Dieter Urban - Polymer Dispersion and Their Industrial Applications - 2002 PDF

Polymer Dispersions and Their Industrial Applications.
Edited by Dieter Urban and Koichi Takamura

Copyright © 2002 Wiley-VCH Verlag GmbH & Co. KGaA
ISBNs: 3-527-30286-7 (Hardback); 3-527-60058-2 (Electronic)
Polymer Dispersions
and Their Industrial Applications
Edited by Dieter Urban and
Koichi Takamura
Polymer Dispersions and Their Industrial Applications. Edited by Dieter Urban and Koichi Takamura
Polymer Dispersions
and Their Industrial Applications
edited by Dieter Urban and

Koichi Takamura
IV Polymer Dispersions and Their Industrial Applications. Edited by Dieter Urban and Koichi Takamura
Editors This book was carefully produced. Never-

theless, editors, authors and
Dr. Dieter Urban publisher do not warrant the information
Dr. Koichi Takamura contained therein to be free of errors.
BASF Corp. Readers are advised to keep in mind that
11501 Steele Creek Road statements, data, illustrations, procedural
Charlotte, NC 28273, USA details or other items may inadvertently
be inaccurate.
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Cover photograph Scanning electron Printed on acid-free paper
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by the deposition of 7.9 µm polystyrene Typesetting TypoDesign Hecker GmbH,
particles on a nitrogen bubble during Leimen
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environment of the Space Shuttle Binding Großbuchbinderei J. Schäffer
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Polymers Institute, Lehigh University,
Bethlehem, PA, USA). ISBN 3-527-30286-7
Polymer Dispersions and Their Industrial Applications. Edited by Dieter Urban and Koichi Takamura V
Contents
Preface XIII
1 Introduction 1
1.1 Names and Definitions 1
1.2 Properties of Polymer Dispersions 3
1.3 Important Raw Materials 8
1.4 Commercial Importance of Polymer Dispersions 10
1.5 Manufacturers of Polymer Dispersions 12
References 14
2 Synthesis of Polymer Dispersions 15

2.1 Introduction 15
2.2 Chemistry 17
2.2.1 Mechanism of Emulsion Polymerization 17
2.2.2 Major Monomers 23
2.2.3 Functional Monomers 26
2.2.4 Surfactants 27
2.2.5 Initiator Systems 30
2.2.6 Other Ingredients 32
2.3 Manufacturing Processes 34
2.3.1 Types of Process 34
2.3.2 Influence of Process Conditions on Polymer/Colloidal Properties 37
2.3.3 Equipment Considerations 39
2.3.4 Safety Considerations 40
References 40
3 Characterization of Aqueous Polymer Dispersions 41

3.1 Introduction 41
3.2 Polymer Dispersions 42
3.2.1 General Characterization of Dispersions 42
3.2.2 Characterization of Polymer Particles 48
3.2.3 Residual Volatiles 56
3.2.4 Aqueous Phase Analysis 57
VI Contents
3.3 Polymer Films 58

3.3.1 Film Formation 59
3.3.2 Macroscopic Characterization of Polymer Films 60
3.3.3 Microscopic Characterization of Polymers 68
References 72
4 Applications in the Paper Industry 75

4.1 Introduction 75
4.2 The Paper Industry 76
4.3 Surface Sizing 79
4.4 Paper Coating 81
4.4.1 Coating Techniques 84
4.4.2 Pigments used in Coating Colors 86
4.4.3 Co-binders and Thickeners used in Coating Colors 87
4.4.4 Binders used in Coating Colors 90
4.4.5 Test Methods 97
4.5 Concluding Remarks 100
Acknowledgments 100
References 101
5 Applications for Printing Inks 103

5.1 Introduction 103
5.1.1 Flexographic Ink 104
5.1.2 Gravure Ink 106
5.2 Ink Composition 106
5.2.1 Pigment Dispersion 108
5.2.2 Emulsion Vehicle 109
5.2.3 Solution Vehicle 112
5.2.4 Waterborne Wax Emulsions and Powders 113
5.2.5 Ink Additives 113
5.3 Physical Properties and Test Methods 114
5.3.1 Typical Properties 114
5.3.2 Application Tests 115
5.3.3 Test Method Abstracts 115
5.4 Inks for Flexible Substrates (Films) 117
5.4.1 Surface Print Film 118
5.4.2 Lawn and Garden Bags 118
5.5 Inks for Paper Board Substrates 118
5.5.1 Folding Cartons 118
5.5.2 Direct Print Corrugated Packages 119
5.5.3 Pre-print Corrugated Packages 119
5.6 Inks for Poly-coated Board 120
5.6.1 Milk Cartons 120
5.6.2 Cup and Plate 120
5.7 Inks for Paper Products 120
Contents VII
5.7.1 Multiple Wall Bags 121

5.7.2 Gift Wrap and Envelopes 121
5.7.3 Newspapers 121
5.7.4 Towel and Tissue 122
References 122
6 Applications for Decorative and Protective Coatings 123

6.1.1 Market Overview 123
6.1.2 Coating Industry Trends 124
6.1.3 Coatings Provide Decoration and Protection 124
6.2 Overview of Coating Formulations 125
6.2.1 Volume Solids and Pigment Volume Content 125
6.2.2 Polymer Matrix 127
6.2.3 Film Formation 128
6.2.4 Typical Polymer Compositions 129
6.2.5 Pigments, Extenders, and Additives 132
6.3 Decorative Coatings 137
6.3.1 Emulsion Polymers in Decorative Coatings 137
6.3.2 Polymer Compositions used for Emulsion-based Decorative Coatings 137
6.3.3 Regional Distinctions in Decorative Coatings 138
6.3.4 Market Size of Decorative Coatings 138
6.4 Interior Decorative Coatings 139
6.4.1 Key Performance Features 139
6.4.2 Interior Decorative Coating Formulations 140
6.4.3 Standard Application and Performance Tests 142
6.5 Exterior Decorative Coatings 146
6.5.2 Exterior Decorative Coating Formulations 147
6.6 Elastomeric Wall Coatings 149
6.6.2 Typical Elastomeric Wall Coating Formulations 150
6.7 Primer Coatings 151
6.7.2 Primer Formulations 152
6.8 Protective and Industrial Coatings 154
6.8.1 Copolymers used in Protective and Industrial Coatings 154
6.8.2 Market Size 155
6.8.3 Industrial Maintenance Coatings 155
6.8.5 Formulation Characteristics for Industrial Maintenance Coatings 156
VIII Contents
6.9 Traffic Marking Paints 158

6.9.1 Description of Traffic Paint Market 158
6.9.3 Typical Traffic Paint Formulation 159
References 161
7 Applications for Automotive Coatings 163

7.1.1 History of Automotive Coating 164
7.2 Automotive Coating Layers 166
7.2.1 Electrocoat 170
7.2.2 Primer 172
7.2.3 Basecoat 173
7.3 Properties of Water-borne Binders used for Automotive Coatings 176
7.3.1 Emulsion Polymers 176
7.3.2 Microgels 177
7.3.3 Miniemulsions 177
7.3.4 Selection of Monomers, Initiators, and Surfactants 178
7.3.5 Secondary Acrylic Dispersions 179
7.3.6 Secondary Polyurethane Dispersions 179
7.4 Rheology 181
7.5 Crosslinking 183
7.6 Application Properties 185
7.6.1 Metallic Effect 186
7.7 Environmental Aspects and Future Trends 186
References 187
8 Applications in the Adhesives and Construction Industries 191

8.2 Pressure-sensitive Adhesives 193
8.2.1 Self-adhesive Labels 194
8.2.2 Self-adhesive Tapes 207
8.2.3 Test Methods 210
8.3 Laminating Adhesives 217
8.3.1 Flexible Packaging 217
8.3.2 Glossy Film Lamination 219
8.3.3 Furniture and Automotive 222
8.4 Construction Adhesives 224
8.4.1 Floor-covering Adhesives 224
8.4.2 Sub-floor and Wall Mastics 231
8.4.3 Sealants 233
8.4.4 Ceramic Tile Adhesives 238
8.4.5 Polymer-modified Mortars 241
8.4.6 Waterproofing Membranes 244
Contents IX
8.4.7 Elastomeric Roof Coatings 247

Acknowledgments 250
References 251
9 Applications in the Carpet Industry 253

9.2 History of Carpet 253
9.3 Present Day Carpet Business 255
9.4 Carpet Backing Binders 256
9.5 Carpet Laminating 259
9.5.1 Background 259
9.5.2 Carpet Terminology 260
9.5.3 Back-coating Applications 261
9.5.4 Back-coating Formulations and Ingredients 262
9.5.5 Industry Issues 264
References 266
10 Non-wovens Application 267

10.2 Manufacturing Systems 270
10.2.1 Web Formation 271
10.2.2 Web Consolidation 272
10.3 Polymer Dispersions for Chemical Bonding 273
10.4 Application Test Methods 275
References 281
11 Applications in the Leather Industry 283

11.2 Market Situation 284
11.3 Leather Finishing 286
11.3.1 Modern Finishing 287
11.3.2 General Construction of Finishing Coats 287
11.3.3 Spray Dyeing 287
11.3.4 Grain Impregnation 287
11.3.5 Base Coat 287
11.3.6 Pigment Coat 288
11.3.7 Top Coat 288
11.4 Application Methods 288
11.4.1 Spraying 289
11.4.2 Roll Coating 289
11.4.3 Curtain Coater 289
11.5 Binders 291
11.5.1 Polyacrylate Dispersions 291
11.5.2 Polybutadiene Dispersions 291
11.5.3 Polyurethane Dispersions 292
X Contents
11.6 Production of Selected Leather Articles 292

11.6.1 Shoe Upper Leather 292
11.6.2 Apparel Leather 293
11.6.3 Automotive Leather 294
11.6.4 Furniture Leathers 295
11.7 Test Methods in Leather Finishing 296
11.7.1 Flexing Endurance 297
11.7.2 Rub-fastness 298
11.7.3 Dry and Wet Adhesion 299
11.7.4 Fastness to Ironing 299
11.7.5 Hot Air Fastness 299
11.7.6 Aging resistance 299
11.7.7 Fogging test 300
11.7.8 Light-fastness 300
11.7.9 Hot light aging 300
References 300
12 Applications for Asphalt Modification 301

12.2 Hot Mix Asphalt Paving 303
12.2.1 Asphalt Specification 304
12.2.2 In-line Injection (Pump-in) 311
12.3 Paving with Asphalt Emulsion 313
12.3.1 Applications of Asphalt Emulsions 314
12.3.2 Asphalt Emulsion Tests 317
12.3.3 Polymer Honeycomb Structure in Cured Asphalt Emulsion 317
12.3.4 Asphalt Emulsion Residue Characterization 319
12.3.5 Application Tests for Chip Seal and Microsurfacing 321
12.4 Eco-efficiency Analysis 323
Acknowledgement 326
References 326
13 Applications of Redispersible Powders 329

13.2 Manufacturing of Redispersible Powders 330
13.3 Dry Mortar Technology 332
13.4 Markets and Application Areas of Redispersible Powders 333
13.4.1 Adhesives for Ceramic Tiles 334
13.4.2 Tile Grouts 340
13.4.3 Exterior Insulation and Finish Systems and Top Coats 341
13.4.4 Self-leveling Underlayments 345
13.4.5 Patch and Repair Mortars 346
13.4.6 Waterproof Membranes 350
13.5 Summary 353
Contents XI
References 354
14 Applications for Modification of Plastic Materials 355

14.2 Emulsion Polymerization and Isolation Technology 356
14.2.1 Isolation Technology 357
14.3 Processing Aids 358
14.3.1 Processing Aids for PVC 359
14.3.2 Processing Aids for Other Resins 366
14.4 Impact Modifiers 367
14.4.1 Impact Modifiers for PVC 368
14.4.2 Engineering Resins 375
Acknowledgment 378
References 379
15 Applications for Dipped Goods 383

15.2 Polymers Used by the Dipping Industry 384
15.3 Principles of Dipping 385
15.4 Dipping Synthetic Polymer Emulsions in Practice 386
15.4.1 Former Design 386
15.4.2 Mix Design 388
15.4.3 Coagulant 390
15.4.4 The Dipping Process 390
15.5 The Testing of Synthetic Gloves 395
15.5.1 Non-safety-critical Gloves 395
15.5.2 Safety-critical Gloves 396
References 398
Index 399
Polymer Dispersions and Their Industrial Applications. Edited by Dieter Urban and Koichi Takamura XIII
Preface
Aqueous polymer dispersions are important raw materials used in a variety of in-
dustrial processes. They consist of very small polymer particles dispersed in water
and appear as milky fluids. When finally processed and providing the function for
which they were selected, they are barely visible. Polymer dispersions are used to
protect metal, wood, and leather against water and microorganisms, and are used as
binders for pigments, fillers, and fibers and to finish the surfaces of metal, wood or
paper. Protecting, binding, and finishing are the essential effects achieved by use of
polymer dispersions.
In most applications the water will be evaporated and a functional polymer re-
mains. This can be hard or tacky, plastic or elastic, transparent or opaque. Accord-
ingly, they are used for coatings or as adhesives, for binders or foams, for clear coat
varnishes or opacifiers. It is even possible to reconcile these classically contradictory
properties by proper design of a single dispersion or by mixing several.
Even small amounts of polymer dispersion are able to improve considerably the
properties of different binders, e.g. starch, bitumen, or cement.
The huge variety of applications continues into the area of solid plastic materials –
impact modifiers are added to improve the properties of plastic materials. Dipping
goods, e.g. gloves, and latex foams for mattresses are polymeric materials which are
made directly from polymer dispersions.
Finally, there are also applications in which polymer dispersions remain in their
liquid form – they are used as drug carriers, in medical diagnosis, and in liquid soap.
This book focuses on the applications of aqueous polymer dispersions. The chap-
ters on synthesis and characterization should be regarded as an introduction and
should aid understanding of the applications. The applications of aqueous polymer
dispersions have developed differently, both historically and regionally. Regulatory
issues have contributed to these differences. The strongest development of polymer
dispersions occurred in Europe and North America in the middle of the 20th centu-
ry. The differences between these two regions are emphasized.
We are specially grateful to all the authors who helped us make this global com-
parison and acknowledge the authors’ companies, for approving and supporting this
work.
Charlotte, North Carolina, USA Dieter Urban

Koichi Takamura
Polymer Dispersions and Their Industrial Applications. Edited by Dieter Urban and Koichi Takamura XV
List of Authors
Peter Blanpain Dr. Christoph Hahner
7834 Covey Chase Drive Wacker Polymer Systems, L. P.
Charlotte, NC 28210, USA 3301 Sutton Road
Adrian, MI 49221, USA
Dr. Mary Burch
Rohm & Haas Company Dr. Do Ik Lee
727 Norristown Road The Dow Chemical Company
Spring House, PA 19477, USA 1604 Building
Midland, MI 48674, USA
Dr. Chuen-Shyong Chou
Rohm & Haas Company Dr. Hermann Lutz
Rt. 413 and Old Rt. 13 Wacker Polymer Systems GmbH&CoKG
Bristol, PA 19007, USA Johannes-Hees-Str. 24
D-84489 Burghausen, Germany
Dr. Dieter Distler
BASF Aktiengesellschaft Dr. Werner Kirchner
GKD - B1 BASF Aktiengesellschaft
D-67056 Ludwigshafen, Germany EV/CS – H201
D-67056 Ludwigshafen, Germany
Dr. Johannes Peter Dix
BASF Aktiengesellschaft Andrew Lanham
EVL/I – G100 Synthomer Ltd.
D-67056 Ludwigshafen, Germany Central Road, Templefields,
Harlow, Essex, CM20 2BH, UK
Dr. Luke Egan
BASF Corporation Dr. Brough Richey
11501 Steele Creek Road Rohm & Haas Company
Charlotte, NC 28273, USA 727 Norristown Road
Spring House, PA 19477, USA
Dr. Onno Graalmann
BASF Nederland B.V. Dr. Jürgen Schmidt-Thümmes
Westervoortsedijk 71 BASF Aktiengesellschaft
NL-6827 AV Arnhem, The Netherland GKD/S – B1
Dr. Sunitha Grandhee
BASF Corporation Dr. Elmar Schwarzenbach
26701 Telegraph Road BASF Aktiengesellschaft
Southfield, MI 48034, USA EDP/MB – H201
Richard Groves
Synthomer LTD Richard Scott
Central Road, Templefields, BASF Corporation
Harlow, Essex, CM20 2BH, UK 475 Reed Road NW
Dalton, GA 30720, USA
XVI
J. Arthur Smith
BASF Nederland B.V.
Westervoortsedijk 71
NL-6827 AV Arnhem, The Netherland
K. Spenceley
Synthomer Ltd.
Central Road, Templefields,
Harlow, Essex, CM20 2BH, UK
Barna Szabo
Flint Ink Corporation
4600 Arrowhead Drive
Ann Arbor, MI 48105, USA
Dr. Koichi Takamura
BASF Corporation
11501 Steele Creek Road
Charlotte, NC 28273, USA
Jim Tanger
BASF Corporation
Michael A. Taylor
BASF Corporation
Dr. Dieter Urban
BASF Corporation
Dr. Jane E. Weier
Rohm & Haas Company
Rt. 413 and Old Rt. 13
Bristol, PA 19007, USA
Dr. Harm Wiese
BASF Aktiengesellschaft
GKD/N – B1
Marilyn Wolf
BASF Corporation
Polymer Dispersions and Their Industrial Applications. Edited by Dieter Urban and Koichi Takamura
Color Plates XVII
Color Plates
Fig. 1-3
Particle
morphologies.
Raspberry structure
Core/shell structure
Acorn structure
Uncoated grade,
supercalendered
Coated grade,
supercalendered
Fig. 4-7 Effect of coated paper on offset printing.

