechanical characteristics.
498
PET films are grease-impenetrable, chemically inert, resistant to organic solvents and acids.
Fats were found not to penetrate a 0.025 mm thick film after two months of storage at a
temperature of 20C. PET films are moisture permeable; the gas permeability of these films
is low, they are considered to be gas-impermeable in practice.
PET films are used for packaging frozen meat, ready-to-eat meat meals, spices.
The known trade marks of PET films are Filmon-C5 (Italy), Melinex and Terilen
(UK), Mylar and Liminen (USA), Terphan-12F (France), Hostaphan and Nalophan (Germany). The (oriented) PET film manufactured in Russian is lavsan.
The disadvantage of PA and PET films is their poor heat sealability.
In the recent years, polyamide and polyethylene terephthalate films have found wide
use in manufacturing of combined packaging materials (polyamidepolyethylene, polyethylene terephthalatepolyethylene, polyethylene terephthalatefoilpolyethylene etc.).
Polystyrene (PS) is a transparent thermoplastic polymer, hard, rigid, brittle; has no
smell or taste; is physiologically inert. The strength characteristics of polystyrene deteriorate with temperature increasing. In practice, it can be used at a temperature no higher than
80C. At the same time, the strength and constant size of polystyrene films do not depend
on humidity of the environment, which is a positive property of this material.
In the recent 1015 years, new types of PS plastics were developed and are used for
packaging food products. They are produced by combining PS with synthetic rubbers. They
possess improved thermal and chemical properties and impact strength (hence the name
impact-resistant polystyrene).
Impact-resistant polystyrene is characterized by a high strength, resistance to alkali,
oils; is well processed into articles by various methods: injection casting, press molding,
extrusion. Russian industries manufacture impact-resistant polystyrene of several grades to
be used for packaging dairy products (cups, trays, etc.) and meat products (trays for packaging meat and meat products).
In Western literature, there are many reports of the use of various containers from PS
and its copolymers for packaging dairy and meat products. At present, two-fold and
multi-fold impact-resistant PS films are successfully introduced into the market. By their
physicotechnical properties, two-fold PS films are in practice analogous to single-fold
films.
Trays for packaging meat and meat semifinished products are also produced from
polystyrene foam with the uniform fine-pore structure (styrofoam). The company Applied
Research (UK) manufactures the polystyrene foam film of 0.873.1 mm in thickness,
which is used not only for fabrication of polymer trays for meat packaging, but also consumer containers for meat products, including after culinary treatment; it can be used to
warm up products in a microwave oven.
Polystyrene foam Styropor (Germany) is used for packaging frozen food products.
15.2 Combined film materials

Each of the above polymer materials possesses a set of valuable properties; however, none
of them is capable of satisfying absolutely all requirements imposed on film materials. If
we take only one industry manufacture of packaging materials for food products even
here the requirements to packaging films are diverse and often contradictory. Films should
satisfy the following requirements:
eye-catching appearance, gloss, transparency
protective barrier properties against the action of oxygen of the air, moisture, aromas,
CHAPTER 15
499
light (especially ultraviolet), fats, microorganisms

resistance to stretching, punctures, cuts, bends
sufficiently low friction coefficient to ensure the sliding of the film in the packaging
machine, but not too low so that packagings could be put one on another, stack up etc.
rigidity low enough for the packaging to be flexible, but sufficient to ensure the passage of the film through the packaging machine and provide for the attractive packaging
ability to endure high temperatures, boiling, warmup in a microwave oven and at
the same time to be formable at sufficiently low temperatures.
When choosing a packaging, one of the most important questions asked by food manufacturers is shelf life. Most often food products manufacturing companies, considering
their production processes, decide in favour of this or that type of packaging, being guided
by the recommendations of packaging manufacturers. However, to make a correct choice,
it is necessary to know the features of various materials used for packaging.
For better preservation of products, usually polymer materials are used, which possess
the greatest barrier properties, i.e., are capable of preventing the penetration of gases (such
as oxygen, carbon dioxide) water vapour and off-flavours. The stable atmosphere inside the
packaging is capable of preventing the development of harmful microorganisms and of preserving the product for further safe use. Especially in the case when a packaging from a
multi-fold barrier film, hermetically sealed under vacuum, is used. Besides, if this packaging would subsequently be pasteurized or sterilized, the shelf life of the product would be
significantly increased.
Thus, the permeability of polymer materials for gases, first and foremost for oxygen,
and for water vapour is the main factor affecting the shelf life, and should be taken into account when choosing the material for packaging.
Taken separately, polymer materials do not possess universal properties to be able to
provide for the entire range of consumer properties. Thus, some of them have excellent barrier properties for oxygen, but at the same time are well permeable for water vapour.
Besides, far from all of them can be used as material well sealable to the material of the
packaging support. Therefore, usually multilayer films are used as packaging material with
good barrier properties.
If we consider various types of widely used polymer materials from the point of view
of their ability to prevent penetration of gases and water vapour and arrange them in a decreasing sequence of the barrier properties with respect to oxygen, we will have the following sequence:
EVOH (copolymer of ethylene and vinyl alcohol)
PVDC (polyvinyl dichloride)
PA (polyamide)
PET (polyethylene terephthalatelavsan)
The column of polymer materials with depleting barrier properties with respect to
water vapour is as follows:
HDPE (high-density polyethylene)
PP (polypropylene)
LDPE (low-density polyethylene).
Table 15.1 presents the values of permeability coefficients for oxygen and water
vapour for various polymer materials (according to the data by Exxon Mobil).
Of the factors affecting the barrier properties of polymer films, we would first note the
temperature of the environment as well as the thickness of polymer material. As is known,
ooo
500
Table 15.1
Type of material
LDPE
HDPE
Nonoriented PP
Oriented PP
PVDC
EVOH
Polystyrene
PA
PET
Vapour permeability coefficient