XVIII Color Plates
Coated
gravure
paper
Uncoated
gravure
paper
Fig. 4-8 Effect of coated paper on rotogravure printing.
Steam
Coating head Dryer
Laminating
station
Release
liner Backing
Fig. 8-9 Schematic representation
of PSA label coater. Unwind Rewind
Latex Polymer
Network
Fig. 12-15 Photo-

micrograph demon-
strating spontaneous
50 µm formation of polymer
network upon curing
of the CRS-2 asphalt
emulsion modified
with 3 % cationic SBR
latex.
Polymer Dispersions and Their Industrial Applications. Edited by Dieter Urban and Koichi Takamura 1
1
Introduction
Dieter Urban and Dieter Distler
1.1
Names and Definitions
Most precisely the subject of this book is called “aqueous synthetic organic polymer
colloids”. The term “polymer colloid” defines a state of subdivision in which polymol-
ecular particles dispersed in a medium have at least in one direction a dimension of
roughly between 1 nm and 1000 nm [1]. The term “organic” needs to be added to ex-
clude inorganic polymers like silica. To be more precise the term “synthetic” will be
added, if organic polymers of natural origin like natural rubber should be excluded.
Finally, the term “aqueous” ensures that the continuous medium is only water, exclud-
ing e.g. organic solvents. However, depending on the language, the geographical re-
gion and the field of application there are many other names commonly used (Fig. 1-1).
In general the term “dispersion” characterizes a two phase system consisting of
finely dispersed solid particles in a continuous liquid phase. An example of a disper-
sion is whitewash, calcium hydroxide above the solubility limit in water. If the finely
dispersed phase and the continuous phase, both are liquid, the term “emulsion”
will be used. An example is milk, which essentially consists of fat droplets in water;
the droplets are stabilized by proteins. In both cases, in dispersions and emulsions,
the continuous phase is therefore a liquid; in all of our examples, the liquid is water.
In dispersions, the finely disperse substance is solid, while in emulsions it is liquid.
Dealing with organic polymers being the dispersed substance it is difficult to de-
fine precisely whether they are solid or liquid. Depending on the glass transition
temperature (Tg) and chain length, polymers are viscous liquids at low Tg and low
molecular weight or they will be tough to brittle solids, if Tg and molecular weight
are high. The temperature and stress duration are other important factors. At tem-
peratures below the glass transition temperature or in the case of very short stress
duration, polymers behave like glasses, while above this temperature or in the case of
long stress times, they are viscous or elastic materials. This behavior of polymers be-
tween liquid and solid is one reason why aqueous synthetic organic polymer colloids
are referred to as dispersions (Danish, Dutch, Finnish, German, Greek, Hungarian,
Japanese, Korean, Norwegian, Polish, Portuguese, Romanian, Russian, Spanish,
2 1 Introduction
Fig. 1-1 Commonly used names for aqueous synthetic organic polymer
colloids.
Swedish, Turkish) and emulsions (Arabic, Chinese, English, Indonesian, Italian,

Malay). Another reason for the use of emulsion or emulsion polymer comes from the
most important production process for these products, the emulsion polymerization.
The products are referred to as emulsion polymers or simply emulsions.
In contrast to this the name latex (Latin: latex, liquid; Greek: λαταξ, droplet) is de-
rived from the naturally occurring rubber milk and is most widely used for aqueous
synthetic organic polymer colloids, especially for the substitution products of natural
latex, butadiene-styrene copolymer emulsions.
The Union for Pure and Applied Chemistry recommends two names: Latex and
polymer dispersion [2]. Latex is defined as “A colloidal dispersion of polymer parti-
cles in an aqueous medium. The polymer may be organic or inorganic.” Since
we will not cover inorganic dispersions, this book should have been called “Organic
Latices and Their Industrial Applications”, which seems to be a pleonasm because
the use of latex is generally associated with organic material. Polymer dispersion is
defined as “A dispersion in which the disperse phase consists of polymer particles.”
The continuous phase can be a liquid, solid or gas. If we want only water to be the
continuous phase, aqueous is added. In industrial applications non-aqueous poly-
mer dispersions are negligible. Therefore this book has been called “Polymer Dis-
persions and Their Industrial Applications”. However, according to the preference of
the authors the terms “polymer dispersion”, “dispersion”, “emulsion polymer”,
“emulsion” and “latex” are used synonymously.
1.2
Properties of Polymer Dispersions
The aggregate state of a polymer dispersion is thermodynamically unstable. The very

large internal surface area of up to 100 m2 mL–1 of dispersion requires stabilization
of the particle surfaces in order to suppress phase separation and coagulation. Dri-
ving force for the agglomeration of particles is the gain of energy by reducing the in-
ternal surface. Finally a polymer block and a substantially polymer-free water phase
will be formed. This coagulation can be accelerated by salts, acids, solvents, freezing,
shear, etc.
To obtain highly stable polymer dispersions, the particles are usually provided
with ionic groups, for example by adsorption of anionic or cationic surfactants, or by
incorporation of ionic groups into the polymer. Another, nonionic type of stabiliza-
tion takes place via hydrophilic groups on the particle surface, for example by amino-
or hydroxyl-containing monomers or protective colloids. Polymer dispersions used
in industry usually are stabilized by both mechanisms (ionic and nonionic). The spe-
cial nature of the particle surface, which differs from the particle interior, plays an
important role in all applications.
Industrially important polymer dispersions usually contain 40–60 % of polymer
in water. Each mL of dispersion contains about 1015 particles with diameters of
50–500 nm. One particle contains 1–10 000 macromolecules, and each macromole-
cule contains about 100–106 monomer units (Fig. 1-2).
4 1 Introduction
Fig. 1-2 What is a polymer dispersion?
These figures give an impression of the possible variation, if just the molecular
weight (or molecular weight distribution) and particle size (or particle size distribu-
tion) of homo-polymers will be considered. The random incorporation of various
monomers in the chains, the possibility of cross-linking between the polymer chains
and finally separated phases of different polymers in a particle allow a virtually un-
limited variety in this product class.
Polymer dispersions normally consist of spherical particles. The dispersed parti-
cles scatter the light and are the cause of the milky appearance. This Mie scattering is
utilized for particle size measurement. Very small polymer particles hardly scatter
visible light at all, those polymer dispersions have a translucent appearance. If all the
particles are of the same size, the term “monodisperse dispersions” will be used.
They are frequently recognized from a certain particle size merely from the irides-
cent appearance, which is caused by Bragg scattering at a crystalline superstructure
of close packing of the particles.
Polymer dispersions with a heterogeneous particle structure – a special particle
morphology consisting of a number of phases – have recently become of interest. Ex-
amples are particles with a core/shell structure or two coexistent polymer phases,
particles with a raspberry structure, etc. The particle morphology may be thermody-
namically preferred; in the case of polymers with reduced chain mobility or even in
the case of relatively low cross-linking, it is mostly kinetically controlled morpholo-
gies that are frozen. This enables product properties with even contradictory require-
ments to be achieved better, for example low film formation temperature, but maxi-
mum blocking resistance or hardness of the polymer (Fig. 1-3).
The flow behavior is also an important parameter. The flow property of polymer
dispersions is a particular advantage of this aggregate state. Dispersions can have a
polymer content which is a multiple higher than polymer solutions, yet still be free-
flowing. Besides the polymer content, particle size, particle size distribution and
electrolyte content, the viscosity is also affected by dissolved constituents in the aque-
ous phase. The water phase of many polymer dispersions contains a whole range of
water-soluble oligomers, auxiliaries and additives which contribute to the application
properties as well.
Fig. 1-3
Particle
morphologies.
Raspberry structure
Core/shell structure
Acorn structure
To obtain readily free-flowing dispersions with low viscosity at high polymer con-
tents of >60 % by volume, very broad or bimodal particle size distributions are need-
ed (Fig. 1-4).
Fig. 1-4 Electron photomicro-

graph of a bimodal polymer
dispersion.
This can be achieved during the polymerization or by partial agglomeration, for ex-
ample, by means of a shear gradient, by freezing or by addition of an agglomeration
aid, so that significantly larger agglomerates are present alongside the small primary
particles.
The viscosity of polymer dispersions is usually dependent on the shear rate. A dis-
tinction is made between pseudoplastic behavior (viscosity decreases with increasing
shear), possibly with a flow limit, thixotropic behavior (viscosity decreases with in-
6 1 Introduction
creasing shear time) and dilatant behavior (viscosity increases with increasing
shear). The rheology of concentrated polymer dispersions is complex, often being de-
pendent on the shear rate and previous history.
Owing to the content of surface-active substances, the foaming behavior is an im-
portant property for many applications. Antifoam agents reduce foaming, while fur-
ther emulsifiers and rheology modifiers increase the foaming or stabilize the foam
once formed.
The biodegradability of many additives makes the dispersions susceptible to attack
by microorganisms (bacteria, yeast). Most dispersions are therefore provided with
biocides.
In most applications, the water is evaporated from the dispersions. Depending on
the composition and/or processing temperature, a polymer film or powder is formed.
The properties of the polymer now come into play:
strength, elongation at break, elasticity, transparency, solvent and environmental
resistance, glass transition temperature, tack, etc.
These properties are determined by the chemical composition of the copolymers,
the molecular weight and the molecular weight distribution, by the morphology of
the polymer particles and by the morphology of the polymer film.
Important polymer classes are:
Styrene/butadiene dispersions are used for their elastic properties since molecular
weight and cross-linking of the polymer can be adjusted widely by choosing the de-
gree of conversion and the amount of chain transfer agents. They are used as syn-
thetic rubber for tires and molded foam. When styrene is replaced by acrylonitrile,
elastic and solvent resistant polymers are obtained, which are used for dipping
goods. Carboxylated styrene/butadiene (XSB) dispersions contain acrylic, methacryl-
ic, maleic, fumaric or itaconic acid. The carboxylic groups provide stabilization of the
polymer particles and a good interaction with fillers (calcium carbonate, clay) and
pigments. The main applications are paper coating and carpet backing. The remain-
ing 1,2 and 2,3 double bonds of butadiene favor autoxidation of the polymer, it be-
comes yellow and brittle. This is prevented by adding antioxidants. This polymer
class is resistant to hydrolysis at all pH values since it does not contain ester units
which tend to hydrolyze especially at very high pH.
Acrylic dispersions (pure acrylics and styrene acrylics) are extremely versatile. The
big variety of available acrylic and methacrylic esters together with styrene offer
almost unlimited opportunities to choose for the glass transition temperature and
the hydrophilic/hydrophobic properties. Acrylic esters tend to form cross-linked
polymers by abstraction of the α-hydrogen atom, methacrylic esters in contrast form
polymer chains which are not cross-linked. Acrylics are resistant against oxidation by
air and degradation by light. The main application areas are coatings and adhesives.
Vinyl acetate dispersions are widely used for coatings and adhesives as well. To
stabilize the polymer particles often polyvinyl alcohol is used as protective colloid.
Most common co-monomers are ethylene, versatic esters, vinyl chloride or acrylic es-
ters. The polymer dispersions are spray dried to obtain a polymer powder, which is
widely used in construction industry. Ethylene/vinyl acetate copolymers form elastic
films and are fairly resistant to oxygen and light.
Polymer dispersion with a high content of vinylidene chloride form polymer films
with crystalline areas. These PVDC films are highly impermeable for both, oxygen
and water vapor, and are used as barrier coatings in packaging materials, especially
for food packaging (Fig. 1-5).
Fig. 1-5Permeability
of polymer films.
Polymer dispersions with a high amount of acrylic/methacrylic acid convert to

aqueous solutions or gels when pH is increased. They are used as thickeners.
Films made from polyurethane dispersions combine elastic properties with high
tensile strength.
Polystyrene dispersions have a glass transition temperature of 105 ºC. They are
used in paper coating to improve gloss, in liquid soaps to provide opacity and in
medical diagnosis as carrier for active ingredients.
Films of acrylic dispersions, which are cross-linked with metal ions and re-dis-
persible with an aqueous solution of ammonia, are used as temporary protective
films.
All those examples elucidate that polymer dispersions are used in both big volume
and small volume applications. They are both commodities and specialties. And the
use of polymer dispersions is increasing worldwide. The main reasons for this are:
the variety of polymer properties achievable by emulsion polymerization is virtually
unlimited, emulsion polymerization is an inexpensive production process for these
products, the fluid form of polymer dispersions is easy to handle, and water is envi-
ronmentally friendly.
The complex colloidal and chemical behavior of polymer dispersions is an inter-
esting working area for many scientific disciplines and is important for many appli-
cations. In addition to excellent reviews [3–13], a whole range of periodicals focuses
on polymer dispersions [14–18].
8 1 Introduction
1.3
Important Raw Materials
The most important production process for polymer dispersions is emulsion poly-
merization [19]. This process is started by preparing a monomer emulsion consist-
ing of monomer droplets in water. The monomer droplets are stabilized by emulsi-
fiers and/or protective colloids. When adding an initiator polymerization is started
converting the monomers into polymer particles (Chapter 2).
The production of polymer dispersions by emulsion polymerization requires de-
ionized water, free-radical-polymerizable monomers, emulsifiers and/or protective
colloids and initiators. Further auxiliaries, such as chain transfer agents, buffers,
acids, bases, anti-aging agents, biocides, etc., can be used.
The most important source of the main monomers used or their precursors is pe-
troleum chemistry, with the steam cracker as reactor. Liquid hydrocarbons (naphtha
or liquefied natural gas LNG) are broken down (“cracked”) into short-chain hydro-
carbons at 800–850 °C with addition of steam as diluent (Fig. 1-6) [20].
Fig. 1-6 Steam cracker products.
There are currently about 200 steam crackers worldwide. In Europe, Latin Ameri-
ca and South-East Asia, the starting material is mostly naphtha, while in North
Africa, the Middle East and North America, predominantly ethane and propane from
natural gas are used. The largest plants have an annual capacity of more than 800 000
tons of naphtha.
Ethene, the most important petrochemical feedstock today, reached a world capac-
ity of about 80 million tons per year in 1995. Almost half is polymerized to give poly-
ethylene. It plays only a secondary role for emulsion polymerization in vinyl acetate-
ethene copolymers and in polyethylene waxes. It is important, however, in this con-
nection as a feedstock for the production of vinyl chloride, styrene and vinyl acetate.
1.3 Important Raw Materials 9
Propene cannot be polymerized by means of free radicals. It is, however, a feed-

stock for acrylic acid, acrylates and acrylonitrile.
Butadiene is extracted from the C4 fraction from the steam cracker, and can be
used directly for emulsion polymerization.
The principal monomers butadiene, styrene, vinyl acetate, (meth)acrylates and
acrylonitrile essentially determine the material properties of films made from the
corresponding dispersions: the glass transition temperature, the water absorption
capacity, the elasticity, etc. Auxiliary monomers, which are only used in a small pro-
portion, usually <5 %, control important properties such as colloid-chemical stabi-
lization (acrylic acid, methacrylic acid, acrylamide, methacrylamide), crosslinking
within the particles (difunctional acrylates, divinylbenzene, etc.) or hydrophilic prop-
erties (OH-containing monomers, such as hydroxyacrylates). Reactive monomers
which still contain a latently reactive group even after incorporation into the poly-
mer, for example glycidylmethacrylate or N-methylol(meth)acrylamide, can form a
network between various particles and polymer molecules after film formation.
These specific polar groups are frequently not distributed homogeneously over the
particle cross-section, but are preferentially moved to the area of greatest effective-
ness, for example the particle surface.
Besides the monomers, the emulsifiers are important constituents. Emulsifiers
(surfactants) consist of a long-chain hydrophobic group (dodecyl, hexadecyl or alkyl-
benzene) and a hydrophilic end group.
The hydrophilic group may be anionic (sulfate, sulfonate, sulfosuccinic acid, phos-
phate, carboxylate) or cationic (quaternary ammonium salts) or have a zwitterionic
structure (betaine groups).
In addition, there is a whole series of nonionic emulsifiers and protective colloids,
which are frequently used in combination with ionic emulsifiers. Ethylene oxide-
propylene oxide block copolymers, amphiphilic 2- and 3-block copolymers, polyvinyl
alcohols, polyvinyl-pyrrolidone, alkylpolyglycol ethers, etc.
For the polymerization to start and maintain, a free-radical initiator which forms
free radicals at elevated temperatures (60–100 ºC) is needed, for example sodium
peroxodisulfate, hydrogen peroxide, organic peroxides or azo compounds, or a redox
system, for example hydrogen peroxide/ascorbic acid with Fe2+ salts.
The polymerization can also be initiated by UV, γ-rays, electron beams or strong
sound or shear fields, although these, apart from UV initiation, have not yet been
used in practice.
The combination of initiator- and surface-active properties (inisurf) or surface-
active and monomer properties (surfmer) in a single molecule is possible, but is so
far mainly of academic interest.
10 1 Introduction
1.4
Commercial Importance of Polymer Dispersions
Polymers were discovered in the 1920s. During World War II large industrial scale
production was established and since the 1950s production and use of polymers have
grown strongly (Fig. 1-7).
Million Metric tons

200
180
189
160
140
120
100 114
80
60 68
40
20 8 32
0
1960 1970 1980 1990 2000
Fig. 1-7 Growth of plastics production.
This growth is ongoing, and production of synthetic polymers has reached about
189 million metric tons with a total value of more than US$ 200 billion worldwide by
the year 2000. This growth is due to two factors: the ability of polymers to combine
properties such as light weight, strength, electrical insulation, etc., and the extreme-
ly low energy content (as product and in production). The possibility of energy recov-
ery, recycling of the raw material or even of the polymer after use conserves re-
sources. We encounter a wide range of polymers every day in the form of fibers, ma-
terials, films, etc., in virtually all products we use in everyday life. Combinations of
the various product classes make a significant contribution toward the variety of end
products made of plastic materials and synthetic fibers. The variety of functional
polymers is even greater than for plastics and fibers. Functional polymers are used
as polymer solutions, polymer dispersions or polymer powders. They essentially per-
form the functions of protecting, binding, bonding and finishing.
The major polymer classes – polyolefins, polyvinyl chloride and polystyrene – are
defined by their monomers; ethene, propene, vinyl chloride and styrene (Fig. 1-8).
These three groups together account for 64 % of synthetic polymers. The class of
polymer dispersions is only described by the state of aggregation, but not by the
chemical composition. In the chapters dealing with applications, we will also see that
for a particular application a number of polymer classes are suitable; the specific
1.4 Commercial Importance of Polymer Dispersions 11
PVC 14%
Polyolefin 43%
Polyester 14%
Polystyrene 7%
Polyurethane 4%
Other 14% Polymer Dispersions (dry) 4%
Fig. 1-8 Production by polymer class [21].
state of aggregation of the dispersions is consequently often more important than

the monomer combinations. 4 % polymer dispersions correspond to about 7.5 mil-
lion metric tons (dry) polymer, or 15 million metric tons (wet), assuming an average
polymer content of 50 %. The most important dispersion, natural latex from Hevea
brasiliensis with about 6 million metric tons (dry), is, as a natural product, not includ-
ed here. The majority is coagulated and used predominantly in the tire industry, only
about 15 % is sold as latex with a solids content of 60 %. These figures also omit im-
pact modifiers for plastics. They are not sold as dispersions, but further processed di-
rectly by the manufacturers. About 1 million metric ton (dry) of impact modifiers is
produced worldwide.
The most important product classes of polymer dispersions are butadiene-styrene
copolymers, vinyl acetate homopolymers and copolymers, and polyacrylates. Other
polymer dispersions contain copolymers of ethylene, styrene, vinyl ester, vinyl chlo-
ride, vinylidene chloride, chloroprene and polyurethane (Fig. 1-9).
12 1 Introduction
Vinylacetate 28%
Acrylate 30%
Other 5%
Styrene Butadiene 37%
Fig. 1-9 Aqueous polymer dispersions by product class.
1.5
Manufacturers of Polymer Dispersions
Worldwide there are far more than 500 companies producing and offering polymer
dispersions. However, only 20 companies account for about half of the global mar-
ket. The leading 3 suppliers – BASF, DOW Chemical, Rohm and Haas – have an an-
nual production capacity of more than 1 million metric tons (wet) and cover about
20 % of the world market. In Fig. 1-10 major suppliers of polymer dispersions are
listed in alphabetical order. The product lines are defined by the main monomers
used. Acrylic dispersions include pure acrylics and styrene acrylics, specialty disper-
sions consist of monomers like vinyl pyridine, vinyl chloride, vinylidene chloride,
chloroprene, etc.. The product lines as well as the information about the main appli-
cation areas and the trade names were mainly taken from the company’s web
sites [22–49].
1.5 Manufacturers of Polymer Dispersions 13
Company Product lines Applications Trade names
Air Products [1-22] VAc, EVA, A Adh, Coat, Con, I/GA, Pap, Tex Airbond, Airflex, Flexbond, Flexcryl,
Valbond, Valtac, Vancryl, Vinac
Asahi Kasei [1-23] A, Sp Adh, Coat Polytron, Sun Wrap
Avecia[1-24] A, PU Adh, Coat, I/GA NeoCryl, NeoRes, NeoPac,
NeoRad, Haloflex
BASF [1-25] A, SB, PU, Sp Adh, Coat, Con, Pap, Tex Acronal, Basonal, Butofan, Butonal,
Diofan, Emuldur, Luhydran, Luphen,
Styrofan, Styronal
Clariant [1-26] VAc, EVA, A, Adh, Coat, Con, Tex Mowilith, Mowiplus, Appretan
Dow [1-27] SB, A, VAc, Coat, Con, Pap, Tex Dow Latex, UCAR Latex
PU,
Eastman Chem. [1-28] A, VAc Adh, Coat, I/GA Eastek, Eastarez, Waterborne
Polymer
Elf Atochem [1-29] A, EVA, VAc Adh, Coat, Con, I/GA, Pap, Tex Repolem
Enichem [1-30] SB, NB Adh, Pap, Tex Intex, Europrene, Latice
Goodyear [1-31] A, SB, Sp Adh, Coat, Con, Tex Pliolite, Pliotec
BFGoodrich [1-49] A, NB, SB, PU, Adh, Coat, Con, Tex Aqueous XPD, Carbotac, Carboset,
Sp Carbobond, Goodrite, Hycar,
now Noveon Hystrech, Sancure, Vycar
JSR Corporation [1-32] A, SB Adh, Coat, Con, Pap Glasca, Dynaflow
S.C. Johnson [1-33] A, PU Adh, Coat, I/GA Joncryl, SCX
Mitsubishi Chem [1-34] A, EVA, VAc, Adh, Coat, Con, Pap, Tex Rikabond
PU
National Starch [1-35] A, EVA, VAc, Adh, Coat, Con, I/GA, Pap, Tex Vinamul, Dur-o-set, Dur-o-cryl,
Nacrylic, Resyn
Nitriflex [1-36] NB, SB, Sp Adh, Tex Nitrilatex
Zeon Corp. [1-37] A, SB, NB Adh, Coat, Con, I/GA, Pap, Tex Nipol
Omnova [1-38] A, SB, NB, Adh, Coat, Con, I/GA, Pap, Tex AcryGen, GenFlo, SunCryl,
VAc, Sp AcrylGen, AcrylPrint, GenCal,
GenCryl, GenTac, OmnaBloc,
Sequabond, Sunbond
Polymer Latex [1-39] A, NB, SB, PU, Adh, Coat, Con, Pap, Tex Acralen, Baystal, Baypren, Bunatex,
Sp Lipaton, Lipolan, Plextol, Perbunan
Raisio Group [1-40] A, SB, Vac Pap, Tex Raisional
Reichold [1-41] A, EVA, NB, Adh, Coat, Con, I/GA, Pap, Tex Elvace, Pace, Plyamul, Synthemul,
SB, VAc, Sp Tylac
Revertex [1-42] EVA, VAc Adh Durabond
Rhodia [1-43] A, VAc, SB Adh, Coat, Con, Pap, Tex Rhodopas, Rhodotak, Rhoximat
Rohm&Haas [1-44] A, VAc, PU Adh, Coat, Con, I/GA, Pap, Tex Lucidene, Primal, Polyco, Rhobond,
Rhopaque, Rhoplex, Rovace
Solutia Inc. [1-45] A Adh Gelva
Synthomer [1-46] A, NB, SB Adh, Con, I/GA, Pap, Tex
UCB [1-47] A, PU Adh, Coat Ucecryl, Ucecoat
Wacker [1-48] EVA, VAc, Sp Adh, Coat, Con Vinnapas, Wacker SMK
Fig. 1-10 Major suppliers of aqueous poly- dispersions, PU polyurethane dispersions,

mers dispersions. Product lines: A acrylic disper- Sp specialty dispersions. Applications: Adh
sions, SB styrene butadiene dispersions, NB adhesives, Coat coatings/paints, Con construc-
acrylonitrile butadiene dispersions, VAc vinyl tion/building products, I/GA inks/graphic arts,
acetate dispersions, EVA ethylene vinyl acetate Pap paper, Tex carpet/textile/non-woven.
14
References
1 Everett, D. H., Pure Appl. Chem. 31(4), 18 J. Dispersion Sci. Technol., Coden.
579–638, 1972. 19 Gilbert, R., G., Emulsion Polymerisation,
2 IUPAC Proposal for The nomenclature A Mechanistic Approach, Academic
for Polymerization Processes and Poly- Press, London, 1995.
mers in Dispersed Systems. See also 20 Weissermel, K., Arpe, H.-J., Industrial
ISO 12000 Plastics/rubber-Polymer dis- Organic Chemistry, Major Organic
persions and rubber latices – Definitions Precursors and Intermediates, Verlag
and review of test methods. Chemie, Weinheim, 1994.
3 Blackley, D. C., High Polymer Lattices, 21 P. Baum, J. Engelmann, Nachrichten
two volumes, MacLaren, London, 1966. aus der Chemie, 49/3, 368f, 2001.
4 Warson, H., The Application of Synthetic 22 http://www.airproducts.com
Resin Emulsions, Benn, London, 1972. 23 http://www.asahi-kasei.co.jp/asahi/
5 Piirma, I., Emulsion Polymerisation, english/kasejusi.htm
Academic Press, New York, 1982. 24 http://www.avecia.com/neoresins/
6 Blackley, D. C., Emulsion Polymerisation, 25 http://www.basf.de/de/dispersionen/
Theory and Practice, Applied Science, products
London, 1975. 26 http://www.clariant.com
7 Hölscher, F., Dispersions of Synthetic 27 http://www.dow.com/emulpoly/
High Polymers, Part I, Properties, Prepara- index.html
tion, Testing, Springer, Berlin, 1969. 28 http://www.eastman.com/
8 Reinhard, H., Dispersions of Synthetic 29 http://www.atofina.com/
High Polymers, Part II, Use, Springer, 30 http://www.enichem.it/english/
Berlin, 1969. 31 http://www.goodyear.com/
9 Buscall, R., Corner, T., Stagemann, 32 http://www.jsr.co.jp/main/english/
J. F., Polymer Colloids, Elsevier Applied 33 http://www.scjohnsonwax.com/
Science, London, 1985. 34 http://www.m-kagaku.co.jp/
10 Athey, R. D., Emulsion Polymer Tech- 35 http://www.Vinamulpolymers.com/
nology, Marcel Dekker, New York, 1991. 36 http://www.nitriflex.com.br/
11 Poehlein, G., Encyclopedia of Polymer 37 http://www.zeon.co.jp/
Science and Engineering; Volume 6, 38 http://www.omnova.com/
Emulsion Polymerisation, J. Wiley, 39 http://www.polymerlatex.de/
New York, 1986. 40 http://www.raisiogroup.com/
12 Lovell, P. A., El-Asser, M. S., Emulsion 41 http://www.reichhold.com/
Polymerisation and Emulsion Polymers, J. 42 http://www.revertexfinewaters.com/
Wiley, New York, 1997. 43 http://www.rhodia.com/
13 Asua, J. M., Polymeric Dispersions: 44 http://www.rohmhaas.com/
Principles and Applications, (NATO 45 http://www.solutia.com/
ASI Series E: Appl. Science, Vol. 335), 46 http://www.synthomer.com/
Kluwer Academic Publishers, Dordrecht, 47 http://www.ucb.be/
1997. 48 http://www.wacker.com/vip/
14 Colloid Polym. Sci., Steinkopf. produktion/wacker/website/polymer-
15 Colloids Surf., Elsevier. systems/index_en.html
16 J. Colloid Interface Sci., Academic Press. 49 http://www.bfgsolutions.com
17 Langmuir, ACS Journal of Surfaces and
Colloids, American Chemical Society.
2
Synthesis of Polymer Dispersions
Mike A. Taylor
2.1
Introduction
The intent of this chapter is to give a short overview of the chemistry and manufac-
turing processes involved in the synthesis of emulsion polymers. While the equip-
ment used in preparing an emulsion polymer is relatively simple, and the mecha-
nism of the important reactions are fairly well understood, the development of new
and improved products is often still carried out in a somewhat empirical fashion.
Recipe and process conditions can frequently be designed, based on a theoretical
knowledge, to produce specific polymeric and colloidal properties, but there are still
large gaps in the knowledge needed to translate this into application behavior. In
general, scale-up from laboratory to manufacturing gives good duplication of poly-
meric and colloidal properties, and laboratory equipment normally consists of sim-
ple stirred reactors, usually glass for non-pressure polymerizations, with a means of
maintaining temperature control of the exothermic reaction. With non-pressure re-
actors, ingredients may be added under gravity, while pumps or inert gas pressure
may be used for pressurized systems. Two important process features that are not re-
produced well between small and large-scale reactors are heat transfer and shear.
Laboratory reactors, with their large cooling surface to volume ratio and the large
heat capacity of the reactor relative to the contents, do not normally pose any prob-
lems for cooling. In fact, heat losses often exceed heat generated by the reaction, ne-
cessitating heat input to maintain reaction temperature. Heat transfer, on the other
hand, often limits production rates in large-scale reactors. In order to achieve a sim-
ilar degree of mixing in vessels of different sizes, the most important scale-up crite-
ria is usually to maintain the same power input per unit volume. Unfortunately, this
translates to a higher agitation speed as reactor size reduces, a consequence of which
is increased shear on the emulsion. Therefore, for the study of process characteris-
tics, laboratory reactors have significant limitations.
Figures 2-1 and 2-2 show modern laboratory facilities for non-pressure and pres-
sure emulsion polymerization. Both batch and semi-batch reactions are regularly
carried out on laboratory scale. The larger quantities involved in continuous poly-
16 2 Synthesis of Polymer Dispersions
Fig. 2-1 Typical laboratory

apparatus for emulsion
polymerization at atmospheric
pressure (photograph courtesy
BASF Corporation).
Fig. 2-2 Laboratory equipment

for emulsion polymerization at
high pressures (photograph
courtesy BASF Corporation).
merization generally rule out this process for laboratory scale reproduction, although
the kinetics of a chain of multiple continuous stirred-tank reactors can be simulated
with a batch reaction (Sect. 2.3.1). Reactions at low temperatures require the provi-
sion of refrigerated coolant.
A simple recipe, which could be used to demonstrate the influence of ingredients
and process on polymer and colloidal properties, is shown in Tab. 2-1. Subsequent
sections of this chapter give greater detail on materials used to produce emulsion
polymers.
This recipe could be utilized for investigating both batch and semi-batch emulsion
polymerization at a range of temperatures. With just these two monomers and one
functional monomer, a very wide range of polymers with significant differences in
polymer and latex properties can be produced (soft/hard, low/high molecular
weight, tacky/non-tacky, stable/unstable, etc.)
2.2 Chemistry 17
Tab. 2-1 Model system for the study of some aspects of emulsion
polymerization.
Ingredient Quantity Influence

(phm1)
Water 100–150 Solids content; viscosity

Styrene 0–95 Glass transition temp;
minimum film-forming
n-Butyl acrylate 0–95 Glass transition temp;
minimum film-forming
Methacrylic acid 0–5 Colloidal stability; viscosity;
reaction kinetics
Sodium lauryl sulfate 0.5–3.0 Particle size; colloidal stability;
reaction kinetics
Ammonium persulfate 0.1–1.0 Particle size; colloidal stability;
viscosity; reaction kinetics;
molecular wt.
t-Dodecyl mercaptan 0–1.0 Molecular wt.; reaction kinetics
Divinylbenzene 0–0.5 Cross-linking/gel
1 Parts per hundred parts of monomer
2.2
Chemistry
2.2.1
Mechanism of Emulsion Polymerization
Strictly speaking, emulsion polymerization can take place in a system with only three
components, a monomer that forms the structure of the polymer, water that acts as
the continuous medium in which the polymer particles are dispersed, and an initia-
tor that produces free radicals which start and maintain the polymerization process.
However, at the very least the system will almost invariably contain a fourth ingredi-
ent, surfactant, which can provide the initial site, from which polymer particles sub-
sequently grow, and/or give stability to the growing particles. In addition, most com-
mercial recipes would normally include other ingredients to impart specific proper-
ties to the final polymer or emulsion, for example, a modifier to control the molecu-
lar weight of the polymer or a cross-linking agent to control the amount of gel. In
many cases, ingredients used to control polymerization behavior will also exert their
own influence on application properties of the final emulsion. Particularly, surfac-
tants, while often determining the number of particles and their stability, can also
have significant effects on such properties as adhesion, rheology, filler tolerance and
many others. The overall formulation of an emulsion polymer is therefore often a
compromise to obtain an optimum balance of properties. Rarely can the best of
everything be achieved.
The basic building block of any polymer is the monomer, characterized as a mole-
cule containing at least one carbon-carbon double bond, C=C, and which, through a
free radical mechanism, can add on to itself, ultimately forming very large molecules
of repeating units. Many different monomers (Sect. 2.2.2) are in use commercially
for producing emulsion polymers, either as the sole monomer or, more usually, as
combinations of monomers to give specifically desired properties. Polymerization is
started when a free radical, originating from the decomposition of the initiator
(Sect. 2.2.5), comes into contact with a monomer molecule and adds on at the site of
the C=C double bond. This creates a monomer unit that is then itself a free radical
and can in turn add on to another monomer molecule. The process continues, build-
ing up long chains of monomer units, until the free radical at the end of the chain
comes into contact with some species other than a monomer molecule, normally an-
other free radical, at which time the growing polymer chain is terminated. The free
radical that terminates the chain can be an original radical, from the decomposition
of the initiator, or a “polymeric radical” when the ends of two propagating chains
terminate each other. Other species, such as inhibitors and short-stopping agents if
present, can also cause termination to occur. These three main stages of polymeriza-
tion are termed initiation, propagation and termination and can be denoted schemat-
ically as follows:
Initiation Ι → 2R• (decomposition of initiator)
M + R• → R–M•
Propagation R–M(n)• + M → R–M(n + 1)•
or transfer to polymer leading to branching
R–M(n)• + R–M(m)–R → R–M(n) + R–M•(m)–R
Termination R–M(n + 1)• + R• → R–M(n + 1)R
or R–M(n)• + R–M(m)• → R–M(n + m)–R
In such a system, the average molecular weight of the polymer chains is controlled
primarily by the temperature of polymerization and the quantity of initiator. To exert
additional control over molecular weight, a molecular weight modifier (chain trans-
fer agent) is used. With chain transfer, a growing polymer chain is terminated but at
the same time another radical is generated which can initiate polymerization of a
further monomer unit, thus starting another polymer chain. Widely used chain
transfer agents are the mercaptans, R–SH, where R is typically a twelve to fourteen
hydrocarbon (t-dodecyl or n-dodecyl being the most common).
Chain Transfer R–M(n)• + R–SH → R–M(n)–SH + R•
These four mechanisms are common to all types of free-radical polymerizations,
for example bulk, solution, suspension and emulsion. The difference between the
processes is the environment. In bulk polymerization there exists only one phase,
initially the monomer, then as polymerization progresses a solution of the polymer
in its own monomer. Both polystyrene and poly(methyl methacrylate) are produced
in large quantities by bulk polymerization. Solution polymerization is similar in that
there is only one phase present, but in this case the monomer is diluted with a fully
miscible solvent and the final polymer is in solution in the solvent. Polyacrylic acid,
with the solvent being water, is produced by this technique. In suspension polymer-
2.2 Chemistry 19
ization, the monomer is dispersed in droplet form in a continuous medium that is

usually water. The size of the droplets is typically in the range ten to one hundred mi-
crons. This process would be favored where an aqueous based polymer is required,
but where the polymer is insoluble in the monomer. Polyvinyl chloride dispersions
are made in this way.
Emulsion polymerization is also carried out in a continuous water phase, but in
this case the site of polymerization is a far smaller entity than dispersed monomer
droplets, as is the size of the final polymer particles. Harkins [1, 2] developed a quan-
titative theory describing emulsion polymerization in an ideal system. This early
model is still basically accepted today, and is described briefly as follows. In this
process, monomer is “solubilized” within clusters of surfactant molecules, termed
micelles, which form the nucleus of the polymer particle. or a pre-formed polymer
particle of very small size, usually less than 50 nm, which is used as the seed for fur-
ther polymerization. In the case of micellar nucleation, many surface active agents,
when dissolved in water above a certain concentration (Critical Micelle Concentra-
tion or CMC), will form ordered clusters of molecules, with the hydrophobic portion
of the molecule oriented toward the center of the cluster and the hydrophilic portion
toward the outside. The size of these micelles is typically about 4 nm, the general
shape being either spherical or lamellar. When a sparingly water-soluble monomer
(which describes most of the monomers used in emulsion polymerization) is added
to an aqueous solution containing these micelles, it becomes distributed in three
sites; relatively large monomer droplets stabilized by surfactant molecules at the
droplet surface, monomer molecules in solution in the water, and monomer mole-
cules that diffuse into the micelles. The inside of the micelle, with the high concen-
tration of the hydrophobic portions of the surfactant, provides an attraction for the
hydrophobic monomer that diffuses through the water and swells the micelle. These
monomer-swollen micelles are limited in size by hydrodynamic forces and interfa-
cial tension. The number of monomer-swollen micelles in such a system is orders of
magnitude greater than the number of monomer droplets present, and as a conse-
quence the ratio of the surface areas is similarly large. For example, a dispersion of
50 weight percent monomer droplets in water would contain typically about 1010
monomer droplets per liter, whereas a system containing water, soap solution at a
concentration greater than the CMC, and monomer could contain 1017–1019
monomer-swollen micelles per liter. This represents a total surface area of the
swollen micelles approximately 105 times that of the monomer droplets. The conse-
quence of this is that when free radicals are produced in the aqueous phase of a sys-
tem containing water, surfactant and monomer, the free radical has a far greater
probability of entering a micelle and initiating polymerization than it has of entering
a monomer droplet. Also, the overall rate of polymerization, which is the rate per
particle multiplied by the number of polymerizing particles, is greatly enhanced in
the micellar system.
In most cases, the initiators used in emulsion polymerization are water soluble,
and the decomposition, either thermal or with the use of a reducing agent, to pro-
duce free radicals takes place in this phase. It is most probable that polymerization
also starts in the aqueous phase, with free radicals initiating monomer molecules in
Fig. 2-3 Emulsion polymerization [7].
solution in water. As monomer units are added on, these “oligomeric radicals” in-
crease in hydrophobicity and hence the probability of entering a monomer-swollen
micelle increases. A radical which enters a micelle will then continue to add on
monomer using the reservoir within. As long as there is a source of monomer out-
side the micelles, such as monomer droplets, the monomer within a growing parti-
cle will be replenished by diffusion from the droplet through the aqueous phase and
into the particle, the driving force being the affinity of the monomer for the polymer.
The solubilization of the monomer in the micelles and the mechanism of growth
of the polymer particles are depicted in Fig. 2-3.
Polymerization will continue within the particle until either all of the monomer
has been depleted or another radical enters the particle and terminates the growing
chain. If termination occurs, the particle will then remain “dead” until another radi-
cal enters and initiates a new chain. With polymerization taking place within a parti-
cle and fresh monomer entering, the particle obviously increases in size during the
process. Stability is maintained by further adsorption of surfactant molecules at the
surface, along with other mechanisms discussed in Sects 2.2.3 and 2.2.4.
Other sparingly water-soluble ingredients, such as chain transfer agents, follow
the same route, diffusion through the aqueous phase, to enter the growing polymer
particles. Diffusion of molecules into particles is not usually a limiting step in the
overall rate of polymerization, but can be a limit on other processes (Sect. 2.2.6).
An alternative to micellar nucleation, and much practiced today in industry, is the
use of preformed polymer particles of very small and uniform size, normally less
than 50 nm, which act as the nucleus for further polymer growth. This is known as
seeded emulsion polymerization.
2.2 Chemistry 21
Within an individual particle, assuming an active radical is present, the rate of

polymerization is dependent on the particular monomer and the concentration of
monomer in the monomer-polymer mixture. The rate of addition of a monomer
molecule onto a growing polymer chain is known as the propagation rate of the
monomer, kp, this being temperature dependent with increasing temperature giving
increasing propagation rate. Thus in a system with N total particles, and with an av-
– , the overall rate of polymerization
erage number of radicals per particle denoted by n
is given by:
R = k p ⋅ N ⋅ n ⋅ [M ]
[M], the monomer concentration in the swollen particles, is normally expressed as
mol L–1, giving the overall rate of polymerization in mol s–1. It is evident that, with a
constant number of particles at a constant temperature, the overall rate will change
according to the average number of radicals per particle and the monomer concen-
tration in the particle.
Smith and Ewart [3] developed an early quantitative theory to predict the rate of
polymerization in an emulsion system, where they describe three regions.
Typically there is a short induction period as the flux of free radicals builds up, fol-
lowing which a period occurs during which the entry rate of free radicals into parti-
cles is less than the exit rate (region 1). During this period the average number of
radicals per particle can be much less than unity. Region 2 is quickly reached, where
exit of radicals from particles becomes negligible. While the particles are small and
still have high concentrations of monomer, diffusion of radicals within the particles
and mobility of the polymer chains is unrestricted. Under these circumstances, a
maximum of one growing radical is thought to exist per particle, that is, when a rad-
ical enters a particle which already contains a growing polymer radical, termination
of the chain will occur almost instantly. On average, therefore, only one half of the to-
tal number of particles will be actively polymerizing at any given instant, that is the
average number of radicals per particle is about one half. It then remains at this val-
ue until overall conversion reaches 50–60 %. As particles grow larger and the poly-
mer/monomer ratio increases, distances within the particle become greater, viscosi-
ty of the mixture increases, and chain entanglement and cross-linking all contribute
toward reduced mobility within the particle. In this case termination is not instanta-
neous, and an entering radical can co-exist with an already growing chain. This gives
rise to an increase in the overall rate of polymerization in the system (region 3), and
is referred to as the gel effect. In a styrene-butadiene system, the average number of
radicals per particle does not usually exceed two, but with butyl acrylate polymeriza-
tion values of twenty and higher often occur.
Figure 2-4 shows this relationship.
Monomer concentration starts off at one hundred percent in the monomer-
swollen micelles, then drops rapidly when polymerization begins. The polymer
formed is not infinitely swellable, the swollen size of the particles being limited by
entanglement and crosslinking of polymer within the chain and by hydrodynamic
forces and interfacial tension. Typically the weight fraction of monomer in the
monomer-polymer mixture is limited to about 0.45 maximum. As long as there is a
1.6 Fig. 2-4 Typifying the