Oxygen permeability coefficient
(g/m2 for 24 h at 90% relative humidity
(cm3/m2 for 24 h at 23C)
and temperature of 38C)
1520
312
810
5
15
1550
120
>150
1530
300013000
5003000
10006000
2400
13
0.22.5
25007700
30100
50150
a decrease of temperature of the environment and an increase of thickness of polymer material increases the barrier properties of film material. It is seen in the table that material of
EVOH has the greatest barrier properties with respect to oxygen. However, its use is somewhat restricted due to its high cost. The undoubted leader in both parameters of the barrier
properties is PVDC; however, this material does not yield to reprocessing, is not in practice
utilizable and its incineration produces poisonous gases.
When choosing a polymer capable of preventing the penetration of water vapour into
the packaging, the most frequently used films are those, which include HDPE. The most
widespread type of barrier films intended for storage of meat and fish products are films,
which have LDPE and PA in their composition. This type of packaging is, in fact, the very
optimal variant from the point of view of cost versus effect.
With the view to ensure the high protective properties of the polymer packaging for
food products, combined films were developed. A combined film consists of the base film
and an applied film. The composition of the combined film can also have other additional
layers with special properties.
The base film is most often characterized by mechanical strength and is, to a greater
or lesser extent, gas-impermeable for oxygen or aromatic substances. The most frequently
used base films are cellophane, PET (biaxially oriented), PA, PP (biaxially oriented).
As packaging materials should be heat sealable, one of the layers of combined film material should be a heat sealable film, as a rule, polyolefin.
The properties of individual layers of the combined film are manifested the most only
if they are strongly joined.
At present, the following multilayer polymer materials are mainly used for packaging
meat products:
PET (lavsan) / PE (polyethylene) for vacuum prepackaging of chilled and frozen
meat products with shelf life from 14 up to 30 days
OPA (oriented polyamide) / PE for vacuum prepackaging of chilled and frozen
meat products with shelf life from 30 up to 180 days and more
PA (nonoriented polyamide) / PE for vacuum prepackaging of meat products followed by heat setting.
Packaging materials can also contain a larger number of layers. Thus, for instance,
portioned sausage articles, ham and other specialty products are, as a rule, with the aim to
CHAPTER 15
501
increase their shelf life, also packaged under vacuum into multilayer films with high barrier
properties, e.g., PE/PA/PE or PE/PET/PE. For products with an increased fat content
(bacon, lard), it is recommended to use films from grease-resistant polymers, such as, e.g.,
saran (PVDC), polyamide. The films based on nonoriented PA and PE are often used for
slicings.
The assortment of packaging combined films is broad. They are conditionally divided
into three groups: flexible films (including those for packaging products under vacuum or
in a modified gas atmosphere); thermoformable films for packaging products under vacuum
or in a modified gas medium; films sterilized or subjected to boiling, including aluminium
foil-based multilayer films.
At present, thermoformable materials are paid special attention in the packaging technique. This is due to the fact that they enable packaging a product into a formable package,
thus providing for the reliable air tightness of the seal, unlike the packaging into a flat bag,
e.g., from C/PE, when creases or folds are possible. Formable polymer materials (PA/PE,
PET/PE, PP/PE) are used in meat industry for packaging meat, meat semifinished products,
sausage articles, frozen meals, etc.
In the recent years, a broad assortment of multilayer combined materials are produced
in Germany, Finland, Italy, the USA and Japan; these materials are distinguished by a high
puncture and impact strength, etc.
Thus, the Finnish company Wihuri OY Wipak developed a special type of multilayer
film based on PA and PE; the film is suitable for reprocessing on thermoformation machines. It is flexible and elastic, possesses a high strength, is readily formed on traditional
thermoformation equipment. The multilayer film is gas-, vapour- and aroma-impermeable;
it has a considerable deep drawing value, is recommended for a broad assortment of food
products, including meat (cuts, large slabs, semifinished products, ham and other items).
The Holland company Krehalon Synclair Packaging manufactures a wide assortment
of high-barrier thermoformed films consisting of 5, 7 and 14 layers. PA, PE and EVOH in
various combinations, joined by an adhesive, are used as the main layers. Thus, for instance,
14-layer films of the following composition: PE/Tie Layer/PA/EVOH/PA/Tie Layer/
/PE/PE/Tie Layer/PA/EVOH/PA/ Tie Layer/PE possess very high barrier properties with
respect to gases, are resistant to punctures, have an increased protection from ultraviolet radiation, which makes them indispensible for packaging diverse meat products, intended for
long-term storage, including large bone-in meat cuts.
A special group of multilayer combined films are Cryovac thermoshrink films based
on PVDC and polyolefins. These films are manufactured in Italy and the USA and are intended for packaging products under vacuum by the Cryovac method. The films are characterized by a high strength and elasticity; vapour, gas and aroma impermeability; grease
resistance. Their distinctive feature is the capability of heat setting and easy heat sealability.
These are a kind of combined materials based on saran in combination with low- and medium-pressure PE. They were developed by Grace Italiana S.P.A. (Italy) and at present are
the most widespread item for packaging dairy and meat products.
In the USA, Standard Packaging Corporation developed a new type of polymer packagings for portioned meat for trading networks. The packaging is a rigid formed bag (e.g.,
from PVC or PS) sealed with the double lid. The outer part of the lid is impermeable and
the inner part is well permeable for oxygen. According to the data by the company, this
packaging enables storage of meat at a temperature of 01C for three weeks. During the
sales, before meat is put into cooled counters, the outer lid is removed and the natural colour
of meat is restored in 510 min.
502
Table 15.2 presents some variants of multilayer films and their application areas.
Table 15.2 Films for vacuum thermoforming packaging machines.
Lower film,
m
F l e x i b l e
p a c k a g i n g
PA/PE 100250
p a c k a g i n g
Properties
of packaging
Application
Note
Vacuum
forming of the
support; if high
setting is used,
mechanical
extrusion is
added; forms
are cut by
blades
OPA/PE 75100
Average barrier
properties;
mechanical
strength, lower
support layer sets
Vacuum
packaging of
fresh meat,
slices,
cheeses, etc.
Cellulose
For sterilization
PA/EVOH/PE
100250
OPA/EVON/PE
75100
High barrier
properties;
mechanical
strength; more
expensive than
PA/PE
Packaging of
medical
preparations
Vacuum
packaging of
foods
PA/PP 100250
PET saran/PE
75100
OPA/PP 75100
PVC/PE 300600
R i g i d
Upper film,
m
PET saran/PE or
OPA/PE 75
PVC/C/PE 300600 PET saran/PE 75

PS 4001000
Lacquered foil
PS/PET 4001000
Lacquered foil
PS/PE 4001000
PET/PE 75
Foil/PE
Average barrier
properties; gloss;
sterilization
allowed
Vacuum
packaging of
medical
preparations
and foods for
subsequent
sterilization
Average
hermeticity; high
strength; high
capability of
thermoforming
The same but high
hermeticity
Packaging of
any foods on
rigid support
Preheating of
film required;
forms are cut by
press tools
The same but

in a modified
atmosphere
No hermeticity;
Yoghurts;
Two stages of
good water
desserts
film preheating
permeability
recommended;
forms are cut by
press tools
The same but fat
Margarine,
resistance
butter, creams
Hermeticity, water Smoked and
permeability,
frozen
aroma/fat
foodstuffs
resistance
503
CHAPTER 15
Table 15.2 Films

for vacuum thermoforming packaging machines.
(continued)
Lower film,
m
PS/EVOH/PE
4001000
Upper film,
m
PET saran/PE 75
PS
modified/EVOH/PE
4001000
PP/EVOH/PP
4001000
PS exp./ EVOH/PE
4001000
PP exp./ EVOH/PE
PET/EVOH/PE
300600
PVC 200400
Lacquered PVC,
cellophane or
paperboard
PVC 100
PETP 200400
PETP 100
Properties
of packaging
Application
Note
Low gas
permeability;
barrier; aroma
resistance;
hermeticity
Packaging in
modified
atmosphere;
replaces
PVC/C/PE
and PVC/PE
Low gas
Packaging of
permeability; can pasteurized
be heated up to
foodstuffs in
8590C
modified
atmosphere
The same but up to Packaging in
120C
modified
atmosphere;
warming up in
microwave
oven; can be
sterilized
Low permeability, Packaging of
hermeticity
foodstuffs for
long-term
storage in
modified
atmosphere
The same but with
warming up in
microwave oven
Gloss,
Packaging in
transparency, low modified
permeability,
atmosphere
hermeticity
Very good
Non-food use
thermoformability of the type of
blister
packaging
The same plus gloss
Special
requirements to
film preheating
stage
High warmup
temperatures
Special
equipment for
for form-cutting
station
Positive
forming, heat
sealing
Special
high-frequency
sealing-off
equipment
The same but

welding is stronger
This is just an insignificant part of multilayer materials in the arsenal of packaging

manufacturers.
15.3 Modern trends in the development of chilled meat packaging technology

Packaging of fresh meat is a special topic. When packaging fresh meat, it is necessary to be
aware that in the living organism it is sterile, because blood leucocytes leave no chances to
504
foreign bacteria to survive. However, after the product was separated, bacteria getting on
the surface of meat from the air or from items with which it is in contact, immediately begin
propagating in geometrical progression. Therefore, when packaging meat, the crucial issue
is the time that passed from the moment of separation and the conditions of product storage.
Investigators pay great attention to the development of the most rational and efficient
technology of packaging chilled meat, because its production in dressed and packaged
shape is one of the ways to increase endurance and to reduce shrinkage in storage.
It is known that the quality of chilled meat changes in the process of storage. The taste
and flavour, tenderness, digestibility and assimilability improve, but the colour of the muscle and fatty tissue deteriorates; there occur shrinkage, oxidation of fat, etc. Packaging into
film materials along with cooling, the main preservation method enables preserving the
quality of chilled meat to a greater extent and increasing its shelf life. However, this term
largely depends on the technology of the refrigeration treatment of meat, gas permeability
of packaging material, method and parameters of packaging and storage conditions.
The main requirements imposed on polymer materials used for packaging chilled meat
are as follows: physiological harmlessness, chemical inertness, high mechanical strength
(especially for punctures and notches), elasticity; vapour, water and grease impermeability;
transparency, impermeability for microorganisms.
Polymer materials used for short-time storage of meat up to one kilogram in weight
and natural semifinished products mainly have a high oxygen permeability and low vapour
permeability. This provides for the preservation of bright red colour and insignificant losses
due to evaporation of chilled meat. Such materials include lacquered viscose films (cellophane), polyethylene, plasticized polyvinyl chloride, plyofilm, etc.
Changes of heme pigments can depend to a significant extent on conditions of meat
storage, in particular, on the gas permeability of packaging material. Oxygen-permeable
films contribute to the preservation of the colour of muscle tissue for 23 days at a temperature of 04C. The quality of chilled meat (bone-in and boneless beef and pork cuts), packaged into oxygen-permeable films, remains sufficiently high for 34 days of storage at a
temperature of 02C.
In further storage, the absorption spectrum characteristic of meat pigments changes,
because oxymyoglobin is reduced to myoglobin and is subsequently oxidized to metmyoglobin. By the same time of storage (35 days), microorganisms on the surface of meat actively develop.
Packaging of chilled meat into film materials with a low gas permeability makes it possible to decrease the oxidative changes of pigments and lipids, shrinkage of meat and inhibits microbial growth to some extent. Herewith, of special interest is the process of
packaging chilled meat under vacuum and in a modified atmosphere (MAP).
Studies carried out in this direction showed that the duration of storage of chilled beef
and pork cuts, packaged under vacuum into a polyethylenecellophane film or saran, at a
temperature of 04C is 23 weeks. Herewith, the quality of beef cuts stored in packages
at a degree of vacuumizing of 98% was noticeably higher than at 8085%.
Studies of the effect of the extent of vacuumizing and storage temperature on changes
of heme pigments of meat showed that the higher the extent of vacuumizing and the lower
the storage temperature are, the smaller the rate of the oxidative changes of muscle tissue
pigments is. The coloration of packaged meat is preserved for 2835 days at the vacuumizing of 9598% and storage temperature of 13C. The predominant colour in the coloration of chilled meat packaged under vacuum at an oxygen partial pressure in the package
0.81.0 mm Hg (1.01.33 kPa) is purple-red colour of reduced myoglobin.
CHAPTER 15
505
A MAP system consists in the replacement of the air in the packaging with a mixture
of gases of an appropriately chosen composition, depending on the type of packaged
product. The appropriate composition of gases chosen for the packaged product inhibits the
degradation processes occurring in the product. Owing to this, it is possible to preserve the
natural properties of the product, which are associated or identified with its freshness.
The composition of gases introduced into the packaging are subject to some changes
during the storage of the product, owing to either the permeability through the material of
the packaging or as the result of processes occurring in the product, such as, e.g., dissolution
of this gas in fresh meat. An obligatory condition of using the MAP system is the use of
packaging materials with the high barrier properties with respect to gases.
The use of MAP contributes to:
an increased safety of products for health, owing to the limited development of
microorganisms
preservation of the nutritive properties by preventing oxidation of fats, biologically
active compounds, vitamins
inhibition of undesirable physicochemical processes
significant extension of the stability period of the product.
The current significance of MAP is indicated by the number of packagings in which
it is used. For instance, in 1997 the British market for it was estimated to be 2.7 billion, and
a growth up to 3.7 billion is envisaged in the next 10 years.
The main gases used in MAP are carbon dioxide, oxygen and nitrogen. Carbon dioxide
(usually used at a concentration higher than 20%, and only in a few cases lower than this)
is distinguished by strong inhibitory properties, which inhibit the development of bacteria
and molds. The mechanism of the inhibitory action has not yet been completely studied;
however, the impact on some anaerobic microorganisms shows that some other factors appear here besides the factor of oxygen removal. The presence of CO2, especially in food
products containing a large amount of moisture, decreases pH of the product as the result
of the formation of acetic acid. Solubility of CO2 decreases the molecular pressure of this
gas in the mixture, leading in extreme cases to a shrinkage of the packaging on the product, which is an effect similar to vacuum packaging. This effect can be balanced by introducing another gas, usually nitrogen, into the packaging. Nitrogen, having no inhibitory
effect on microbial development, has no direct impact on the stability of the packaged product. However, the use of this gas for bathing the products in the packaging prior to filling
it with the gas mixture provides for the maximally possible elimination of the remaining
oxygen, thus countering the development of anaerobic bacteria and also preventing oxidation of fats. At a higher content of N2 in the packaging (Table 15.3), it is easier to maintain
a constant concentration of the gas mixture owing to the fact that the molecular pressure of
N2 is closer to the equilibrium condition. In the cases when it is possible to use a higher
content of N2, one should bear in mind the economic factor due to the lower cost of N2 as
compared with other gases used.
When packaging many products, it is possible to avoid the presence of oxygen responsible for oxidation and rancidity of fats and spoilage of products as the result of anaerobic
bacterial growth. However, there are cases when it is recommended that the content of
oxygen involved, e.g., in the enzymatic oxidation of fresh meat is respectively greater. Preservation of the bright-red colour of beef, which is associated with its freshness, requires the
content of oxygen in the packaging to be even up to 80%. The oxygen entering the reaction
is consumed, its amount in the packaging decreases, but the content of CO2 dissolved in the
506
product increases. In MAP, it is required especially thoroughly to set the content of oxygen
in the packaging.
Introduction of carbon dioxide into the gas mixture is estimated to be positive. Formation of carboxymyoglobin provides for the stability of meat coloration. The presence of carbon dioxide not only has an inhibitory action on microorganisms but is also cytocidal. This
effect is achieved at 210% of CO2. It is also promising to use ethylene oxide in MAP, as
it provides for a bactericidal action.
Application of ozone. The antimicrobial action of ozone is associated with the disturbance of the physiological function of cytoplasmic membranes as the result of involving
the lipid fraction in the ozonolysis, as well as with the oxidation of thiol groups of enzymes.
To increase the storage life of chilled beef, it is suggested to perform ozonolysis by maintaining the concentration of ozone for 4 h at a level of 1020 mg/m3 daily for the first four
days, and then on the level of 46 mg/m3 by 3 h with an interval of two days. Taking into
account the specific features of the reactions occurring in ozonolysis, the issue of using
ozone for increasing the storage times of chilled meat can be solved positively on condition
of a direct proof of preserving the biological value of the product and the absence of the
development of toxic substances in it.
At present, there is a sufficiently large experience of choosing the composition of gas
mixtures depending on the type of product. As it follows from information by various sources, this composition can, however, vary for the same products (Table 15.3). The data presented in the table can be considered as general recommendations, which are to be
confirmed in concrete applications.
Table 15.3 Composition of the gas mixture in packaging of various groups of foodstuffs in a
modified atmosphere.
Foodstuff
Meat and meat products