variation of average
n - Av. radicals/particle
1.4
number of radicals per
1.2 particle with conver-
1 sion. (SB system).
0.8
0.6
0.4
0.2
0 20 40 60 80 100
% Conversion
greater quantity of monomer in the total system, the weight fraction in the particles
will remain at 0.45, with the excess in the form of monomer droplets. When the
monomer droplets have been exhausted, the weight fraction of monomer in the par-
ticles will reduce, reaching zero at one hundred percent conversion. This is depicted
in Fig. 2-5.
1
Weight Fraction Monomer
0.8
M/(M+P)
0.6
0.4
0.2
Fig. 2-5 Typical
0 monomer concentra-
0 20 40 60 80 100 tion in the polymer
particles as a function
% Conversion of conversion.
It can be seen in Figs. 2-4 and 2-5 that, very shortly after the start of polymeriza-
– and [M] become constant, usually to beyond 50–60 % conversion. The re-
tion, both n
sult of this is a constant rate of polymerization over this period. The normal type of
conversion-time curve for a batch polymerization is shown in Fig. 2-6. After a short
induction period, the rate of reaction increases as n – increases. This is followed by a
constant rate period. At around sixty percent conversion, the rate often shows an in-
crease, where an increasing n – has a greater influence than decreasing [M]. Finally the
decreasing monomer concentration has the biggest influence on rate, which there-
after decreases.
In his book on emulsion polymerization, Blackley [4] gives a comprehensive re-
view of the development of the theory of the subject.
2.2 Chemistry 23
Fig. 2-6 Conversion- 100

time curve for a typical
batch emulsion poly- 80
% Conversion
merization.
60
40
20
0
0 1 2 3 4 5 6 7 8 9 10 11
Time h
2.2.2
Major Monomers
The major monomers are considered as those that make up the bulk of the final
polymer chains, being normally greater than five percent of the final polymer com-
position. Not included here are the so-called functional monomers, discussed in
Sect. 2.2.3, which are generally used at levels of less than five percent of the total
composition, and which are used to impart certain special properties to the latex or
polymer.
A large number of major monomers are used in emulsion polymerization, either
by themselves to give homopolymers containing recurring monomer units of
the same type or, more frequently, as mixtures giving copolymers (two different
monomer units), terpolymers (three different monomer units) or polymers with
even higher order. Generally, free-radical polymerization is a random process with
the different monomer units distributed randomly in the polymer molecules. How-
ever, the different reactivities of free radicals with different monomers does lead to
uneven distribution of monomers throughout the polymer chains. One of the major
determining factors in the choice of a monomer is the glass transition temperature,
Tg, of the homopolymer. This is the temperature at which the polymer changes from
a glassy state to an elastomeric material, a change that takes place over a relatively
narrow temperature range. Table 2-2 lists a number of widely used major monomers
in order of increasing Tg.
The Tg of polymers made up from mixtures of different monomers can be approx-
imated by use of the Fox equation [5]:
1 Wm1 Wm2 W
= + + … + mn
Tg Tg1 Tg2 Tgn
where Tg refers to the final polymer, Tg1, Tg2 … refer to the individual homopolymers,
and Wm1, Wm2 … are the weight fractions of the different monomers making up the
final polymer composition. It can be seen that, with 1,3-butadiene and methyl
methacrylate as monomers, a copolymer can be made with any desired Tg in the
Tab. 2-2 Some major monomers used in emulsion polymerization.
Monomer Structure Normal Tg of homo-

b.p. (°C) polymer (°C)
1,3-Butadiene CH2=CH–CH=CH2 –4.4 –85

n-Butyl acrylate CH2=CH–C(O)–O–(CH2)3–CH3 148 –54
2-Ethylhexyl acrylate CH2=CH–C(O)–O–CH2–
CH(CH2CH3)–(CH2)3–CH3 216 –50
Methyl acrylate CH2=CH–C(O)–CH3 80 10
Vinyl acetate CH2=CH–O–C(O)–CH3 73 32
Vinyl chloride CH2=CH–Cl –13 81
Acrylonitrile CH2=CH–CN 77 97
Styrene CH2=CH–(C6H5) 145 100
Methyl methacrylate CH2=C(CH3) CH3C(O)–O–CH3 100 105
range –85 °C to +105 °C. One of the important attributes of polymers which is relat-
ed to the Tg is the film-forming temperature, normally very close to the Tg. As a poly-
mer latex dries and the water evaporates, if the polymer is at a higher temperature
than the Tg then the molecules in an individual particle have enough freedom of
movement to penetrate and intertwine with molecules in an adjacent particle. In this
way, the polymer can form a coherent film. Below the Tg, the movement of mole-
cules is too restricted to allow this interpenetration between particles, and a coherent
film cannot form.
Of course in the design of a polymer, the choice of monomers is not only made on
the basis of the required Tg. Many other polymer properties are of importance. For
example, vinyl chloride may be used where fire retardency is required; acrylonitrile
can impart solvent resistance; acrylates tend to give good heat and light aging prop-
erties. All of the monomers listed in Tab. 2-1, apart from one, are characterized by
having only one C=C double bond, and are known as vinyl monomers. However, 1,3-
butadiene is a member of the diene group of monomers, characterized by having
two C=C double bonds. Isoprene is another common diene monomer. The presence
of this second double bond results in both differences in the polymerization mecha-
nism of a diene relative to a vinyl monomer and in the subsequent behavior of the
polymer. During free-radical polymerization, the butadiene molecules become in-
corporated into the polymer chain through one of the C=C bonds. This can occur in
one of three different ways:
First, by a process of electron transfer, the molecule can be linked into the chain
through carbon atoms 1 and 4, the remaining C=C double bond being between car-
bon atoms 2 and 3. This repeat unit is called 1,4 and there are two possible isomeric
forms, cis-1,4 with the carbon atoms of the double bond both on the same side of the
backbone chain, and trans-1,4 with the carbon atoms of the double bond on opposite
sides of the chain. A third alternative, with the butadiene linked into the chain
through carbon atoms 1 and 2, has the C=C double bond hanging off the chain as a
pendant vinyl group. This incorporation is known as 1,2. Figure 2-7 shows these
three possibilities. Isoprene can be incorporated in four different ways.
2.2 Chemistry 25
Fig. 2-7 Possible *

cis -1,4
methods of incor- n H
poration of butadiene H H * H
C C
during free-radical H
polymerization. * C C * n C H
C H H C
H
H C
H H
*
H H 1,2 (pendant vinyl)
C C H
H C C
H Hn
trans -1,4 *
The presence of these additional C=C bonds in the polymer, generally referred to
as unsaturation, can be of benefit or it can be deleterious to polymer properties. The
double bonds in the backbone chain can be used to give controlled crosslinking be-
tween chains. The process of vulcanization uses controlled amounts of sulfur to
achieve a desired degree of crosslinking and producing a thermosetting polymer.
Also, during free-radical polymerization, the 1,2 pendant vinyl groups compete with
monomer for addition onto a growing free radical, so that crosslinking actually oc-
curs during propagation. This can be controlled to some degree by the choice of
process conditions (Sect. 2.3.2), but cannot be completely eliminated. On the nega-
tive side, the presence of unsaturation in diene polymers leads to inferior heat and
light aging properties relative for example to acrylics, the residual double bonds be-
ing attacked by oxygen, UV radiation etc., eventually leading to yellowing and brit-
tling of the polymer.
The general characteristics that control a polymer’s behavior are basic chemical
composition, crystallinity, glass transition temperature, molecular weight and distri-
bution, gel and crosslinking. Some ways in which desired properties can be achieved
are shown in Tab. 2-3. Of course this Table only shows a few possibilities in polymer
Tab. 2-3 Some aspects of polymer design through composition.
Desired property Possible polymer design
Stiffness Use methacrylates, acrylonitrile, styrene

Soft hand Use n-butyl acrylate, ethyl acrylate, butadiene
Tackiness Use 2-ethylhexyl or hexyl acrylate
Water resistance Use crosslinking monomers N-methylol(meth)acrylamide.
Use hydrophobic monomers like n-butyl acrylate or styrene
Resistance to organic solvents Crosslinking monomers and/or acrylonitrile
High tensile strength High Tg monomers like styrene, acrylonitrile or methyl
methacrylate
High elongation Low Tg monomers like n-butyl acrylate or butadiene
Thermoformability Avoid crosslinking. Use thermoplastic monomers like styrene
High alkali swellability Use high amounts of polymerizable acids like acrylic acid
design. There are vast numbers of different potential combinations of monomers

available to choose from, each with variations in molecular weight, branching,
crosslinking etc., giving almost infinite possibilities in the balance of properties ob-
tained.
2.2.3
Functional Monomers
Certain monomers are characterized as functional monomers, so called because in

addition to having the polymerizable C=C double bond they contain a functional
group such as a carboxylic acid or amide. These monomers are important because
they can impart special properties to both the polymer and the colloidal system. They
are normally used in relatively small amounts, typically 2–5 % of the dry polymer.
Table 2-4 lists some of the commonly used functional monomers. Acrylic and
Methacrylic acids are the most widely used monobasic carboxylic acids, with Itacon-
ic and Fumaric acids as common dibasic acids. These acids, through the C=C bond,
participate in the free-radical polymerization and become incorporated in the main
polymer, but due to the highly polar carboxyl group (COOH) tend to be at the surface
of the polymer particles (polymer-water interface) with the carboxyl group orientated
toward the aqueous phase. The acid group is ionized in water, so that the particle
surface has a negative charge at each acid site (–COO–). The negative charge at the
surface imparts a high degree of stability to the polymer particles, particles repelling
each other due to the like charges. This stabilizing influence is the same as that pro-
duced by surfactants, but with the added advantage that the carboxylic acid is bound
into the polymer chains, not just adsorbed at the particle surface. To maintain over-
all electrical neutrality across the interface, the layer of negative ions is balanced by
an adjacent layer of cationic counterions. The ions and counterions are referred to as
the electric double layer and the thickness of this layer is very dependent on the pH
of the continuous medium. At low pH (high H + concentration) the layer is com-
pressed and at its minimum thickness. As the pH is increased (reducing H + con-
centration), the layer expands outward from the particle. The thickness of this double
layer contributes to the effective diameter of the latex particle, and is one reason for
increasing viscosity as pH increases. It should be noted that the presence of water-
soluble polymer in the latex could also contribute strongly to viscosity increase with
increasing pH, due to stretching of the chains.
Tab. 2-4 Commonly used functional monomers.
Functional monomer Structure
Acrylic acid CH2=CH–C(O)–OH

Methacrylic acid CH2=C(CH3)–C(O)–O–H
Itaconic acid CH2=C(C(O)–OH)–CH2–C(O)–O–H
Fumaric acid H–O–C(O)–CH=CH–C(O)–O–H
Hydroxyethyl acrylate CH2=CH–C(O)–O–CH2–C(OH)H2
Acrylamide CH2=CH–C(O)–NH2
2.2 Chemistry 27
In addition to the greatly enhanced mechanical stability imparted to the emulsion

by these functional monomers, stability to electrolytes is generally improved, as is
filler tolerance of the latex. Mechanical strength of the polymer films is increased,
and in fact can be increased further by the use of, for example zinc oxide, which gives
an ionic crosslink between carboxyl groups. The presence of the carboxyl groups also
allows crosslinking through the use of urea-formaldehyde, phenol-formaldehyde,
melamine-formaldehyde and various epoxy resins. Polymerization of the acid func-
tional monomers is usually carried out under conditions of relatively low pH. Neu-
tralization of the acid favors partitioning in the aqueous rather than the organic
phase, reducing incorporation into the polymer and at worst, where homo-polymer-
ization of the acid is a possibility, as with acrylic and methacrylic acids, the formation
of polyacrylic acid salts in the aqueous phase. These high molecular weight polyelec-
trolytes can act as very effective coagulants for the latex.
2.2.4
Surfactants
As first discussed in Sect. 2.1.1, surface-active materials are normally an essential

ingredient in emulsion polymerization. They can be used in any or all of the follow-
ing roles:
– micellar solubilization of monomers, forming the primary sites for nucleation
– stabilization of growing polymer particles
– enhancement of application properties of the finished latex
A single surfactant may satisfy all three roles, or there may be a requirement for
multiple surfactants. The optimum choice of surfactant for one role may produce
undesirable performance in other roles, and there may be positive or negative syner-
gism exhibited when multiple surfactants are used. As with many other aspects of
emulsion polymerization, a compromise is often required in the choice of surfac-
tant.
A key phenomenon observed with surfactants is a marked change in a number of
physical properties of an aqueous solution that takes place at a certain critical con-
centration. For example, with ionic surfactants, equivalent conductivity exhibits a
sharp reduction, surface tension reaches a minimum then begins to increase, inter-
facial tension reaches a minimum and osmotic pressure almost plateaus. Below this
concentration, surfactant molecules are in normal random solution in the water. As
the critical concentration is reached, the surfactant molecules aggregate into ordered
clusters known as micelles, normally considered to be spherical but other geometry
such as lamellar is also possible. The break in the behavior of solution properties rep-
resents the change from a true solution to a colloidal solution. The concentration of
surfactant at which this change takes place is known as the Critical Micelle Concen-
tration (CMC), and the number of molecules of surfactant which form one micelle is
called the agglomeration number. Addition of further surfactant above the CMC all
goes toward increasing the number of micelles.
The main characteristic of a surfactant is that its molecular structure consists of
two parts, a lyophobic (solvent hating) portion and a lyophilic (solvent loving) por-
tion. When the solvent is water, these two groups are referred to respectively as hy-
drophobic and hydrophilic. The hydrophobic portion of a surfactant is usually a long-
chain hydrocarbon or oxygenated hydrocarbon, although other structures are possi-
ble. The hydrophilic group is either ionic or highly polar.
Surfactants are classified according to the nature of the hydrophilic group of the
molecule:
– Anionic, where the hydrophilic group has a negative charge. Examples are car-
boxylic, sulfate, sulfonate and phosphate groups.
– Cationic, where the hydrophilic group has a positive charge. Long chain quater-
nary ammonium salts and long chain amines and amine salts, with or without in-
corporation of ethylene oxide units.
– Non-ionic, with no charge on the hydrophilic group, often polyoxyethyleneated
long chain alcohols or alkylphenols, the hydrophobic/hydrophilic balance being
controlled by the number of moles of ethylene oxide.
– Zwitterionic, with both positive and negative charge on the hydrophilic group.
Anionic and cationic surfactants are not compatible with one another. Non-ionic
and zwitterionic types are compatible and can be used with either anionics or cation-
ics. Certain zwitterionics become cationic at low pH and anionic as the pH is in-
creased.
Some of the structures that can make up the hydrophobic group are straight or
branched long alkyl groups, long chain alkylbenzene residues, alkylnaphthalene
residues, rosins and high molecular weight propylene oxide polymers. The alkyl
groups are generally 3–20 carbon atoms long, and in most cases, because of the
source of the alkyl group, a particular surfactant will actually be a mixture of various
chain lengths. The properties of the surfactant depend on the length of the hy-
drophobic group, branching or unsaturation, the presence of an aromatic group or
the incorporation of propylene oxide units. Rosen [6] discusses the influence of dif-
ferent hydrophobic and hydrophilic groups in detail. Table 2-5 gives an example of
the influence of some different structures on agglomeration number and CMC. The
effect of increasing linear alkyl chain length in a series of sodium alkyl sulfonates is
Tab. 2-5 Some structural influences on surfactant properties (Rosen [6]).
Surfactant Formula Agglomeration CMC at 40 °C

number / T (°C) (mol L–1)
Sodium octyl sulfonate C8H17SO3– Na+ 25 / 23 1.6 × 10–1

Sodium decyl sulfonate C10H21SO3– Na+ 40 / 30 4.0 × 10–2
Sodium dodecyl sulfonate C12H25SO3– Na+ 54 / 40 1.1 × 10–2
Sodium tetradecyl sulfate C14H29SO3– Na+ 80 / 60 2.5 × 10–3
Sodium hexadecyl sulfate C16H33SO3– Na+ 7.0 × 10–4
Sodium dodecyl sulfate C12H25SO4– Na+ 8.6 × 10–3
Branched sodium alkyl sulfate C12H25CH(SO4– Na+)C3H7 1.7 × 10–3
Sodium dodecyl ethoxylate (2EO) C12H25(OC2H4)2SO4– Na+ 2.8 × 10–3
Dodecyl alcohol ethoxylate (5EO) C12H25(OC2H4)5OH 5.9 × 10–5
2.2 Chemistry 29
seen, increasing carbon number giving rise to reducing agglomeration number and
CMC. The sulfate group is seen to give a lower CMC than the sulfonate. Inclusion of
the sulfate anion on a non-terminal carbon atom increases the CMC, and the intro-
duction of polyethylene oxide (2 mol) into the sulfate reduces CMC. Finally, increas-
ing the moles of ethylene oxide in the non-ionic series of polyoxyethyleneated
straight chain alcohols is seen to increase the CMC.
In emulsion polymerization, anionic and non-ionic surfactants are the most com-
mon choice during the polymerization stage. Cationics are used in polymerization
for some applications, but the use of cationics and anionics in the same equipment
is generally avoided. It is possible to produce an emulsion polymer with either an an-
ionic or a cationic surfactant, and subsequently switch to an oppositely charged
species along with a controlled pH change. Zwitterionics are not common in
emulsion polymerization. If the surfactant is serving the dual purpose of providing
nucleation sites and subsequently stabilizing the growing particles, balancing the
two requirements can be difficult. For micelle formation, the concentration of
surfactant must be at or above its CMC. Then, as a general rule, for a specific surfac-
tant the number of polymer particles initiated is approximately proportional to [sur-
factant concentration]0.6. It is therefore often the case that the amount of surfactant
required to give the desired ultimate particle size is insufficient to provide continued
stabilization as the particles grow. This can occur almost anywhere within the nor-
mal particle size range, and as a consequence it is usually necessary to add addition-
al surfactant as polymerization progresses. Addition of too much surfactant during
polymerization can, if the CMC is exceeded, cause another family of particles to be
initiated. The difficulty of balancing nucleation and stability is exacerbated by
the fact that many factors influence nucleation, for example temperature, concen-
tration of initiator/surfactant/electrolyte, pH and any impurities that either retard or
increase polymerization. Seeded processes significantly reduce this variation and
eliminate the requirement for the initial surfactant. Overall, with seeded processes,
the total amount of surfactant is often considerably less than with micellar nucle-
ation.
Some common surfactants used in emulsion polymerization are:
– Sodium and potassium salts of naturally occurring fatty acids (oleic, linoleic) and
rosin acids. These soaps are used in large quantities in the production of styrene-
butadiene latex for both dry rubber production and latex applications. These mate-
rials are only useful at pH values greater than 7, normally being used at pH 10–12.
Below pH 7, the insoluble acids are precipitated, and all stabilizing function is
lost.
– Salts of sulfated linear alcohols, for example sodium lauryl sulfate, are widely used
in the emulsion polymerization of functionalized styrene–butadiene polymers and
many acrylic esters.
– A range of the salts of alkylbenzene sulfonates and alkylnaphthalene sulfonates,
which give improved electrolyte stability and are not subject to hydrolysis in acid
media as are the sulfated alcohols. Sodium dodecylbenzene sulfonate is widely
used.
– Salts of alkylphosphates, usually polyoxyethyleneated.
– non-ionic surfactants in wide use in emulsion polymerization include polyoxyeth-