Raw meat
Fresh beef or pork
Fresh meat and sausage from raw meat
Beef, pork, veal steaks
Fresh minced meat (not frozen)
Raw chicken gobbets
Boiled ham
Smoked sausage and ham
Roast sausage
Lunchmeat
Pelmeni with minced meat filling
Boiled meat
Poultry
Gas mixture composition, %

O2
CO2
N2
6085
70
80
70
70
80
20
50
4015
20
20
30
30
20
30
40
30
25
30
2530
75
25
10
50
60
70
70
100
70
7570
25
25
Packaging of chilled meat in a medium of carbon dioxide or nitrogen significantly

extends its shelf life at a temperature of 04C. Packaging of portioned meat in a gas
CHAPTER 15
507
medium with an increased content of oxygen (7080%) and a relatively high concentration
of carbon dioxide (2030%) increases the shelf life at a temperature of 2C up to eight days.
Of special interest is the technology of packaging boneless cuts of 23.5 kg in gas media. Exudation of meat fluid from boneless beef cuts stored for 1520 days in packagings
with carbon dioxide or nitrogen is 12.2%, which is 1.5 times lower than from cuts packaged under vacuum.
Packaging of meat into gas-impermeable materials under vacuum and in a modified
atmosphere can contribute to a great extent to the preservation of the colour of chilled meat
and a decrease of oxidative changes of lipids, makes it possible to slow down microbial
spoilage of meat and increase its shelf life. Herewith, the parameters of packaging, as well
as the qualitative characteristics of packaged meat have a significant effect on the duration
of its storage.
For packaging meat, of interest is the use of heat-sealed combined materials
(polyesterpolyethylene, polyamidepolyethylene, polyamidesaranpolyethylene, multilayered polyester). These materials are the most cost-efficient and can be used on mechanized processing lines, where the processes of fabricating containers, packaging of the
product, weighing and labelling of packagings makes one whole. The productive capacity
of such mechanized lines is 1525 and more packagings per minute.
The most classical materials used as packagings for vacuumizing were considered for
many years to be:
cellophanepolyethylene laminate
PTE/PE laminate
films from VDC copolymers
PET and PA films as hoses, the air from which is removed by heat setting of the packaged article
PA/PE laminate.
The appearance of PA/PE laminates suitable for deep-draw forming initiated the introduction of a process, in which vacuum packaging and later MAP packaging was united
with preliminary thermal forming of a complex-shape article, whose size, the depth including, corresponded to the size of the packaged product. At present, the assortment of packaging materials, which can be used for vacuum packaging and are mainly intended for
MAP, is much broader. There is no drastic difference between materials used in both systems, though MAP packaging requires higher barrier properties.
In both cases, there is a possibility of using ready-made packages from laminates,
though much frequently used systems are those of thermoforming, filling with or introduction of a mixture of gases, as well as heat sealing. Part of thermoformed packagings can be
made from flexible or rigid material. Rigidity in this case, as increased strength, is the result
of not only using thicker materials, but also due to using higher elasticity-modulus polymers, such as PS, PP, PEHD, PVC. Packaging in a mixture of gases also makes use of the
horizontal system of forming, filling and heat sealing. Table 15.4 compares multilayer materials used in MAP as well as in vacuum packaging. The table covers both rigid materials
and flexible materials intended for the thermoformed layer, as well as flexible materials intended for heat sealing of thermoformed packagings and for package production.
Thus, the currently available methods of packaging chilled meat can be conditionally
divided into three types: packaging into gas-permeable films for short-term storage of meat;
packaging into gas-impermeable films under vacuum; packaging in a modified gas atmosphere; which provide for an increase of the shelf life of meat products.
508
Table 15.4 Laminates used as thermoformed packaging layers in the MAP system.
Rigid and semirigid laminates
PVC/PELD
PS/E\VAL/PTLD
PP/E\VAL/PP
PS/PVDC/PELD
PS/E\VAL/PS/PELD
Flexible laminates
PA/PELD
PA/PP
OPA/PELD
OPAmet/PELD
PET/PELD
PETmet/PELD
PET/A1/PELD
PA/E\VAL/PELD
PA/E\VAL/surlyn
PET/PVDC/PELD
PET/AI/PP
Comments
Very small trays

Very small trays
Very small trays
Very small trays
Very small trays

Very small trays
15.4 Methods and equipment for packaging of meat and meat products
One of the methods of packaging portioned meat and meat semifinished products is their
wrapping on the tray with a transparent polymer material.
The most widespread material for this packaging is the PE thermoshrink film of
0.0250.035 mm in thickness and lacquered cellophane (4045 g/m). Support trays can be
fabricated from paperboard or polymer materials. Of greatest interest are trays from
impact-resistant polystyrene 0.0400.055 mm thick. They are fabricated on thermoforming
equipment by the method of deep draw formation.
The method of packaging meat on support trays is at present widely used in the USA,
Italy, France, Germany and other countries. High-production packaging equipment has
been developed for this purpose.
Packaging machines Automac 22 and Automac 44 developed in Germany produce, respectively, 28 and 50 packagings per minute, to provide packaging of meat and
meat products into support trays with wrapping them with a thermoshrink PE film.
Delford Div. (UK) together with its German branch Sanpack GmbH developed the
horizontal packaging machine Delford SF-600, which wraps polymer trays with the product (fresh-killed and chilled meat, meat semifinished products) into PE or plasticized PVC
films. The performance of the machine is 65100 packagings per minute.
Hayssen Europa Ltd (UK) manufactures automatic machines of T7 series for packaging chilled meat into PE and PVC thermoshrink films. The high performance of the machine
is combined with the possibility of using packagings of different sizes, quick adjustment
and tuning. The product intended for packaging is supplied directly into the drum with the
film, is wrapped into the film (with its margins overlapped), after which the longitudinal
and transverse heat sealing of the seam is performed. The packaged product is weighed. The
productivity of the machine, models PT-414 and PT-110, is respectively 80 and 120 packagings per minute.
Taking into account that the shelf life of meat and meat products packaged into oxygen-permeable film materials is rather limited and makes 4872 h at a temperature of 24C,
research is under way in this country and abroad to increase the shelf life of meat in such
materials.
In Germany, a method was developed to enable increasing twofold the storage time of
CHAPTER 15
509
meat in oxygen-permeable films. The new method is known under the name of a conserving packaging, i.e., the packaging providing the preservation of freshness of the product.
The conserving packaging is a package from an oxygen-permeable film with an inserted
SMS filter (limestone subjected to calcination at a temperature of 1500C) with a high moisture-absorbing capacity. The SMS filter, absorbing moisture (meat fluid) deprives microorganisms of the nutrient medium, which in turn contributes to the decrease of the rate of
microbial growth in the package. Using this method of packaging, the amount of microorganisms per 1 g of product after 46 days of storage at a temperature of 24C is 20,000
microbial cells, which corresponds to the sanitary requirements and food regulations. The
new method was recognized as an invention and was protected by a patent.
The use of modern instrumental equipment enabled Russian and Western researchers
to prove that in packaging meat under vacuum its purple-red colour is due to the presence
of myoglobin on the surface. The content of this pigment at a partial oxygen pressure of
about 1.9 GPa is 7080%; under these conditions, formation of metmyoglobin on the surface of meat practically does not occur, as the concentration of oxygen is very low.
When meat is removed from the packaging and kept for 2025 min in the air, its colour
changes to bright red as the result of interaction with oxygen of the air and formation of
oxymyoglobin. As the concentration of oxygen in the packaging goes up, the possibility of
restoring the original (natural) coloration decreases.
The technology of vacuum packaging of meat products into combined film materials
(polyethylenecellophane, polyethylenepolyamide, polyethylene terephthlatepolyethylene) is assimilated by meat-processing enterprises in 1970s. Portioned meat (0.51.0 kg)
was first packaged on semiautomatic vacuum packaging machines operated according to
the chamber principle, of the type of Negro, Darvac (Italy); Eurovac TV, Multivac B-6
(Switzerland); Supervac (Germany). The mass of the product to be packaged was limited
by the size of the vacuum chamber, whose height (depth) was 100150 mm.
In subsequent years, vacuum packaging equipment was modernized and the above machines were replaced by two-chamber vacuum packaging machines of the type of Autovac
variant (Kramer+Grebe, Germany); Supervac GK and Multivac (Austria), etc., and then the
vacuum packaging machines Autovac X4 and Compack (Kramer+Grebe), Multivac B-7
(Multivac R) and others equipped with conveyors for the automatic supply of packagings
with the product to the vacuum chamber and the removal of ready packagings. Taking into
account that the depth of the vacuum chamber of such machines is about 150280 mm, they
can pack products of 3.55.0 kg in weight.
A number of enterprises in Germany, Great Britain, the USA tested and use the method
of vacuum packaging into thermocaked packages from the combined polyamidesurlyn
film.
Surlyn is a heat sealed ionomeric film developed by Du Pont. At present, it is widely
used in manufacturing combined materials. By its protective properties, surlyn considerably exceeds films from polyethylene compositions.
A characteristic property of packaging into polyamidesurlyn packagings is that after
vacuumizing the package with the product comes into the thermotunnel, where the seam of
the package is caked but not heat sealed as in PVDC films. This additional treatment of
packagings makes it possible to guarantee their air tightness in long-term storage of products.
According to the specialists of the Federal Scientific and Research Center for Nutrition
and Food (Kulmbach, Germany), packaging into a caked package makes it possible
to preserve the high quality of the product. For instance, meat for steaks is stored at a
510
temperature of 02C for three weeks, and at a temperature from 1C up to +1C for four
weeks. According to the available data, about 10% of steak meat supplied to the Western
European market and about 25% to the US market is packaged at present into packages from
the polyamidesurlyn film.
One of the later methods of packaging meat products under vacuum into combined materials is packaging into the thermoformed film of the type of polyamidepolyethylene.
This method of packaging is widespread in the meat industry of the USA, Germany, Italy,
France, Finland, Sweden and other countries, which is due first and foremost to the fact that
it is performed on high-performance equipment, into a formed package fabricated directly
in the packaging machine. This equipment enables combining the entire complex of packaging operations: fabrication of the package, filling it with the product, vacuumizing,
weighing, labelling.
The principle of operation of the vacuum thermoforming line is as follows:
the rolls of packaging material, usually two multilayer films upper and lower are
loaded; the films can be of different thickness and different composition
the lower film is heated and stretched by compressed air (or simultaneously using
additional mechanical pressure, if the film is sufficiently rigid) to take the given shape of
the support
the supports pulled out of the film are moved to the loading section, where the product
is placed
then the supports are sealed by the upper film; vacuum or an inert gas medium is created if it is necessary
packaged products are separated one from another and come to the outlet conveyor;
wastes of film are collected.
This is a continuous process.
Packaging of products in thermoforming lines gives the following advantages:
low prime cost of packaging materials (sometimes two times as low) due to the use
of film rolls, which in the previous case are only a semifinished product for package preparation
the possibility of labelling on the upper film to save on self-adhesive labels
the appearance of the package is by an order of magnitude higher, because the product is placed into the prepared container and sealed uniformly on all sides
this is a continuous process, where the rate of work is set by the machine but not by
man
the automatic machines are equipped with replaceable formation units for fabricating
packages of different sizes.
The widespread use of the method of packaging into a combined thermoformed film
was contributed to by the reliable air tightness of the heat seal in contrast with packaging
into flat packages from combined materials, where folds and wrinkles are possible in the
heat sealing region and, therefore, air tightness of the package can be disturbed.
The main group of thermoformed combined materials (0.0110.013 mm) have the formation depth of up to 60 mm. The most widespread thermoforming machines manufactured
abroad are Multivac, models R67, F70, R70, M72; Tiromat VT (Germany) and others.
As we reported above, a new group of multilayer combined materials manufactured in
the USA, Finland, Japan and other countries appeared on the world market in the 1980s.
These materials are characterized by the low gas permeability with respect to oxygen and
have the formation depth of up to 180 mm. The use of these materials on thermoforming
CHAPTER 15
511
machines makes possible the packaging of cuts (or group packaging of boneless meat), as
well as large slabs of semifinished products of 2.58 kg in weight.
The most known brands of packaging equipment for deep draw formation of packaging (up to 380 mm) are Multivac, models R 5100, M 8551, R 7000; Hammer, models
VT-50, VT-55, VT-100 (Austria); Tiromat VA, models 430T, 560T and Tiromat, models
CS 430, CS 430SLT (Germany) and many others.
In the recent years, the technological properties of multilayer materials were improved
by introducing an additional layer an ionomer surlyn. Besides the properties characteristic
of traditional thermoformed materials based on polyamide, multilayer materials with surlyn
possess not only an increased strength, which is required for deep draw formation (up to
380 mm) of packagings, but are also capable of heat setting (1030%) at a temperature of
8095C and, which is no less important, are heat sealable within a broad temperature
range.
It should be noted that such type of multilayer film is sealed even with the sealing seam
contaminated (by meat, fat, salt), which provides for an increased performance of packaging machines.
In new packaging automatic machines (e.g., Tiromat VA, Germany) operated by the
principle of deep draw and making use of multilayer films with ionomer surlyn, heat setting
is performed without using the setting tunnel, but using a special device, which works as
follows: after vacuumizing and heat sealing, ready-to-use packages are irrigated with water,
whose temperature is 8595C (depending on the thickness of the film). Irrigation with water is done by a turbulently sprayed flow, as the result of which the film is rapidly and evenly
heated. Heat setting occurs without forming folds, the films closely adheres to the product,
taking its shape; therefore, the shelf life of the product increases and its vendibility improves. Despite the relatively high temperature of water, the product is not warmed up, as
the time of contact of water with the film is 25 seconds, and the film itself possesses good
isolation properties.
In the West, the main machines used for packaging meat products in a gas medium are
Multivac, models R 7000, R 5100; Tiromat VT, Swissvac and others.
In Denmark, the method Atmas-pak was introduced for packaging portioned meat; the
method provides for the use of a gas mixture consisting of 7580% O2 and 2025% CO2.
When introducing the method, the multilayer films used were improved by applying
an outer coating, which adsorbs the condensate formed in storage of meat to improve the
vendibility of the product.
Thus, based on available information on the equipment and technology for packaging
meat and meat products, it can be concluded that packaging under vacuum and in a gas medium provides for the preservation of a high quality of meat in long-time storage. Herewith,
the parameters of the packaging process, as well as the qualitative characteristics of meat,
have an effect on its shelf life.
In most meat-processing enterprises, packaging of products in a modified atmosphere
is performed at the same thermoforming machines as packaging under vacuum, as almost
all of their types and models are equipped with gas-filling devices. No adjustment of equipment is required. The packaging process is regulated, which provides for the complete control of the level (pressure) of gas in the package.
Current developments in the field of packaging technology for meat products and
equipment used for this are aimed at the broader use of polymer film materials with high
barrier properties, assimilation and series production of the most advanced packaging materials, as well as development of new efficient equipment and polymer materials with a
512
given set of physicotechnical characteristics.