yleneated alkylphenols and straight chain alcohols, where the length of the alkyl
group and the moles of ethylene oxide can be varied, and polyoxyethyleneated
polypropylene glycols, block copolymers where the moles of ethylene and propy-
lene oxides can be varied to adjust the hydrophilic/hydrophobic balance.
This list is by no means exhaustive, there being an almost limitless choice of sur-
factants or combinations of surfactants available. From the aspect of particle stabi-
lization during the emulsification process, and even to a large extent nucleation, the
choice of surfactant is usually not too critical. By far the biggest factor in the choice
of surfactant is the application performance of the final product. Unfortunately as a
general rule, the presence of surfactant in the final dry polymer causes reduced wa-
ter resistance. Also, there is a tendency for surfactant molecules to diffuse to the
polymer/air or polymer/substrate interface, where deleterious effects (cloudiness at
the surface, loss of tack, etc.) are often caused. This again demonstrates the compro-
mise often necessary in emulsion polymer synthesis.
In an attempt to mitigate against migration of surfactant, there are certain prod-
ucts available, known as “polymerizable surfactants”, where the molecule contains a
polymerizable C=C double bond. (This is a functional monomer because it does not
form micelles.) Examples are the Noigen and Hitenol series of products from Dai-
Ichi Kogyo Seiyaku (polyethoxylated alkylpropenyl phenyl ethers and polyethoxylated
alkylpropenyl phenyl ether sulfates respectively).
2.2.5
Initiator Systems
The initiator system in emulsion polymerization is the source of free radicals. There
are two major types of system used, substances which thermally decompose to pro-
duce free radicals and substances which produce free radicals when part of a redox
system. Light or other radiation can generate free radicals, but is not widely used for
emulsion polymerization.
By far the most common thermal systems are peroxy compounds; ammonium,
sodium and potassium persulfate and a wide range of organic peroxides and hy-
droperoxides. The rate of decomposition of these materials is usually specified by the
“half-life”, defined as the time taken at a particular temperature for the concentration
of a solution of the material to reduce to one half of its initial value through thermal
decomposition. The three persulfates have a similar half-life and their effectiveness
in emulsion polymerization is therefore also similar. However, the lower water solu-
bility of the potassium salt makes it less commonly used than the others. Persulfates
are generally used for polymerization in the temperature range 50–100 °C, and pro-
duction of free radicals takes place in the aqueous phase of the emulsion. At higher
temperatures, decomposition is usually too fast to give efficient use of the free radi-
cals due to radical recombination. At lower temperatures, persulfates can still be
used in conjunction with a reducing agent such as sodium bisulfite.
The organic peroxides and hydroperoxides cover a wide range of half-life, and can
provide an appropriate choice for most normal polymerization temperatures. The
2.2 Chemistry 31
Tab. 2-6 A range of thermally dissociating initiators (from manufacturers’ product literature).
Substance Half-life (h)1
40 °C 50 °C 70 °C 90 °C 110 °C 130 °C 150 °C
Dicyclohexyl peroxydicarbonate 18 4.1 0.27

Ammonium persulfate 192 8.4 0.55
Dilauryl peroxide 50 3.2 0.29
Dibenzoyl peroxide 14 1.2 0.13
t-Butyl peroxybenzoate 70 6 0.7
Dicumyl peroxide 23 2.3 0.26
Cumene hydroperoxide 570 100 20
t-Butyl hydroperoxide 520 70
1
Approximate values only. pH and the presence of other components can significantly influence
decomposition
differing solubilities in water also determine if the free radicals are produced in ei-
ther the aqueous or the monomer phase. Table 2-6 lists some of the commonly used
thermally dissociating initiators, along with their half-life. Most commonly, the per-
oxides and hydroperoxides are used at lower temperatures, 0–50 °C, as a part of a re-
dox system.
Often persulfates are chosen in preference to the organic peroxides because of the
increase in colloidal stability that results from the sulfate end groups on the polymer
chains. On the negative side, these sulfate groups also increase the water sensitivity
of dried polymer films.
The thermal decomposition of persulfate produces both sulfate and hydroxyl radi-
cals, according to the mechanism:
S2O82– → 2SO4–•
SO4 + H2O → HSO4– + HO•
–•
2OH• → H2O + 1⁄2O2

It is generally accepted that the primary initiating species is the sulfate anion radi-
cal, and to the extent that termination is predominantly caused by another sulfate
initiated radical species, it is expected that most polymer chains would contain two
sulfur atoms. This is generally found to be the case.
An organic peroxide decomposes as follows:
ROOR → 2RO•
and the reduction of a hydroperoxide by iron(II):
ROOH + Fe2+ → RO• + HO– + Fe3+
During the nucleation stage of emulsion polymerization, the concentration of ini-
tiator exerts an influence on the number of polymer particles formed. An initiated
particle grows very rapidly as polymer is formed. As the particle increases in surface
area, it adsorbs surfactant from solution thus reducing the possible number of mi-
celles in the system. Therefore, the faster that initiation occurs, then the greater will
be the number of polymer particles formed before micellar surfactant is exhausted.

Because the thermal decomposition of the initiator is first order with respect to its
concentration, the higher the concentration, the greater will be the rate of radical
production and the shorter the initiation period. The number of polymer particles
formed is approximately proportional to the concentration of initiator to the power of
0.4. As discussed in Sect. 2.2.1, the overall rate of polymerization is proportional to
the number of polymer particles, and therefore the consequent rate of polymeriza-
tion is also proportional to [Initiator]0.4. However, after completion of the nucleation
stage, subsequent changes in the initiator concentration (assuming a certain mini-
mum) have little effect on the rate of polymerization. This is due to the fact that the
number of particles remains fairly constant, and the average number of radicals per
particle is dependent on the environment within the particle, not the rate of radical
production. The molecular weight of the polymer is however influenced by the ini-
tiator concentration, because, neglecting other influences, the time available for a
polymer chain to grow is dependent on the rate at which free radicals enter the parti-
cle. One entering radical initiates polymerization, the next normally terminates the
chain. The higher the concentration of initiator, the higher the rate of production of
radicals and the higher the rate of entry of radicals into a particle. Although this ef-
fect on molecular weight is significant, chain transfer agents often exerts a bigger in-
fluence.
2.2.6
Other Ingredients
The use of chain transfer agents in emulsion polymerization was briefly discussed in
Sect. 2.2.1. As stated, the most commonly used chain transfer agents are the mer-
captans (thioalcohols) RSH, although a wide range of other compounds also exert a
modifying effect during polymerization, for example carbon tetrachloride, certain
disulfides, rosin acid salts, 4-vinylcyclohexene (butadiene dimer) amongst many oth-
ers, which may also include impurities in other raw materials.
The effectiveness of a chain transfer agent is denoted by its transfer constant, ε,
which is the ratio of rate of the chain transfer step to the propagation step:
R–M(n) • + R–SH →Ks
R–M(n)–SH + R•
R–M(n) + M → R–M(n + 1)•
• Kp
Ks
=ε
Kp
It can be shown that, neglecting all other reactions of monomer and chain transfer
agent, that a plot of log [S] against log [M], where [S] and [M] are the concentrations
of modifier and monomer respectively, should be a straight line with slope ε. This
linear relationship is generally found to hold true in emulsion polymerization, but
the slope is often not equal to ε as determined from bulk polymerization. This is be-
cause the rate-determining step for mercaptan consumption can often be the diffu-
sion of mercaptan through the aqueous phase into the reaction zone in the polymer
particle. In general, the fewer the number of carbon atoms in the alkyl group of the
2.2 Chemistry 33
mercaptan, the closer the apparent transfer constant in emulsion polymerization be-
comes to that measured in bulk (faster diffusion). This means that the shorter chain
mercaptans tend to disappear more quickly than the longer chains. Thus the short
chain modifiers tend to exert a greater modifying influence during the early stages of
a batch emulsion polymerization, whereas the longer chain alkyl groups tend to be
more effective toward the end of polymerization. C12 chains often show the best bal-
ance between these extremes, hence the very common use of n-dodecyl and t-dodecyl
mercaptans. Of course, the overall effect of the chain transfer agent can also be con-
trolled by making injections at appropriate times during polymerization, or with
semi-batch reactions by having continuous (linear or non-linear) feeds of modifier.
Polymerizable cross-linking agents are often included in emulsion polymerization
recipes, either to form cross-links during the polymerization (increasing the gel in
the polymer, or increasing the so-called “green strength”) or to form cross-links sub-
sequent to polymerization, by heat application or chemical means. As previously dis-
cussed, when a diene is one of the monomers in an emulsion polymerization, the
second double bond in the diene will lead to a considerable degree of cross-linking
during the polymer formation. In the absence of a diene, other monomers that are
commonly used to produce cross-links during the polymer formation are divinyl
benzene and a range if diacrylates and triacrylates, for example butanediol diacrylate
and trimethylolpropane triacrylate. These materials would normally be incorporated
at low levels, <0.1 weight percent of the monomer, so one can see that, on average,
the number of cross-links introduced would be less than one per thousand
monomer units.
To introduce heat sensitivity into the polymer (cross-linking which occurs after
polymerization, usually when a dried polymer film is heated), two commonly used
monomers are N-methylolacrylamide and N-methylolmethacrylamide. The structure
of N-methylolacrylamide is as follows:
CH2=CH–C(O)–NH–CH2–OH
Incorporation into the polymer backbone takes place through the vinyl double
bond. Cross-linking then takes place between two methylol groups.
| |
CH2–CH–C(O)–NH–CH2–NH–C(O)–CH–CH2 
Electrolytes, most often alkali metal phosphates or sulfates, are utilized in emul-
sion polymerization systems for a variety of reasons. When present in a micelle-
forming surfactant solution, electrolytes can increase the aggregation number of the
micelles (the number of soap molecules per micelle). Thus with increasing elec-
trolyte concentration the number of micelles is reduced, and this is an additional
means of controlling the number of polymer particles formed. Electrolytes are also
used to reduce the viscosity of the polymer emulsion, especially during the polymer-
ization process, an effect that is achieved through compression of the electric double
layer. Finally, electrolytes are often used as part of a buffer system to minimize pH
variation during polymerization. High concentrations of electrolytes will generally
cause de-stabilization and agglomeration of polymer particles.
It is common to include a chelating agent, normally a salt of ethylenediamine

tetraacetic acid (EDTA), in emulsion polymerization recipes. Use of this compound
to chelate metal ion impurities in the system, particularly calcium, magnesium and
iron, generally leads to lower coagulum levels in the final latex, and often gives more
consistent initiation of polymerization. It is fairly common practice in the manufac-
ture of emulsion polymers at higher temperatures to use untreated (non-deionized)
water as the continuous media. The use of a chelating agent protects against the
“hardness” salts. In low temperature systems with redox initiators, a chelating agent
is often a part of the redox system, used to complex the iron component and prevent
precipitation.
2.3
Manufacturing Processes
2.3.1
Types of Process
Compared with many other types of chemical manufacture, the production of emul-
sion polymers is relatively simple in terms of the unit operations required. Typically
there is a reaction stage, where the polymer is made, a purification stage to remove
residual organic volatile components, some type of filtration or screening to remove
any coagulum from the latex and a final stage where post additions of other ingredi-
ents may be made along with final adjustment of latex properties such as pH and
solids content. Occasionally there may be a concentration of the latex to reduce the
water content, and for some processes there may be some purification of raw mate-
rials, or recovery and recycling of raw materials.
Industrial chemical processes are categorized as batch, semi-batch or continuous,
and the manufacture of emulsion polymers is carried out in all these process types.
The processes differ not only in equipment type and economics of operation but also
in the specific properties imparted to the polymer and the emulsion. In a batch
emulsion polymerization, all ingredients are added to a vessel, polymerization is ini-
tiated and the reaction proceeds to completion over a period of time. Thus, condi-
tions in the reactor gradually change from monomer + water → polymer + water,
passing through all intermediate ratios of monomer/polymer.
A continuous polymerization may be carried out in a continuous, stirred-tank re-
actor, where the reactants continuously enter a stirred vessel and the product contin-
uously exits. Here the conditions in the reactor remain constant with time, the com-
position being equal to the exit composition. There may be only one CSTR, or multi-
ple CSTRs in a chain, the product from one being the feed for the next in the chain.
The greater the number of CSTRs in a chain, the closer the properties approach
those from a batch reaction. A plug-flow continuous reactor is one in which the re-
acting mixture passes through the reactor without any forward or backward mixing,
as for example in a tubular reactor. In this type of system, at any given position in the
reactor, the composition is constant with time. Distance along the reactor is equiva-
lent to time in the batch reactor. Although emulsion polymerization in a continuous

tubular reactor has been the subject of much research in the past, this process is not
commonly used because of the poor degree of mixing, heavy fouling of the reactor
and the difficulties of cleaning.
In a semi-batch process, only a portion of the total ingredients is added to the re-
actor initially, polymerization is initiated and the remainder of the ingredients is
added over a period of time until the desired filling volume is reached. The material
is then discharged and the process repeated. In the semi-batch process, conditions in
the reactor change rapidly when the feeds start (monomer → monomer + polymer),
remain relatively constant for the majority of the feed period, and change rapidly
again when the feed stops (monomer + polymer → polymer). For safety reasons
(Sect. 2.3.4) semi-batch is the preferred manufacturing process.
Figure 2-8 shows the typical progression of the monomer/polymer composition
profile in these main process types and Fig. 2-9 is a diagrammatic representation of
the processes.
(A) (B)
100 100
% Conversion
% Conversion
80 80
60 60
40 40
20 20
0 0
0 1 2 3 4 5 6 0 1 2 3 4 5 6
Time Time
(C) (D)
70 100
60
% Conversion
% Conversion
CSTR 5 80
50
CSTR 4
40 60
30 40
CSTR 3
20
CSTR 2 20
10
CSTR 1
0 0
0 1 2 3 4 5 6
Reactor number in chain Distance along reactor
Fig. 2-8 Variation of monomer/polymer in different processes expressed

as % conversion of added monomer: (A) batch; (B) semi-batch;
(C) chain of five CSTRs; (D) continuous plug flow.
There are novel variations of these processes in use, as are combinations of the
processes. The reactor type and the process conditions exert large influences on the
resulting properties as discussed in Sect. 2.3.2.
The product from emulsion polymerization reactors usually contains a small
amount of non-reacted monomers, along with volatile impurities from many
sources. Such impurities may include a range of solvents originating from various
raw materials, dimers and co-dimers either present in monomers or formed during
the polymerization, alcohols from hydrolysis of vinyl esters, products formed from
Feed Feed
Final Level
a) b)
Initial Level
Product Product
Product
c)
Feed
Feed
d)
Product
Fig. 2-9 Types of process used for emulsion polymerization: (a) batch;
(b) semi-batch; (c) continuous stirred tank (chain of three); (d) continuous
plug flow (tubular).
organic initiators, and a whole range of saturated and unsaturated organics coming
from the monomers. In many cases, polymerization is taken to a high degree of con-
version in the reactors (>99 %), so that the residual monomers are often <1 %. How-
ever, it is normal to further polymerize this residual monomer, often using a redox
initiator system. Because of the low monomer concentration at this stage, the rate of
polymerization is relatively slow, and with reactor time normally being at a premium
this “chemical stripping” is carried out in separate, lower cost equipment. Of course
many of the organic impurities are either not polymerizable or cannot be polymer-
ized under typical emulsion polymerization conditions. To remove these contami-
nants, physical separation techniques are often employed. Steam distillation is the
most widely used technique, either in batch strippers or in continuous processes
such as a column stripper. In some cases, solvent extraction, membrane separation
or adsorption processes may be used.
The production of styrene-butadiene rubber emulsions is one case where poly-

merization is deliberately stopped at a low conversion, typically 70–80 %, in order to
limit the crosslinking reaction from the pendant vinyl groups in the butadiene units.
With such large amounts of residual monomer, economics force the recovery and re-
cycling of both butadiene and styrene. After the polymerization stage, residual buta-
diene is flashed off under vacuum, compressed, cooled and returned to the reactor
feed, and styrene is steam stripped in a column stripper, condensed and also re-
turned to the reactor.
Coagulum formed during the manufacture of emulsion polymers can cause prob-
lems with application processes, and although much progress has been made in the
industry to minimize these problems, (improved recipe design, better stabilization
systems, improved control of process parameters), there still exists the need to re-
move coagulum during various stages of the process. All types of filtration equip-
ment are used in the industry, from simple filter bags and static screens through
wiped screens, band filters, vibrating screens, filter presses to quite complex self-
cleaning filters of various types, both with and without the use of filter aids such as
diatomaceous earth. Centrifugation is also used, although with many lattices, the
density difference between polymer and the disperse medium is too small to make
this an efficient process.
Post additions to the latex product, and final adjustments to properties such as pH
and solids content are carried out usually in simple stirred tanks, although continu-
ous in-line mixing may also be practiced.
2.3.2
Influence of Process Conditions on Polymer/Colloidal Properties
As shown in Sect. 2.3.1, the three main types of reaction process differ in the
monomer/polymer concentration profile throughout the reaction. Because many of
the chemical reactions occurring during emulsion polymerization, such as branch-
ing, crosslinking and propagation, are competitive and dependent on the relative
quantities of monomer and polymer at the reacting site, it can be seen that all of
these will be influenced by reactor type. Branching and crosslinking are favored at
high polymer concentrations. Therefore, given the same reaction temperature, a
batch process, which has the highest average monomer concentration through the
process, will give the least branched polymer with the lowest degree of crosslinking.
The opposite end of the scale is represented by a single CSTR operating at a high
conversion which will tend to give a highly branched and crosslinked polymer. In-
creasing the number of CSTRs in a chain will lead to a reduction in branching and
crosslinking. A semi-batch process can be operated at both ends of the scale. With
very fast feed rates, the system is monomer flooded and the product will be close in
properties to the batch reaction. Slow feed rates (monomer starved) lead to high
branching and crosslinking. In particular, in systems containing butadiene where
the pendant vinyl groups contribute strongly to crosslinking, the influence of
monomer/polymer ratio is highly significant. Crosslinking increases rapidly as con-
0.00045 Fig. 2-10 Variation in

the relative degree of
0.0004
crosslinking with per-
0.00035
Relative X-linking
centage conversion
0.0003 during the emulsion
polymerization of
0.00025 styrene/butadiene
0.0002 25:75 in a batch
system at 30 °C.
0.00015
(average number
0.0001 of cross-links per
0.00005 monomer unit in
polymer)
0
0 20 40 60 80 100
% Conversion
version increases (Fig. 2-10) necessitating shortstopping of the polymerization at low