Analysis of Russian and Western data made it possible to reveal the main directions
of studies in the field of chilled meat packaging technology. All of them have certain advantages; however, it should be admitted that of special interest is meat packaging into
gas-impermeable film materials under conditions of a minimal oxygen content under vacuum and in a modified atmosphere, in particular, carbon dioxide or nitrogen, proceeding
from the possibility of preserving high consumer qualities of meat (colour, taste, consistence, etc.) and an increase of its shelf life.
15.5 Active packaging technology

Systems associated with the use of active packaging are a new field of development of packaging equipment. They are a refutal of the existing tendencies to exclude all interactions
between the packaging and its contents. The purpose of active packaging is a directed impact on the product to provide for its higher quality, as well as to extend the period of stability and usability for consumption.
The technologies related to active packaging broadened the functions of packagings
from a passive barrier with respect to external effects to the active protection of the product.
Only part of the emerging solutions, in view of the applied chemical means, was recognized
to be suitable for contact with food products; however, already at present it is envisaged
that technologies in this field will have a significant effect on the further development of
food industry.
The packaging technologies using active packaging can embrace:
introduction of chemical or enzymatic substances into the package or into packaging
materials to adsorb and eliminate atmospheric oxygen inside the packaging
introduction of substances, which create or adsorb carbon dioxide
monitoring the content of ethylene in the package, by means of adsorption to oxidizing substances or organometal compounds, application of ethanol as a vapour inside the
package as a factor inhibiting the development of microflora
use of preservatives, bactericidal substances and antioxidants to be oozing from the
packaging material
application of moisture regulators
application of a technology enabling the control of taste and smell
use of light adsorbants
application of films releasing a mineral substance to preserve the colour of the product
refinement of the surface of the film to change its permeability
use of susceptors, i.e., films controlling the warming-up of the product in a microwave oven.
It is impossible to describe all the listed technologies; therefore, taking their importance into consideration, below we shall characterize systems of active packaging associated with the elimination of remaining oxygen from the packaging.
Complete elimination of oxygen, even in the case of vacuum packaging, as well as
flushing with inert gas, is impossible in practice. In many cases, even a minor amount of
oxygen remaining in the packaging renders a harmful effect on the quality of the product.
Prior to injection of a chemical substance reacting with oxygen, its content in the packaging should be decreased to a minimum. This is done, e.g., using iron compounds, such as
CHAPTER 15
513
iron oxide and iron carbonate together with catalytic systems, which initiate the reaction.
Nonmetal and organometal substances are also used. Depending on the type of substance
and method of introducing it into the packaging, a decrease of the oxygen content in the
package could be even up to several tens of ppb.
There are also many commercially available preparations intended for these applications. An example could be Mitsubishis Agelles and Freshinax. Agelles used in the form
of a sachet is introduced into packages with a higher barrier properties and makes it possible
already in several hours to decrease the content of oxygen to a level of less than 0.1%, preserving this content for several months. Freshinax can be, e.g., in the coating layer, in the
inner wall of the packaging or in a piece of paperboard saturated with this substance and
introduced into the packaging. Its application makes it possible to decrease the content of
oxygen in the packaging to a level of 0.01%.
An interesting solution is the preparation Freshhiiztr C of the Japanese company Toppan Printing. Eliminating oxygen, it simultaneously creates carbon dioxide, which prevents
the collapse of the wall of the flexible packaging owing to the vacuum emerging as the result
of a decrease of oxygen concentration.
The packaging with an antimicrobial coating is a promising form of active packaging
for food products, in particular, meat products. As microbial contamination emerges predominantly on the surface as the result of transportation after technological treatment, it has
been attempted to increase the safety and delayed spoilage development by using antimicrobial sprays or impregnation solutions. The direct application of antimicrobial substances
on the surface of food products yielded a limited advantage, as during the contact the active
substances were neutralized or quickly absorbed from the surface deeper into the product.
On the other hand, addition of bactericidal or bacteriostatic substances to the formulation
of a product can lead to a partial inactivation of active substances by components of the
product and, therefore, expectedly, only a limited effect on the surface microflora will be
obtained.
Therefore, the use of packaging films with antimicrobial substances can be more effective owing to the slow transfer of the substances from the packaging material onto the
surface of the product; thus, it helps to preserve a high concentration on required sites. If
the antimicrobial substance can be released from the packaging at the time of a more prolonged shelf life, the activity can also propagate to the stage of transportation and storage
during the delivery of the food products.
Antimicrobial substances introduced into packaging materials are capable of controlling microbial contamination, decreasing the growth coefficient and the maximal growth of
the population and/or increasing the lag phase of the sought-for microorganism, or else inactivating microorganisms during the contact.
Introduction of an antimicrobial substance into the packaging system for food products
is carried out by a number of methods. One of them is application of the active substance
by placing it into the extruder during the fabrication of the film or the film subjected to coextrusion. A disadvantage of this method is its economic inefficiency, because the antimicrobial substance not deposited onto the surface of the film does not completely exhibit its
antimicrobial properties. An alternative is introduction of an antimicrobial additive into the
controlled material; e.g., it can be introduced into the layer contacting with the foodstuff
(usually serving as the inner heat sealing layer) of the multilayer packaging material.
According to Han, when developing or modelling a film or packaging with antimicrobial properties, the following factors should be taken into account.
The chemical nature of films/coatings, conditions of the casting process and residual
514
antimicrobial activity.
The choice of an antimicrobial substance is often limited by the instability of the component to the action of heat or by the incompatibility of the substance with packaging material. For instance, 1% potassium sorbate in an LDPE film inhibited the growth of yeasts
on agar plates. The LDPE resin and potassium sorbate can be mixed, subjected to extrusion
and used to press granules for production of the mother batch. These granules can be added
into LDPE resin. The mother batch should be produced at a low temperature to avoid the
decomposition of potassium sorbate under the action of heat. But in the course of another
study (Weng and Hotchkiss) it became clear that relatively polar sorbate, benzoate and propionate are incompatible with nonpolar LDPE. It had been believed that acid anhydrides
are more compatible than free acids and their salts, due to their lower degree of polarity.
The residual antimicrobial activity is the efficient activity of an antimicrobial substance used after press molding (extrusion) and reprocessing (lamination, labelling, drying).