conversion when a polymer with high elongation is required.
Temperature similarly influences branching and crosslinking, both normally re-
ducing with lower temperatures. Molecular weight tends to increase with reducing
temperature. In a semi-batch and a CSTR, the influence of temperature is enhanced
because reducing the temperature at a constant feed rate causes a reduction in poly-
merization rate and hence a reduction in the instantaneous conversion.
The number of particles in the polymerization system influences the rate of reac-
tion; the larger the number (smaller final particle size) the faster the overall rate.
Therefore in a semi-batch reactor or a CSTR, for a given feed rate, the number of par-
ticles exerts an influence on instantaneous conversion and thus all of the properties
previously discussed under conversion. Figure 2-11 shows this influence.
This control over polymer properties by the number of particles in the system
makes it critical to control particle number, and has been one of the driving forces to-
100
% Instantaneous Conversion
90
80
70
60
50
40
30
20 Fig. 2-11 Influence of
number of particles on
10
the instantaneous con-
0 version in a semi-batch
0 2 4 6 8 emulsion polymeriza-
Time in Hours tion of styrene-butadi-
ene 45:55 with a feed
PD = 135 nm PD = 155 nm PD = 175 nm time of 4.5 h at 85 °C.
ward the use of seed polymer. The use of seed reduces the variability of the nucle-
ation stage, making it less dependent on temperature, surfactant concentration, elec-
trolyte concentration etc. Of course this is in turn dependent upon the seed itself be-
ing a consistent raw material.
2.3.3
Equipment Considerations
The reactors used for the manufacture of emulsion polymers are normally relatively
simple, agitated vessels, ranging in size from 5 m3 (less than this is normally consid-
ered to be pilot plant scale) to 200 m3, with the majority being in the range
15–100 m3. Carbon steel, glass-lined construction used to be the standard (the glass
surface minimizing polymer deposition) for polymerization under acid or slightly al-
kaline conditions. For high pH systems (for example those based on the alkali metal
salts of fatty acids and using redox initiator systems) carbon steel reactors are the
standard. As emulsion stability has been improved over the years, and better clean-
ing techniques have been developed (high pressure water jets), it has become com-
mon to replace glass-lined reactors with either stainless steel or carbon steel with
stainless steel cladding. Typically, to avoid contamination from metal ions, all
pipework associated with feeds into and product from the reactor would be stainless
steel construction.
Pressure ratings of reactors range from atmospheric to >100 bar with temperature
of operation in the range 5–200 °C. (in certain special cases sub-zero temperatures
may be achieved through the use of anti-freeze agents in the emulsion). The most
common temperature range for emulsion polymerization is 60–100 °C.
To control the temperature of these highly exothermic reactions, reactors are fitted
with a variety of cooling systems. This may be a jacket around the reactor (annular,
dimpled, half-pipe); the reactor may be fitted with internal cooling coils or cooled
baffles; there may be supplemental cooling systems such as reflux condensers, or
heat exchangers of various types through which the reaction mixture is circulated.
For agitation, a wide variety of impeller types are in use; both axial and radial flow
turbines, propellers, paddles, anchor agitators and many other proprietary designs.
The choice of impeller is very much dependent on the properties of the emulsion
polymer being made (stability, viscosity etc.).
Latex may be transferred through subsequent parts of the process either using in-
ert gas pressure or with a variety of low shear pumps. It is normal to neutralize the
latex after the reaction stage, thus greatly increasing stability. High-pressure equip-
ment is not usually necessary downstream of the reactor, although some operations
will require full vacuum rating.
As discussed in Sect. 2.3.1, batch strippers, stripping columns, filtration equip-
ment and mixing vessels are all in use to a varying extent downstream of the reaction
stage. Because of the tendency of emulsion polymers to cause deposits in the
process, the secret of successful operation is usually to keep equipment simple. Ease
of cleaning is paramount, and “moving parts”, particularly if high shear is imparted
to the latex, should be avoided where possible.
2.3.4
Safety Considerations
To carry out emulsion polymerization safely, the pressure which can develop under
a worst case scenario should always be less than the design pressure of the reactor.
As with any highly exothermic chemical reaction, if the generated heat is not re-
moved from the system, the temperature (and in an enclosed system, the pressure)
will increase in an exponential manner. The pressure can rapidly exceed the design
pressure of the containing vessel, resulting in rupture of the vessel or its associated
piping if the system is not protected by appropriate relief devices. It has to be ques-
tioned whether or not relief devices are ever really appropriate – in reality, although
the reactor may be protected, a potentially hazardous situation is being transferred
elsewhere (vent tanks, quench tanks, environment). The correct sizing of relief sys-
tems for emulsion polymerization reactors is also not a trivial exercise, in part be-
cause it is difficult to define a worst case scenario and in part because emulsion and
polymer properties at extreme reaction conditions are not well known. Very large re-
lief devices are often indicated, which in turn means a large problem outside the re-
actor.
A major driving force for the change from batch to semi-batch polymerization
processes, despite the loss in some polymeric properties which often accompanies
this change, has been the inherently safer aspects of semi-batch, with smaller quan-
tities of monomer in the reactor at any given time.
Thus, the major capacity limitation in the process can be seen to be a function of
the pressure rating of the reactor, the rate and efficiency of removing heat from the
system, and the safety systems which are in place to ensure that the maximum reac-
tor working pressure can never be exceeded.
References
1 W. D. Harkins, J. Am. Chem. Soc. 1947, 5 T. G. Fox, P. J. Flory, J. Appl. Phys.

69, 1428. 1950, 21, 581.
2 W. D. Harkins, J. Polym. Sci. 1950, 5, 6 M. J. Rosen, Surfactants and Interfacial
217. Phenomena, John Wiley and Sons,
3 W. V. Smith, R. H. Ewart, J. Chem. Phys. 1989.
1948, 16, 592. 7 The schematic diagram is a courtesy
4 D. C. Blackley, Emulsion Polymerisation of C. D. Anderson, M. S. El-Aasser,
Theory and Practice, Applied Science, Emulsion Polymers Institute, Lehigh
1975. University, Bethlehem Pennsylvania.
3
Characterization of Aqueous Polymer Dispersions
Harm Wiese
3.1
Introduction
Aqueous polymer dispersions and the polymer films that form from them exhibit a
diverse and complex range of properties. Moreover, these systems possess a marked
heterogeneity at the mesoscopic level and their characterization is therefore a diffi-
cult task. In addition to determining the macroscopic properties of the dispersion
(Sect. 3.2.1), characterization requires investigating the polymer particles themselves
(Sect. 3.2.2), the residual volatile content (Sect. 3.2.3) and the aqueous phase
(Sect. 3.2.4). It is also important to understand the process of film formation
(Sect. 3.3.1) and to be able to describe the macroscopic and microscopic properties of
the film (Sects 3.3.2 and 3.3.3).
Given the large number of parameters and the numerous techniques employed to
measure them, this article can only hope to provide a broad overview of this vast sub-
ject area. For more detailed descriptions of the various measurement methods, the
reader is referred to the literature.
Beyond the general physical and chemical characterization of dispersions and
polymer films, a large number of application-specific tests exist. In this chapter,
space does not permit discussion of these tests nor of the wide variety of the formu-
lations used in the different applications. Other areas which have had to be excluded
are the on-line and off-line methods of monitoring emulsion polymerization [1] and
techniques for determining the microbial contamination of polymer dispersions.
42 3 Characterization of Aqueous Polymer Dispersions
3.2
Polymer Dispersions
3.2.1
General Characterization of Dispersions
Solids content
In most of the applications the determination of the solids content is the first part of
any routine characterization of emulsion polymers, since it is the polymer and not
the water which is used in the final product.
Typically, the dispersion is dried to constant mass at a temperature of between 100
and 140 °C (see, for example, ISO 1625) and the solids content is then expressed as
the percentage ratio of the dry matter to the total mass of the sample.
The dry matter comprises the polymer, emulsifiers and inorganic salts (formed by
the decomposition of the initiators and from neutralization). The volatile part in-
cludes the water and monomers which were not converted during the polymeriza-
tion reaction. A comparison of the theoretical solids content (that is assuming com-
plete monomer conversion) to the experimental value therefore provides a means of
assessing how far polymerization has proceeded to completion.
To accelerate the drying process, most modern laboratories make use of alterna-
tive drying techniques such as halogen lamps, microwaves and infrared radiators.
Because of a possible thermal decomposition of the polymer or emulsifiers however
the temperature of the sample must not be allowed to rise much above the tempera-
ture range specified above. Furthermore, the drying rate should not be too high since
this may cause skin formation on the surface of the sample. If the skin bursts mate-
rial can be lost from the sample tray.
Coagulum and grit

In many applications polymer dispersions must only contain a very small fraction of
agglomerates with diameters greater than 1 µm. Coarse components may be re-
moved by filtration. Mesh sizes of between 45 and 180 µm are typical. The filter
residue is known as the coagulum content or sieve residue.
A determination of sieve residue according to ISO 4576 may involve pre-diluting
the dispersion with water before filtering it through stainless steel filters having the
above mesh size. The residue is rinsed with water, dried and weighed. The amount
of residue is expressed as a fraction of the original dispersion mass. The type of filter
and the mesh size should be specified.
Fine agglomerates or large polymer particles which cannot be separated by filtra-
tion but are still visible in the wet or dry polymer film are known as grit. The grit is
undesirable in many applications, particularly in transparent coatings and must be
prevented during the polymerization process. To characterize the fraction of grit
present, the filtered dispersion is cast on to a glass plate using film applicators with
specified gap size (for example 45 or 125 µm). When viewed with transmitted light,
grit particles can be detected by their refraction and diffraction effects. Normally, the
assessment is performed on the dry film. The number of grit particles per unit area
is counted or the grit pattern classified by comparison with standard samples. Possi-
ble sources of error in assessing grit content are wetting defects and occluded gas
bubbles.
pH, density and surface tension

pH is an important factor in both the stabilization and the formulation of polymer
dispersions. For example, dispersions that contain carboxylic acids are usually ad-
justed to a pH of between 7 and 9 in order to improve their stability and to increase
viscosity. pH measurements can be performed using a standard combination elec-
trode (see ISO 976). Problems however often arise due to film formation on the glass
membrane.
The densities of most polymer dispersions are close to 1 g cm–3 as the corresponding
polymers (with the exception of polyvinyl chloride and poly(vinylidene chloride))
have densities in the range 1.0 to 1.2 g cm–3 [2]. Since the densities of the polymer
particles almost match the density of the aqueous phase, sedimentation is usually
only a problem in emulsion polymers if they contain very coarse particles. Density
measurements have been used in the past to follow the course of emulsion polymer-
ization reactions, because the density of the monomer is usually lower than that of
the polymer (densitometry [1]). Densities can, for instance, be determined quite sim-
ply with a pycnometer (see ISO 2811). Very high precision density measurements
(±5 × 10–6 g cm–3) are possible with a vibrating-tube densimeter [3]. In this method,
the change in the resonant frequency of the tube, which depends on its total mass, is
measured when the dispersion is placed in it. It is essential that the sample is whol-
ly free of gas bubbles.
The surface tension of a polymer dispersion is of major importance in the coating
of substrates. Good wetting of the substrate is achieved with a dispersion of low sur-
face tension (Sect. 3.3.2). A general approach to obtain information on the wetting
properties of a dispersion is by measuring its surface tension in air, which is gener-
ally easy to determine experimentally. As a result of the emulsifiers used in emulsion
polymerization, the surface tensions of polymer dispersions generally lie some 20 to
40 units below that for water (73 mN m–1).
Surface tension measurements can be made by the Du Nouy ring method (see ISO
1409), the hanging drop method or by using a stalagmometer [4]. In the latter two
techniques, the shape or volume of a drop of the dispersion as it emerges from a cap-
illary is used to compute the surface tension. In the Du Nouy ring method, a thin
ring of platinum wire, suspended in the dispersion parallel to the surface, is with-
drawn from the dispersion and the tensile force exerted by the liquid lamella that ex-
tends from the ring to the bulk liquid is measured just before it ruptures. As this
method requires relatively low dispersion viscosities (< 200 mPa s), it is often neces-
sary to dilute the dispersion before measurement.
The ring method enables the static surface tension of the dispersion to be deter-
mined. When polymer dispersions are applied on large-scale coating machines, it is
also important how fast the surface tension of a freshly generated surface is able to
decrease. A device which permits this dynamic surface tension to be measured is the
maximum bubble pressure tensiometer [5]. In this method, gas bubbles are blown
through a capillary into the dispersion. The surface tension can be calculated on the
basis of the pressure changes during bubble formation. By varying the gas speed, the
dynamical processes during the growth of the surface can be accessed. It is worth
noting that the hanging drop and stalagmometer techniques are also dynamic meth-
ods, because the dispersion is continuously emerging from the capillary, albeit much
more slowly than the gas exiting the capillary in the maximum bubble pressure ten-
siometer.
Flow behavior
The flow behavior of a polymer dispersion or of its formulation is a central, and often
critical, processing parameter [6]. Paints, for example, must be easy to apply, should
form smooth surfaces, but should not sag when applied to a wall and should not
spatter during brush application. In contrast to conventional liquids, the rheological
properties of dispersions with a solids content above roughly 25 % are complex and
strongly dependent upon the forces applied, developing, in certain cases, a “memo-
ry” of these forces. This behavior is caused by the particle interactions that become
apparent when the solids content is high. Apart from solids content, particle size and
particle size distribution play a crucial role. Other factors affecting flow behavior are
the electrostatic charges of the polymer particles, their surface composition and wa-
ter-soluble oligomers in the aqueous phase. In practice, particle charge has only a
relatively minor influence because the ionic strength of the aqueous phase is gener-
ally high enough (due to the presence of ions arising from the decomposition of the
initiator and from neutralization) to restrict to a few nanometers the range over
which the electrostatic forces are effective. Even relatively small amounts of water-
soluble polymers have a pronounced influence on the flow properties of a dispersion
and this fact is used in practice to adjust the viscosity of the dispersion to the desired
level (thickeners). In contrast to polymer solutions, molecular weight and polymer
composition do not have a significant effect on the rheology of a polymer dispersion.
A simple crude assessment of flow behavior can be achieved on-site using so-
called flow cups – funnel-shaped vessels with specified orifices in their bases. The
measurement variable is the efflux time, that is the time taken for a known volume
of dispersion to exit the cup through the orifice. It is important to be aware of the fact
that a variety of cups are in use and that each type of cup produces a different efflux
time. The most common types are the ISO cups (complying with ISO 2431) and the
Ford cups used in the ASTM D 1200 test procedure.
The efflux time characterizes the low-shear flow behavior of a dispersion flowing
under its own weight. In many industrial applications, however, much greater shear
forces are applied (for example in coating machines) and these forces often have a
strong effect on the rheological properties of the dispersion (non-Newtonian behav-
ior, see below). The effect of shear forces can be investigated by measuring a flow
curve with a rotational viscometer (Fig. 3-1 and ISO 3219). The dispersion is sheared
in a cup by an immersed rotating cylinder (spindle). In the measurement the veloci-
ty gradient (or shear rate) between the outer surface of the cylinder and the inner sur-
face of the stationary cup is varied. The flow curve is the plot of the torque acting on
the cylinder (or the shear stress τ which can be derived from it) as a function of the
Rotational Flow curve

viscometer
shear stress τ
shear
stress
shear
rate
shear rate D
Fig. 3-1 Measuring a flow
0
curve using a rotational
viscometer. viscosity η = τ / D
shear rate D. The (dynamic) viscosity is defined as the quotient of shear stress and
shear rate at every point along the flow curve. As both low viscous aqueous-like and
highly viscous dispersions are used, a measurement range of between one and
several thousand mPa s must be accessible. Because of the technical limitations of
the shear-force transducers, different cylinder/cup sizes are usually required in or-
der to cover both low-viscosity to high-viscosity dispersions. Shear rates of up to
about 1000 s–1 can be accessed with conventional rotational viscometers.
The Brookfield type of viscometer, in which one of a number of different spindle
types (RV, LV and so forth) is rotated in the sample dispersion, also enjoys wide-
spread use for viscosity measurements (see ISO 2555 and 1652). The disadvantages
associated with this type of viscometer are that the shear rate is not well defined and
that the results of measurements made using different spindle types cannot be com-
pared with one another.
Figure 3-2 presents a number of τ/D and η/D curves which summarize the vari-
ous phenomenological descriptions of how dispersion viscosity depends upon shear
rate or time. In many cases, one observes shear thinning (viscosity decreases with in-
creasing shear rate) and thixotropic behavior (viscosity falls with time at a constant
shear rate). For this reason, the flow curve is recorded (as shown in Fig. 3-1) by meas-
uring the shear stress both as a function of increasing shear rate and as a function of
decreasing shear rate. The hysteresis visible in Fig. 3-1 is typical of thixotropic dis-
persions.
Figure 3-3 shows a viscosity/shear rate dependence which is often observed for
polymer dispersions. In this log-log plot, an high initial plateau at low shear rates is
followed by a region of shear thinning which leads to a lower plateau at high shear
rates. Increasing the shear rate further induces a strong dilatancy and possibly also
coagulation. The shear thinning is assumed to be caused by the onset of ordering
within the dispersion as the polymer particles align themselves in parallel layers
(Fig. 3-3). The dilatancy is thought to be the result of the temporary formation of ag-
gregates which can only pass by one another with difficulty.
Shear rate dependence Fig. 3-2Phenomenological

τ τ τ τ classification of the flow
behavior of polymer disper-
η sions (τ, shear stress; D, shear
D D D
yield stress rate; η, viscosity; t, time).
D
Newtonian pseudoplastic, dilatant, plastic
shear thinning shear thickng.
η η η η
D D D D
Time dependence (constant shear rate)

η η
thixotropy
rheopexy
t t
log (viscosity)
shear dilatancy
thinning
log (shear rate)
Fig. 3-3 Typical dependence

statistical shear-induced aggregation of the viscosity of a polymer disper-
distribution ordering sion on the shear rate.
When processing dispersions, a particular viscosity is often desired both at low

and at high shear rates, and these viscosities may be very different. A key objective in
the formulation and production of polymer dispersions is therefore to adjust the
shear-rate profile to meet the demands of the particular application. One way in
which this can be achieved is by the addition of polymeric thickeners, which influ-
ence the viscosity at low and at high shear rates differently depending upon their
structure and molecular weight.
Figure 3-4 shows schematically how the viscosity of a polymer dispersion varies as
a function of the volume fraction φ of the particles. The volume fraction is normal-
ized to unity. In rheology it is more commonly used than the alternative solids
content of the dispersion. A characteristic steep increase in the viscosity is observed
as one approaches a maximum volume fraction φm. Semi-empirical expressions
Fig. 3-4 Dependence of viscosity on viscosity

the particle volume fraction.
shear rate:
low
high
φm
volume
fraction φ
exist which provide more or less reasonable approximations of the experimental

curves. For the purposes of illustration the Dougherty–Krieger equation is repro-
duced here:
−2.5φm
η  φ 
= 1 −  (3-1)
η0  φm 
where η0 is the viscosity of the aqueous phase.
The theoretical upper limit for the maximum volume fraction φm of monodisperse
spheres is 0.74, which is the value associated with hexagonal close packing. Howev-
er, the steep rise in viscosity can occur at smaller volume fractions (often at around
0.55 to 0.6), depending upon the type of packing and the distance over which the
interparticle forces act. If the volume fraction is constant, decreasing particle size
results in a decrease in the distance between the particles and an increase in the
total particle surface area. This is the reason why dispersions containing fine
particles have higher viscosities than those containing coarser ones. Low viscosity at
high volume fractions can be achieved with a bimodal or broad size distribution
where the interstitial spaces between the larger particles are filled with the smaller
ones.
Machine processing exposes dispersions not only to shear but also to tensile
stresses (extensional flow). Because of the lack of commercially available test equip-
ment, studies of the extensional flow of polymer dispersions are still in their infancy.
Little use is also made of viscoelastic techniques where the sample is subjected to
low-amplitude oscillatory shear and the amplitude and phase of the oscillating stress
is measured (usually as a function of the frequency of the oscillation).
Stability
The production, transport and processing of polymer dispersions expose these mate-
rials to significant degree of mechanical and thermal stress, which can lead to coag-
ulation, sedimentation, phase separation or changes in viscosity. These changes are
generally due to instabilities of the polymer particles.
To avoid these problems, polymer dispersions are routinely tested for mechanical
and storage stability and, for certain applications, also subjected to freeze-thaw cycles.
After testing, any changes can be inspected visually or quantified using the methods
available for assessing the coagulum, the viscosity or the particle size distribution.
Mechanical stability: The dispersion is subjected to intensive, defined stirring (us-

ing a serrated stirring disk or rotor/stator units) as, for example in ISO 2006 where
the sample is agitated for 10 min at 14 000 rotations min–1.
Storage stability: Accelerated testing is achieved by storing the dispersion at
enhanced temperature for a particular time (for example for 15 h at 80 °C).
Freeze-thaw stability: This test provides information about the re-dispersibility of a
dispersion after having been frozen. The test involves subjecting the dispersion to
repeated freeze-thaw cycles (for example 16 h at –20 °C followed by 8 h at + 23 °C).
See, for example ISO 1147.
Stability with respect to additives: For many formulations, the stability of the disper-
sion with respect to various additives, such as electrolytes, solvents, fillers and pig-
ments, must be tested. The additives are added either directly or, where necessary,
appropriately diluted, with any changes of the dispersion being assessed as described
above. Testing is often conducted on diluted dispersions to permit simple visual in-
spections to be carried out, though the conclusions that can be drawn from these
qualitative assessments are naturally limited.
Foaming behavior
Because of the presence of emulsifiers, polymer dispersions tend to foam. For many
applications (for example spray coating) foaming must be suppressed by the addition
of defoaming agents. The tendency of a dispersion to foam can be assessed by a
number of application oriented methods which can be used for relative measure-
ments [7]. One common method uses a graduated cylinder whose base is sealed by a
porous glass frit through which gas can enter the cylinder. A known quantity of the
dispersion is placed on the frit, the gas flow initiated and the height of the foam with-
in the cylinder is then recorded as a function of time. Good reproducibility requires
careful temperature control and thoroughly clean cylinders and frits. An alternative
approach is to measure the foam height after beating the dispersion within a cylin-
der with a perforated plate for a set time.
3.2.2
Characterization of Polymer Particles
This chapter restricts itself to a presentation of the methods used to characterize the
size and the surface of the polymer particles. Analysis of the polymer itself or the
particle morphology is usually performed on the polymer film or on the dried parti-
cles and is therefore treated later in Sect. 3.3.3.
Particle size
Polymer dispersions contain particles with diameters ranging from 10 to about
1500 nm. Typically, the particle size is between 100 and 250 nm. In the majority of
applications, particle size and particle size distribution are highly significant factors
that determine the properties of a polymer dispersion, such as its flow behavior or its
stability (Sect. 3.2.1). Measuring particle size is thus an important element when de-
veloping polymer dispersions and is also used in in-process control. A broad range of
methods are available for determining particle size [8] of which only light-scattering
and sedimentation techniques as well as modern fractionation methods will be dis-
cussed here. Electron microscopy is dealt with later in Sect. 3.3.3 which discusses the
characterization of particle and film morphology.
Light transmission
A distinctive feature of polymer dispersions is their turbidity. It is caused by light
scattering of the polymer particles due to the difference in the refractive indexes of
the polymer (typically 1.4 to 1.6 [2]) and water (1.33), and provides a simple way of
accessing the mean particle size in the dispersion. The link between the scattering
behavior of a dispersion of spherical particles and their diameter is provided by Mie
theory [9] and is shown in Fig. 3-5 for the relative transmission of white light through
various 0.01 %, w/w dispersions. Transmission increases as particle size falls or with
decreasing relative refractive index (refractive index of the polymer/refractive index
of water). If the relative refractive index is known, Fig. 3-5 can be used to determine
the mean average particle size from the observed relative light transmission. The
measurement can be performed within a matter of seconds using a simple arrange-
ment of lamp, cell and photocell detector.
LT / %
100
80
Fig. 3-5 Relative light transmission LT 60

of 0.01 % polymer dispersions as a m =1.10 (polyacrylate)
40
function of particle diameter for differ-
m =1.20
ent relative refractive indexes, m. 20 m =1.15
(polystyrene)
LT = transmission through water/trans-
mission through dispersion (2.5 cm cu- 0
vette, white light). m = refractive index 0 100 200 300 400 500 600
of the polymer/refractive index of water. diameter / nm
For polydisperse dispersions, the measured light transmission is the inverse geo-
metric mean of the relative transmissions LT1, LT2, … of the respective mass frac-
tions m1, m2, …:
−1
LT = LT1− m 1 ⋅ LT2− m 2 ⋅ … (3-2)
Laser light scattering

Of the many methods based on laser light scattering, dynamic light scattering
(DLS, also called quasielastic light scattering QELS or photon correlation spec-
troscopy PCS) has established itself as the most important technique of measuring
particle size in polymer dispersions [10]. The measurement (Fig. 3-6) involves direct-
ing a laser beam into a highly diluted sample of the dispersion and recording the
scattered light impinging on a photomultiplier at a particular angle.
laser sample Fig. 3-6 Dynamic light scattering.

Experimental set-up and intensity
fluctuations.
scattering angle
polarizer
analyzer
intensity
photo-
multiplier
time
The intensity of the scattered light reaching the detector is determined by the mu-
tual interference of the light waves scattered from the individual particles in the dis-
persion. Because laser light is highly coherent, the scattered waves have a fixed phase
relationship to one another which is determined by the geometrical arrangement of
the scattering particles. The Brownian motion of the particles causes a statistical vari-
ation of the phase relationship in time, producing corresponding fluctuations in in-
tensity at the detector (Fig. 3-6). The mean frequency of these fluctuations, which in
DLS is determined by autocorrelation of the scattering intensity, is proportional to
the diffusion coefficient of the particles. A hydrodynamic particle diameter d can
then be calculated from the measured diffusion coefficient, D, using the Stokes–Ein-
stein equation:
kT
D= (3-3)
3πηd
where k is Boltzmann’s constant, T temperature, and η the viscosity of the aqueous
phase. If the approximation of hard, non-interacting spheres is assumed, the hydro-
dynamic diameter is equal to the particle diameter.
The measurement, which takes only a few minutes to perform, can be used to de-
termine particle diameters of between 5 nm and 5 µm. In order to avoid complica-
tions due to multiple scattering of the laser light and due to particle interactions,
which influence diffusion, the measurements must be carried out on highly dilute
samples (10–5 to 10–2 %, w/w).
DLS is used as a routine means of determining particle size in monodisperse poly-
mer dispersions. Typical systems employ a red helium-neon laser (wavelength:
633 nm) and a scattering angle of 90°. However, the resolution achievable with such
systems when measuring polydisperse samples is generally quite low. As a rule of
thumb, the particle diameters of two fractions must differ by a factor of 3 or 4 if they
are to be clearly differentiated.
A further fact which complicates the analysis of polydisperse samples is that the
diffusion coefficients are weighted according to the scattering intensity. According to
Mie theory, the scattering intensity of light on particles whose diameter d is approxi-
mately equal to the wavelength λ of the light is a complex function of d, λ, the refrac-
tive indexes of the particles and the scattering angle. This fact considerably compli-
cates the calculation of the exact mass fractions. For this reason, most equipment
manufacturers make use of simple approximate descriptions of the dependence of
scattering intensity on particle size. A more accurate approach is to measure the ab-
solute scattering intensities and intensity fluctuations at a number of angles and
then to use Mie theory (assuming that the refractive indexes of the particles are
known) to convert the measured data to a particle size distribution [11].
Compared with DLS, static light scattering, in which the absolute intensity of the
scattered light is analyzed as a function of scattering angle, has become less relevant
as a method of determining polymer particle size. Static measurements are today
mainly used for characterizing dissolved macromolecules (with gyration radii
<100 nm) and for particles with a diameter greater than 1 µm (Fraunhofer diffrac-
tion). The reader is referred to the literature for further details on these tech-
niques [12, 13].
Centrifugation
Centrifugation methods allow a detailed and comprehensive characterization of
polymer dispersions. Figure 3-7 is a schematic view of an analytical ultracentrifuge
(AUC) equipped with two types of optical detection systems (schlieren optics and tur-
bidity measurement at fixed radial position, “turbidity optics”) [14]. Particle size
determination with an AUC exploits the different sedimentation rates of the parti-
cles in the centrifugal field. According to Stokes’ law, the sedimentation time, ts, for
the path between the radial position of the meniscus, rm, and the position of the de-
tection optics r (Fig. 3-7) in a centrifuge rotating at a constant angular velocity, ω, is
given by:
18η ln(r/rm )
ts = (3-4)
( ρ – ρm )d 2ω 2
where η is the viscosity of the aqueous phase, ρ – ρm the difference in density be-
tween the particles and the aqueous phase, and d is the particle diameter. Thus par-
ticle size determination requires the precise knowledge of the particle densities.
schlieren optics turbidity optics
video camera photomultiplier
schlieren
plate
sample ω
cuvette rm
Fig. 3-7 Schematic diagram
of an analytical ultracentrifuge r
(ω is the angular velocity of
the rotor). lamp laser
The measurement of the particle size distribution (PSD) is performed on dilute

samples (typical concentration: 0.05 to 2 %, w/w) in a so-called sedimentation veloci-
ty analysis using the turbidity optics (Fig. 3-7). At the start of the measurement the
dispersion is uniformly distributed throughout the cell and the detector registers an
attenuated laser beam. As soon as the first particle fraction has migrated under the
influence of the centrifugal field out of the optical path, the signal at the detector in-
creases. Particle size can then be determined by measuring the time at which the sig-
nal begins to rise. By applying Mie scattering theory (knowledge of particle diameter
and refractive index required) the mass fraction of that particular particle fraction
can be computed from the increase in signal amplitude.
Measurements can be performed with high resolution in the diameter range be-
tween 20 and 2000 nm. Figure 3-8 illustrates the result of a sedimentation velocity
analysis on a mixture of ten polystyrene calibration latexes. Measurements on such
broadly distributed samples are usually performed with an exponentially increasing
rotation speed and require centrifuges capable of reaching 60 000 rotations min–1
(Eq. 3-4); a measurement typically lasts 1 h. Machines designed to allow simultane-
ous determinations with eight sample cells per rotor are described in the litera-
ture [14].
Fig. 3-8 Particle size

distribution (differen-
tial and cumulative)
of a mixture of ten
polystyrene calibration
latexes (sedimentation
velocity analysis).
By carrying out the sedimentation velocity analysis not only in H2O but also in
D2O and in a 1:1 H2O:D2O mixture (H2O/D2O analysis), both the PSD and informa-
tion on the density (and thus chemical uniformity) of the individual particle fractions
may be obtained.
Apart from the sedimentation velocity analysis, the AUC may also be used to per-
form a so-called density gradient analysis. In a density gradient analysis, a water-sol-
uble substance of high density (CsCl or the iodinated sugar metrizamide) is added to
the sample so that in the liquid phase a radial density gradient is established at equi-
librium in the centrifugal field. The various particle fractions migrate along the gra-
dient to the point having their own density, thus allowing the densities – as in the
H2O/D2O analysis – to be determined. I this case the schlieren optics (Fig. 3-7),
which detect changes in the refractive index along the radial axis, is used for the
analysis. In contrast to the turbidity optics, a photo of the entire cell is taken once
equilibrium has been established. Normally between 10 and 20 h are needed to
achieve equilibrium.
The advantage of using the schlieren optics is that in addition to the particle frac-
tions also dissolved macromolecules can be studied with respect to chemical compo-
sition and molecular weight. Like the polymer particles, the macromolecules migrate
along the density gradient to their isodensity point. However, the small size of the
macromolecules means that the bands are diffusion broadened. If the scaling law
that relates the diffusion coefficient to the molecular weight is known, the latter can
be calculated.
The considerable amount of information obtainable by AUC analyses must be
viewed in the light of the considerable technical expense and effort needed to run
such a machine. At present, only a few laboratories have access to this technology.
Disc centrifuges are a cost-effective alternative (rotation speeds of up to 15 000 rota-
tions min–1).
Because of the lower rotation speeds in a disc centrifuge a different analysis tech-
nique has to be employed. The cell is first filled with a spin fluid and then a sample
layer is injected on top of the fluid while the disc is rotating. By this means the parti-
cle fractions migrate past the detection optics layer by layer according to their differ-
ing sedimentation velocities. Unfortunately, it is often difficult to achieve a uniform
injection layer in practice (because of disruptions of the sample flow front). For this
reason, and also because of the low density difference between the polymer particles
and the aqueous phase, disc centrifuge sedimentometry is not widely used for the
characterization of polymer dispersions.
Modern fractionation methods

In recent years a number of new fractionation techniques, such as capillary hydro-
dynamic fractionation (CHDF) [15] and field field-flow fractionation (F-FFF) [16],
have established themselves as reliable alternatives to centrifugation in PSD analy-
sis. Only CHDF will be discussed here. The technique involves injecting a small
amount of the sample into an aqueous eluent containing an emulsifying agent. The
eluent is pumped through a glass capillary tubing (inner diameter 7–10 µm) and in
so doing adopts a laminar flow profile (Fig. 3-9). The larger the particles, the less able
they are to approach the capillary wall during thermal Brownian motion. Large parti-
cles are therefore, on average, flowing in faster stream lines than smaller ones and
are transported more rapidly through the capillary. The particle fractions are detect-
ed using a UV-detector. Complications due to specific interactions between the par-
ticles themselves or between the particles and the wall are eliminated by using a par-
ticular type and amount of emulsifier and working at low ionic strength.
When the apparatus has been calibrated with particles of known size, the PSD of a
sample can be determined from its elution curve. As is the case for AUC, calculating
the mass fractions requires application of Mie scattering theory, but this is not im-
plemented in CHDF equipment currently available on the market. The manufactur-
ers content themselves with a relative conversion based on the extinction coefficients
glass capillary Fig. 3-9 Capillary

hydrodynamic
fractionation (CHDF):
the principle.
inaccessible regions
parabolic
(shown for two
flow field
different particle sizes)
particle
of polystyrene calibration latexes. Typically, CHDF is able to measure particle diam-

eters in the range 10 to 400 nm. By using capillaries with a larger inner diameter, the
range can be extended to include particles about 1 µm in diameter, but the resolution
achievable at the lower end of the particle size range is then reduced. A measure-
ment takes about 10 minutes to complete.
Particle surface
The surface characterization of a polymer particle involves investigating the adsorp-
tion of ions and amphiphilic molecules (emulsifiers, oligomers), determining the
number of covalently bonded functional groups and acquiring information on the
structure of the interfacial layer (swollen state or ‘hairy layers’). Presently this task
can not be solved satisfactorily. The main methods used are titrimetric analyses on
purified dispersions, soap titration and electrokinetics.
Titrimetric methods
Titrimetric analysis of polymer dispersions is mainly used to quantitatively deter-
mine acidic and basic groups covalently bonded to the particle surface (from initia-
tors or comonomers). Before titration the dispersion has to be cleaned thoroughly,
that is all traces of amphiphilic and ionic components have to be removed. The rec-
ommended purification technique employs a combination of anionic and cationic
ion-exchange resin beads [17]. The beads have to be thoroughly purified themselves
before use.
After purification, the dispersion is titrated potentiometrically to determine the
quantity of residual, that is covalently bonded, acid or base groups [17]. When titrat-
ing for acids, the different pKa values enable distinction of sulfuric/sulfonic acid and
carboxylic acid. Fundamental questions that arise in connection with this method
are (1) whether all of the bonded acid groups can be neutralized because of the high
resulting charge density, and (2) to what extent the particle surface reorganizes dur-
ing neutralization. The increasing hydrophilicity might, for instance, cause particle
swelling and a migration of acid groups from the particle interior to the surface.
Soap titration
Soap titration is employed to determine the emulsifier coverage of the polymer
particles in the dispersion. Emulsifier coverage is defined as the percentage of the
particles’ total occupiable surface area that is covered by emulsifier. In soap titration
the surface tension of the dispersion is measured, for example using the Du Nuoy
ring method [4], as a function of the emulsifier added (Fig. 3-10). The emulsifier
molecules distribute themselves between the particle surfaces, the aqueous phase
and the dispersion/air interface where the surface tension is measured. As a rule the
equilibrium lies well over in favor of adsorption on the particle surface, so that if the
surfaces are not fully covered, only a few of the added emulsifier molecules are
found at the dispersion/air interface where, as a consequence, relatively high surface
tension values γ are recorded. As more and more emulsifier is added, γ gradually de-
creases (Fig. 3-10). When the surface of the particles is completely covered, the ex-
cess emulsifiers must be taken up by the aqueous phase, leading eventually to the
formation of micelles. From this point on the aqueous phase can accommodate large
amounts of emulsifier and γ remains essentially constant. The sharp change in the
gradient of the curve shown in Fig. 3-10 determines the critical micelle concentra-
tion (CMC) of the particular emulsifier in the dispersion under test.
The soap titration is usually carried out at a series of solids contents (for example,
2.5, 5, 7.5 and 10 %, w/w) in order to eliminate the amount of emulsifier required for
micelle formation. Plotting the resulting CMC values against the solids content pro-
duces a straight line whose slope is inversely proportional to the emulsifier coverage
α (Maron plot, see [18, 19]). If the size of the particles is known, the effective molec-
ular surface area of the emulsifier occupied on the particle can be calculated. Studies
have shown that the emulsifier molecular surface area is determined not only by the
type of polymer, but also by the way in which comonomers and initiator residues are
incorporated into the particle surface.
air
emulsifier
polymer
particle
model 100% coverage of micelle
dispersion particle surface formation
surface
tension
Fig. 3-10 Soap titra-

tion. Determination of
the emulsifier coverage cmc
of the polymer parti-
cles. log(emulsifier conc.)
The soap titration technique is strictly only applicable for dispersions which con-
tain one type of emulsifier. However, many polymer dispersions are stabilized by a
combination of emulsifiers, often both ionic and non-ionic types. One approach in
such cases is to perform the study with the emulsifier mixture, though there is the
problem of exchange processes occurring on the particle surfaces if one of the emul-
sifiers is preferentially adsorbed. The results may also be affected by adsorbed am-
phiphilic oligomers generated during the emulsion polymerization.
Electrokinetics
Electrokinetic measurements [20] are used to access the electrophoretic mobility
µe of the polymer particles and thereby to get information on their charges. Because
of the relatively small particle size of 100 to 250 nm, the measurement technique
used for polymer dispersions is laser Doppler electrophoresis. Sample preparation
and experimental set-up correspond to those of a dynamic light scattering experi-
ment (Sect. 3.2.2, Fig. 3-6). The only difference is a pair of electrodes immersed in
the sample between which the particles are moved backwards and forwards by an al-
ternating voltage.
The electrophoretic mobility, µe, is related to the zeta potential, ζ, which is defined
as the electric potential at the surface of shear of the particles and is therefore a
measure of their total charge. Unfortunately, the electrophoretic mobility of disper-
sion particles does not depend solely on the zeta potential, but also in a complex way
on particle size and on the ionic strength and viscosity of the aqueous phase [21]. It is
only at the limits of very high and very low ionic strength that ζ can be directly com-
puted from the measured µe values (Helmholtz–Smoluchowski or Hückel approxi-
mations).
These complex dependencies and some experimental difficulties (for example,
due to electro-osmotic convection) are the reason why electrokinetic measurements
are still of only minor importance in the characterization of polymer dispersions. On
the other hand, the technique provides a simple means by which the adsorption of
amphiphilic components (emulsifiers, protective colloids and so forth) on the parti-
cle surfaces can be followed at least qualitatively.
3.2.3
Residual Volatiles
The increased attention paid to ecological and environmental issues in recent years
has lead to a growing significance of residual volatile determination in polymer dis-
persions. Depending upon the production process, polymer dispersions may contain
small quantities of residual monomers, monomer impurities, substances formed by
the decomposition of the initiator or from chemical reactions between the various
components in the reaction mixture. The European Union has defined such sub-
stances as volatiles, if they have a boiling point below 250 °C.
The determination of the residual volatiles is usually performed by capillary col-
umn gas chromatography [22]. Different sampling techniques are described. In the
headspace technique (see ISO 13741-2) a diluted dispersion sample is mixed with an
internal standard and a polymerization inhibitor. The sample is then heated in a

sealed vial (for example at 90 °C for 1 h) and, after equilibration, a small part of the
headspace vapors is introduced into the chromatography column. In the direct liquid
injection method (see ISO 13741-1) a diluted dispersion sample is mixed with an in-
ternal standard and directly injected on to the hot insert liner (temperature
150–200 °C) of the chromatograph causing the dispersion to vaporize instantly. In
both techniques the column (typically coated with a 1 µm thick layer of polydi-
methylsiloxane, PDMS) is initially thermostatted at 50 °C causing the injected
volatiles to condense at the entrance part of the column. The temperature of the col-
umn is then raised linearly to 250 °C and the component substances are fractionated
by the column in the order of their volatility and detected for example by a flame ion-
ization detector (FID). Careful calibration is necessary in order to assign elution time
and signal height to the type and amount of the components. With this technique,
the typical residual volatiles of polymer dispersions can be quantitatively determined
in a range between 10 and approximately 10,000 ppm (measurement duration about
45 minutes).
3.2.4
Aqueous Phase Analysis
In common practice the aqueous phase, or serum, of a polymer dispersion is only in-
vestigated for its pH (Sect. 3.2.1). On the other hand, the aqueous phase contains a
host of substances which play an important role in many applications. These sub-
stances include: (a) emulsifiers, (b) initiator residues, (c) electrolytes from the neu-
tralization process or from initiator decomposition (for example sodium sulfate from
sodium peroxodisulfate), (d) unreacted water-soluble monomers such as acrylic acid
or vinyl sulfonic acid, and (e) water-soluble oligomers formed from this kind of
monomers.
To analyze the aqueous phase for any of these substances, it must first be separat-
ed from the polymer particles. Both flocculation and membrane filtration techniques
can be used for this purpose and they are described in more detail below. The detec-
tion of the substances listed above can then be performed with the usual array of an-
alytical methods used for characterizing aqueous media. For the determination of
emulsifiers, electrolytes and water-soluble monomers, ion chromatography (IC) and
high-performance liquid chromatography (HPLC) are particularly suitable. The tech-
niques of choice for characterizing oligomers are gel permeation chromatography
(GPC) and capillary electrophoresis (CE). As these analytical techniques are not spe-
cific to colloidal chemistry, they will not be described further here and the reader
should consult the literature for more information.
Serum separation techniques
Flocculation techniques
The dispersion is for instance flocculated by the addition of acids or salts (typically
containing polyvalent ions). Examples of salts of this type are aluminum sulfate or
the combination of K4Fe(CN)6 and ZnSO4 (Carrez precipitation). Subjecting the dis-
persion to freeze-thaw cycles also often proves successful. A further possibility is
centrifugation. If the centrifugal forces are high enough, the dispersion flocculates at
the base of the cell allowing the aqueous phase to be subsequently drawn off. In the
case of well-stabilized dispersions, high-performance centrifuges are required. Two
disadvantages of the flocculation methods should be mentioned. First, the flocculat-
ed polymer particles can release considerable amounts of emulsifier into the aque-
ous phase. Secondly, centrifugation may cause components in the aqueous phase to
be flocculated along with the polymer particles.
Membrane filtration techniques