The qualitative analysis of the effect of adhesives and solvents is also required.
The characteristics of antimicrobial substances and food products.
Components of food products seriously affect the efficiency of antimicrobial substances and their release. The physicochemical characteristics of food products can change the
activity of antimicrobial substances. For instance, the level of pH can affect ionization (dissociation/association) of most active chemical substances and is capable of changing the
antimicrobial activity of organic acids and their salts. The antimicrobial activity and chemical stability of introduced active substances can also be affected by the activity of water.
Besides, each food product has its own characteristic microflora. The kinetics of releasing
antimicrobial substances should be developed in such a way so that to preserve the concentration at a level exceeding the critical inhibitory concentration, with account for the possible presence of infecting microorganisms.
Storage temperature.
The storage temperature is capable of affecting the antimicrobial activity of chemical
preservatives. In general, an increased storage temperature can accelerate migration of active substances in the film / layers with a coating, whereas cooling slows it down.
It is necessary to predict the temperature regime in production and delivery and to determine its effect on the residual antimicrobial activity of active substances.
The physical properties of packaging materials.
During the introduction of substances with an antimicrobial activity into packaging
materials to decrease microbial growth, these substances may affect the general physical
properties of packaging materials. Han and Floras, performing their study, found out that
transparency of the film decreased in the introduction of an active substance. The characteristics of packaging material should be preserved after the introduction of active substances even despite an inhomogeneity of the composition.
As we mentioned above, approaches to the development of packagings with an antimicrobial coating can be attributed to one of two types. The first consists in a substance
binding to the surface of the packaging; this requires the sufficiently large molecular structure to be capable of maintaining its activity on the surface of the microbial cell, even bound
to the plastic. Probably, these substances are reduced to enzymes or other proteins with antimicrobial properties. The second approach consists in releasing active substances and
their contacting with the surface of the food product.
Packaging materials of inedible packaging systems can contain any types of food-category additives. Some chemical substances naturally occur in plants or fermented food
products. But mainly they are obtained by chemical synthesis and are attributed to the cat-
CHAPTER 15
515
egory of chemical additives; in some cases, rules for restricting the use of these additives
are required.
In Japan, silver-substituted zeolite was developed, silver being the most widespread
antimicrobial substance imbedded into a plastic. Silver ions inhibiting the activity of quite
a number of metabolic enzymes is a broad-range potent antimicrobial factor. Ceolite, on the
surface of which a number of atoms are substituted for silver, is imbedded as a thin layer
(36 nm) into the surface of the polymer contacting with the food product and, as it appears,
silver ions are (gradually) released as fluid from the surface of the food product penetrates
unprotected depressions of the porous structure. The coating layer itself contains less than
0.001% of silver.
A rather promising approach is also to use these active shells as edible coatings. Edible
films based on natural polymers possess a high sorptivity, which predetermines their positive physiological effect. Thus, when getting into the organism, these substances adsorb and
excrete metal ions, radionuclides (products of radioactive decay) and other harmful compounds, thus playing the role of a detoxicant. Addition of flavouring and coloring agents
into the polymer shell can adjust the taste and flavour of the meat product in the edible film,
thus changing the sensory perception of the product by the consumer, which is especially
important during the intake of dietary products, e.g., foods with reduced content of fat, saccharose, with addition of plant (e.g., soybean) protein. Besides, the ability of edible film to
retain various compounds makes it possible to enrich food products with minerals, vitamins, trace elements etc., thus compensating the deficit of required food components.
In spite of its evident advantages, active packaging has not yet found wide use in Russia. The problem is that the demand for this kind of packaging is yet hidden, potential consumers either know little of home technologies or are not aware of the advantages of
investing into this field. Having a possibility to compare imported and domestic meat products, one can see for oneself that Russian products are not inferior to imported stuff in quality, and in many cases exceed it. Evidently, using advantages of active packaging, home
food products would find its consumer not only in Russia but also beyond its borders. Possibly, this is one of the ways for Russian products to the world market.
516
Conclusion
Modern packaging materials are developed using eco-friendly resource-conserving technologies. Their characteristic feature is that, at minimal practicably justified consumption
rates of polymer film materials, they can be developed only using scientific principles and
physicochemical bases of forming an ordered regular structure in polymer systems.
In the works by Academician V.V. Korshak, it has been shown that in Russia and
abroad chemical production of polymer materials of various compositions is at present
based on methods of synthesis, which enable producing polymers only with the heterounit
structure of macromolecules. Under these conditions of the chemical reaction, produced
polymers of one brand differ by their molecular mass, chemical composition; number, character of distribution and alternation of the functional groups in the chain; conformation and
configuration of macromolecules, and, therefore, morphology and architecture of supramolecular structure they form.
Taking these regularities into account, for imparting packaging materials with the required set of performance properties we proposed methods of regulating the structure of
polymers, based on introduction of small amounts of modifying structure formers into compositions.
In accordance with the phenomenon of the thixotropic decrease of internal stresses in
polymer systems, discovered by us, their mechanism of action is based on creating a supramolecular structure in coatings, with uniform distribution of chemical and physical
bonds within the volume between the structural elements of the polymer matrix. These
bonds determine the impermeability of films for various reagents, structure imperfection,
biochemical endurance in food media, protective and physicomechanical properties of
films and coatings.
It has been shown that internal stresses emerging during the formation and use of polymer materials are a criterion of homogeneity and imperfection of their structure and determine the set of performance properties of articles.
The scientific principles of decreasing internal stresses in various polymer systems
have been worked out.
A method has been proposed for the determination of internal stresses in various polymer composite materials under conditions of their formation and use. An instrument for the
automatic registration of internal stresses has been designed and fabricated.
Based on the analysis of the regularities establishing the relationship between the
structural transformations in polymer systems with the set of performance properties, the
scientific bases for modification of compositions have been worked out. These scientific
bases were used in developing packaging materials for production and storage of food
products.
518
Special attention has been given to consideration of advanced compositions based on

polymerized oligomers, whose solvents are involved in the formation of the three-dimensional network during the buildup of coatings. They also include modified powder systems,
which make it possible to produce coatings with high performance characteristics at a transient impact of a short-wavelength radiation.
Of great practical significance in production of packaging materials are modified
self-crosslinking dispersions of polymers with a polyfunctional set of properties.
The above compositions are the most ecologically safe and enable production of packaging polymer materials with the lowest consumption of heat, electrical energy, labour input and high performance characteristics.
Advanced methods have been developed for recycling and reuse of wastes of packaging materials as secondary raw materials for production of industrial packaging for transportation, prepackaging of products in the trading network and in agricultural enterprises.
Biodegradable packaging materials have been created, whose composition includes
biodegradants as packagings service-life regulators. The purpose of bioregulators is to prevent the formation of molds in packaged food products and contribute to the biodegradation
of utilized packagings in soil.
References
Krivoshey, V.N. et al., Handbook of Polymer Packaging, 232 pp., Kiev, Tekhnika (1982)
(in Russian).
Briston, J.H. and Catan L.L., Polymer Films, 382 pp., Moscow, Khimiya (1993)
(translated from English).
Handbook on Modern Packaging, issue 4, Moscow, Information-Analytical Centre
Avgust Borg (2001) (in Russian).
Gul, V.E., Polymers for Food-production Packaging, Tara i Upakovka, No 3 (1993) (in
Russian).
Leonova, O.G. et al., Combined Packaging Materials with Enhanced Protective
Properties, Plast. Massy, No 4 (1993) (in Russian).
Modern Packaging Materials, Pakindustriya, December (1998) (in Russian).
Novelties on the Market of Shrink Films, Pakindustriya, August (2001) (in Russian).
Thermosetting and Shrink PVC Films, Pakindustriya, August (2001) (in Russian).
Meat Packaging Methods, Pakindustriya, May (2001) (in Russian).

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New Concepts in Polymer Science

Polymers for Packaging and Containers

New Concepts in Polymer Science

Modern Polymer Flame Retardancy

Radiation Chemistry of Biopolymers

Polybutilene Therephthalate (PBT),

Biodegradation and Durability of

Thermal Oxidation of Polymer Blends. The

Polymers Derived from Isobutylene.

Biocide Guanidine Containing Polymers:

Ecological Aspects of Polymer

Active Sites of Polymerization.

Molecular Dynamics of Additives in Polymers

Stationary and Non-Stationary Kinetics

Structure and Properties of

The Concept of Micellar-Sponge

Radiation Chemistry of Polymers

Structure of the Polymer Amorphous State

Diffusion of Electrolytes in Polymers

Cyclolinear Organosilicon Copolymers:

Chemical Physics of Polymer

New Concepts in Polymer Science

Polymers for Packaging

LEIDEN BOSTON - 2008

Printed and bound In The Netherlands

3.3 Modification of cellulose diacetate for packaging materials

4 Compositions for decorative finish and protection of packaging products

5 Technology of the development of canning containers

6 Structure and properties of compositions for protection of canning

Effect of the structure of the block copolymer chain on the properties

8 Ways of modifying the properties of metallized packaging materials

10.4 Methods of developing an optimal gas medium and the technology of

11 Structure and properties of oligomer compositions for protection of transport

13 Technology of the protection of large-tonnage foodstuff containers

14 Ecology and safety of utilization of container/packaging materials

14.6.3 Economic assessment of secondary plastic raw materials

dehydrated beverages (tea, coffee) with readily assimilable carbohydrates added.

Methods and Technology

The nutritive value of foodstuffs

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Methods and technology of preserving food products and raw

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

physicochemical and physicomechanical properties and the possibility of providing a

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

containers. Above, we mentioned the necessity to maintain the temperature of a frozen

Technology of preserving the quality of foodstuffs in manufacturing,

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

of antiadhesion coatings which by their sanitary characteristics are permitted to be used in

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Raw materials for production of

Endocrine / enzyme raw

Foodstuffs of plant origin

Classification of objects of drying.

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Application of chemical preservatives in food industry

1.4.1 General information on chemical food preservatives

Non-dissociative (real) part, %, at pH

POLYMERS FOR PACKAGING AND CONTAINERS IN FOOD INDUSTRY

Cationic and anionic surfactants