In this case, the polymer particles are separated from the aqueous phase by a
membrane through which the particles cannot permeate. Suitable membranes in-
clude dialysis tubes (molecular weight cut-off: 10 000–15 000 g mol–1) or, for exam-
ple, Nucleopore membranes, which are available with pore diameters from 15 nm to
several micrometers.
In dialysis the dispersion is placed in a well-sealed tube and immersed for several
days in water, which should be changed regularly. Before being analyzed, the
dialysate usually has to be concentrated. Changing the water and concentrating the
dialysate can both be carried out easily if the dialysis tube is placed inside a Soxhlet
apparatus.
In the diafiltration method [23], which uses the Nucleopore membranes, the dis-
persion is filtered under pressure through the membrane. Like the dialysis method,
diafiltration can be used not only to separate the aqueous phase, but also to ‘purify’ a
polymer dispersion, that is to separate all the water-soluble components. When used
for the latter purpose, the dispersion is continuously rinsed with water during the di-
afiltration process. Filter cake formation is prevented by adopting a cross-flow filtra-
tion arrangement in which, for example, a stirrer is used to create a convective cur-
rent parallel to the surface of the membrane.
3.3
Polymer Films
In the typical applications such as paints, adhesives, textiles and non-wovens the dis-
persions or their formulations are subjected to a drying process. The properties of
the dispersion itself are for this reason only of relevance during processing. It is the
properties of the polymer film that are of importance to the end product, and these
properties are essentially determined by the polymer itself. Characterizing the prop-
erties of the polymer films is thus a subject of central relevance to the typical disper-
sion applications.
In the description of methods presented in this chapter, the focus is on pure poly-
mer films. However, these methods are equally applicable to characterizing formu-
lated films such as paints.
3.3.1
Film Formation
In the drying stage at the end of water evaporation the particles adopt a hexagonal
close-packed geometry. Good subsequent film formation requires a high level of
polymer particle deformability and the rapid interdiffusion of polymer chains be-
tween the particles. Emulsion polymers therefore possess a so-called minimum film
formation temperature (MFT), below which no compact film can be formed. The de-
termination of the MFT is discussed below.
Immediately after its formation, the properties of the polymer film are still mainly
determined by the particulate structure of the dispersion. The interstitial regions will
still house the water-soluble components (salts, emulsifiers, oligomers and so forth)
and multiphase particles, for example, will initially give films with micro domains.
The phases formed directly after drying are not in thermodynamic equilibrium with
one another. Changes in these micro domains can occur gradually with time, or more
rapidly if subjected to higher temperatures. An example of such changes is the ten-
dency of the water-soluble components to group together or to migrate to the surface
of the film. In multiphase films, the micro domains can merge to form macro domains.
The quality of a polymer film is therefore influenced not only by the properties of
the constituent polymer, but also by the conditions under which the dispersion is
dried. To achieve reproducible results when characterizing polymer films, it is nec-
essary to control such parameters as wet film thickness, drying temperature, air hu-
midity, air convection currents, and drying and storage times. Rapid drying, in par-
ticular, can cause a skin to form on the surface of dispersion, thus hindering the con-
trolled drying of the dispersion below. If low-volatility substances, such as certain
film-forming agents, are present, thorough drying of the film is essential if the meas-
urement results are to be meaningful.
To create a film with a defined (dry film) thickness of up to about 200 µm, the dis-
persion is usually cast on to the substrate using either a drawdown film applicator or
a roller applicator. Suitable substrates are glass, polyethylene, polyethylene tereph-
thalate or teflon. Films with thicknesses in the millimeter range, such as are used for
mechanical strength testing, can be formed by pouring the dispersion into flexible
polyethylene or silicone rubber trays, which facilitate the removal of the film after
drying.
Minimum film formation temperature (MFFT)

The minimum film formation temperature is determined according to ISO 2115 by
spreading the dispersion at defined layer thickness (for example at 200 µm wet) on a
plate along which a linear temperature gradient is established (for example from 0 to
40 °C). Commercial equipment usually has shallow channels engraved in the plate
which facilitate the spreading of the dispersion. The drying has to be performed in a
controlled atmospheric environment. Once completely dry, the film is visually in-
spected for the presence of cracks and cloudiness. The MFFT is the lowest tempera-
ture at which a homogeneous and crack-free film forms. The MFFT is either dis-
played by built-in temperature sensors or can be determined using a surface temper-
ature probe. The method also enables the so-called white-point temperature to be
determined. This is the temperature below which a cloudy film forms and above
which a clear, transparent film results. The white-point temperature always lies a few
degrees below the MFFT.
As an aqueous dispersion can only dry above 0 °C, the MFFT and white-point tem-
perature are only defined above this value. The control of the polymer layer thickness
is crucial for the measurements. Mechanical stress may develop during film forma-
tion (particularly when crosslinking is involved) which leads to crack formation
above a certain layer thickness. A further point which should be considered is that
very short drying times are often used in dispersion processing, for example on coat-
ing machines. In this case, the MFFT may well lie above the value determined
according to ISO 2115. The discrepancy is caused by kinetic limitations in water
evaporation and polymer interdiffusion [24].
The main factors determining the MFFT of an emulsion polymer are the compo-
sition, molecular weight and crosslinking density of the main copolymer [24]. How-
ever, particle size and the water-soluble substances such as auxiliary monomers or
emulsifiers also play an important role. The effect of these substances is to retard the
rate at which water leaves the interstitial region. As long as the water is present the
mobility of the polymer chains is increased and interdiffusion thus favored. The
MFFT of a dispersion can therefore be lowered by inclusion of auxiliary monomers.
In the case of multiphase polymer particles, the MFFT is strongly dependent upon
morphology. An example of this type of system are the core-shell particles with
copolymers of differing glass temperature discussed below.
3.3.2
Macroscopic Characterization of Polymer Films
Thermal characterization
Thermal characterization of an emulsion polymer essentially means the measure-
ment of the glass transition temperature Tg, that is the temperature above which the
hard, glass-like polymer film becomes viscous or rubber-like. Polymers whose Tg lies
well above room temperature are designated as ‘hard’, those with a Tg much lower
than room temperature as ‘soft’. Normally Tg is measured by differential scanning
calorimetry (DSC [25]). In this technique, the difference between the heat absorbed
per unit time by the polymer film to that absorbed by a thermally inert reference ma-
terial is recorded during a linear temperature ramp. The sample and the reference
are placed on a sensor plate of defined thermal resistance R, and the temperature dif-
ference ∆T between the sample and the reference is then recorded over the tempera-
ture ramp. Usually, the heat flow difference, which is the negative quotient of ∆T and
R, is plotted as a function of temperature (Fig. 3-11).
Figure 3-11 is a schematic representation of a DSC measurement in which a glass
transition and a melting process are shown. A glass transition is not a second-order
transition between two defined equilibrium states. It therefore occurs over a relative-
ly wide temperature range and depends upon the rate of temperature change. For
this reason a number of different definitions of the glass transition temperature can
Fig. 3-11 DSC. Investigation melting process

of glass transitions and melting heat flow
processes in polymer films difference
(β, heating rate; Tg, glass
transition temperature; β∆Hs
∆Cp, heat capacity difference
endothermicity
of the polymer in the tempera-
ture regions below and above glass transition
increasing
Tg; Tonset and Tpeak, different
definitions of the melting
point; ∆Hs, enthalpy of
Tpeak
melting).
β∆Cp Tonset
Tg
temperature
be found in the literature. The Tg shown in Fig. 3-11 is that of the so-called “mid-
point” definition. The ISO 11357-1 standard specifies a heating and cooling rate of
between 0.5 and 20 K min–1 and recommends the repeat heating of the sample (that
is heat/cool/heat). This repeat heating helps to eliminate any influence of the ther-
mal history and the drying process, for example due to the presence of residual wa-
ter. Tg should always be determined during the second heating ramp. The investigat-
ed temperature range, in the case of soft adhesives, should start at –110 °C and, in
the case of hard coatings, should extend to 150 °C.
Melting processes are uncommon in the emulsion polymers described in this
book. Exceptions are the melting and crystallization phenomena observed with eth-
ylene oxide chains when highly ethoxylated emulsifiers or protective colloids are em-
ployed in the polymerization process.
The glass transition temperature of an emulsion polymer is the temperature above
which the polymer chains become mobile and it is therefore directly related to the
minimum film formation temperature MFFT. In contrast to Tg, which is essentially
determined by the main copolymer, the MFFT is influenced by the drying process.
If, for instance, water is able to solubilize part of the copolymer during the coales-
cence of the particles at the end of the drying stage, the MFFT can be lowered signif-
icantly. This phenomenon, which is known as “Tg/MFFT splitting”, is typical of vinyl
acetate emulsion polymers but also observed for other polymer types when large
amounts of hydrophilic monomers are used in the polymerization process.
“Tg/MFFT splitting” is important for all applications in which a hard film with a low
MFFT is required.
Tg values of several important homopolymers are listed in reference [2]. The values
were determined on samples of non-crosslinked emulsion polymers. In crosslinked
polymers, Tg is shifted to higher temperatures as a result of the restricted chain mo-
bility. A number of approximations for calculating the Tg of copolymers have been
proposed in the literature [26]. The Gordon–Taylor equation usually produces reli-
able results:
Tg(1)m 1 + αTg( 2)m 2

Tg = (3-5)
m 1 + αm 2
Here m1 and m2 are the mass fractions of the monomers 1 and 2 and α is defined
as ∆β(2)/∆β(1), with ∆β the difference in the coefficient of expansion of the molten
and glass states of the respective homopolymer. If α is not known, the Fox equation
can be used to provide a simple estimate:
1 m1 m 2
= + (3-6)
Tg Tg(1) Tg( 2)
For statistical copolymers, the width of the glass transition corresponds approxi-
mately to that of the homopolymers. The transition broadens with increasing
inhomogeneity of the monomer distribution within and between the polymer
chains.
Beyond enabling the glass transition temperature to be measured, differential
scanning calorimetry also provides a simple means of investigating polymer com-
patibility and phase separation in polymer films. If a film contains two phases, this
shows up as two glass transition regions in the DSC scan. The relative fraction of the
phases can be determined by the ratio of the measured heat capacities. If, on the oth-
er hand, the constituent polymers are wholly compatible, only one glass transition is
recorded and this lies between those of the individual components. In a similar way,
the compatibility of the polymer to low molecular weight substances such as plasti-
cizers can be examined.
Mechanical characterization
The mechanical characterization of a polymer film is performed on a free film. This
requires drying of the dispersion on a substrate of low surface energy (such as Teflon
or silicone rubber) from which it can be lifted without applying strong mechanical
forces. Great care is required when preparing such free films as defects or deforma-
tions caused by mechanical stress have a detrimental effect on the reproducibility of
the measurements. Mechanical characterization is typically performed by recording
the stress-strain curve up until film rupture takes place (large deformations) or by
dynamic mechanical analysis within the elastic limit (small deformations).
Stress-strain measurements
A stress-strain measurement on a free polymer film is performed as a uniaxial ten-
sile test. The film (typical geometry: 250 µm thick, 30 mm long and 5–10 mm wide)
is loaded into a tensile testing machine and the stress (force per unit area) recorded
as a function of tensile strain (elongation over original length) at a constant drawing
speed (typically 10–100 mm min–1) until the test sample ruptures [27]. Figure 3-12
shows a typical form of a stress-strain diagram measured for a polymer film. At
small levels of deformation, the stress-strain curve is linear and the film behaves
elastically. The gradient of the curve in this region is called the elastic modulus (or
Young’s modulus) of the material under test. Other parameters available from this
test are the tensile strength and the elongation at break. The integral under the curve
Fig. 3-12 Typical stress-strain stress tensile strength

curve for a polymer film.
work of fracture
elongation
at break
strain
to failure represents the energy per unit volume required to rupture the sample
(work of fracture or toughness).
The stress-strain behavior shown in Fig. 3-12 is typical of the elastomeric response
of a polymer film. Curves of this type are found in crosslinked films above the glass
transition and in non-crosslinked films in the so-called entanglement region (see
dynamic mechanical analysis below). Hard, highly crosslinked films below their
glass transition temperature are characterized by their relatively small elongation at
break and their high tensile strength. These materials show essentially elastic be-
havior up until rupture. On the other hand, non-crosslinked films (in the vicinity of
Tg) are elastic at small elongations and start to deform plastically above a critical val-
ue. This phenomenon is known as necking. In this case, the tensile stress passes
through a maximum after which it remains relatively constant over a certain defor-
mation range (before rising again shortly before rupture).
Stress-strain measurements are also a useful tool for studying film formation in
polymer films. Such an investigation, in which the process of polymer chain inter-
diffusion in n-butyl methacrylate films was followed by monitoring the films work of
fracture, has been reported elsewhere [28].
Dynamic mechanical analysis

In dynamic mechanical analysis (DMA [27]) of a polymer film, a sample with the
same dimensions as in the tensile stress-strain analysis described above is slightly
pre-tensioned and then subjected to a low-amplitude and low-frequency sinusoidal
deformation (typically 0.1 % and 1 Hz respectively). As the measurement is per-
formed below the material’s elastic limit, the stress follows the strain in a sinusoidal
manner. The amplitude ratio and the phase difference between the stress and strain
oscillations enables the dynamic elastic modulus E* to be calculated:
E* = E′ + iE″ (3-7)
––––––
where E′ is the so-called storage modulus, E″ the loss modulus and i = √(–1). E′ is a
measure of the (recoverable) energy stored in the film during deformation and E″ is
the (irrecoverable) energy that is dissipated in the film as heat.
In conventional DMA, the storage and loss moduli are recorded as a function of
the oscillation frequency. Of more widespread application are DMA measurements
Fig. 3-13 Dynamic mechanical

analysis. Storage (E′) and loss
(E″) moduli as a function of
temperature for a polymer film
of poly(2-ethylhexyl methacry-
late).
in which E′ and E″ are measured at a constant frequency over a temperature range.

As a result of the time-temperature superposition principle, the temperature scan
provides the same information as the frequency scan. Figure 3-13 shows a typical
DMA measurement (temperature scan) on a non-crosslinked polymer film.
The storage and loss moduli can be seen to vary over several orders of magnitude
across the temperature range. A high storage modulus is measured in the glassy
state. It decreases rapidly in the glass transition region as the film softens. The loss
modulus passes through a maximum at the beginning of the glass transition region.
This maximum can be used as an alternative definition of the glass transition tem-
perature of the sample (compare with Sect. 3.3.2).
After passing through the glass transition region, the moduli decrease more weak-
ly with temperature as a result of polymer chain entanglement and crosslinking
within the film. In the case of non-crosslinked polymers, a further increase in tem-
perature causes the film to undergo plastic flow.
For non-crosslinked polymers, the entanglement region is only observed above a
critical molecular weight (typically between 2000 and 10 000 g mol–1). This molecu-
lar weight corresponds to the polymer chain length above which physical chain en-
tanglement (temporary crosslinking) can occur (entanglement molecular weight).
For crosslinked polymer films, the storage and loss moduli measured above the
glass transition region remain relatively constant or exhibit a slightly positive tem-
perature dependence (crosslinking plateau). E″ assumes significantly lower values
than E′. According to the theory of rubber-elasticity, the storage and loss moduli in
this region have the following values:
E′ = 3ρRT/Mc; E″ = 0 (3-8)
where ρ is the film density, R the gas constant, T the temperature and Mc the average
molecular weight between two crosslinking sites. Equation (3-8) shows that in this
ideal case the storage modulus of a crosslinked film increases linearly with tempera-
ture and provides a direct means of accessing the crosslinking density ν of the poly-
mer (ν = ρ/Mc).
When analyzing multiphase samples, it may be possible to detect several glass

transitions in a DMA measurement as was the case in the thermal characterization
of multiphase polymer films described above. DMA is also able to provide informa-
tion on the effects of plasticizers, resins and fillers on the polymer film.
In the case of soft films which tend to flow it is easier to measure the dynamic
shear modulus G* = G′ + iG″ than the elastic modulus E*.
The advantage is that the film is placed between two plates rather than being
clamped at its ends. G* is measured by exerting a small sinusoidal torsional dis-
placement of one of the plates. The information content of the shear moduli curves
corresponds to that of the elastic moduli ones.
Optical characterization
The transparency, gloss and color of a film are important in many applications. The
complete optical characterization of a polymer film would require measuring the op-
tical response of the film as a function of wavelength, angles of incidence and detec-
tion (relative to the surface normal), film thickness and type of substrate. Despite the
fact that a multitude of optical techniques are available for such measurements (UV-
visible spectroscopy, ellipsometry, laser scattering and so forth), in most applications
simple techniques using white light are employed [29].
Film opacity is usually measured by the transmission of white light through a free
film. The back-scattering power is determined using an integrating sphere photome-
ter, that is diffuse illumination and detection of the scattered light at 0° to the film
surface normal. Measurements of film gloss are performed by recording the intensi-
ty of light reflected at a specified angle to the normal (usually 20, 60 or 85°). In color-
measuring instruments, wavelength-dependent measurements are conducted at
known angles of incidence and detection and the results then converted to color val-
ues. It is important to realize that when investigating films that are not wholly
opaque to the wavelength concerned, the results will be influenced by film thickness
and by the choice of substrate (color, transparency and so forth). For this reason, op-
tical measurements on polymer films are often performed using black foils as sub-
strate (for example pigment blackened PVC).
Behavior with respect to liquids

In a multitude of applications, polymer films get in contact with water or organic
solvents. These liquids can wet, swell, permeate or even dissolve the film. To charac-
terize these processes (with the exception of wetting) simple gravimetric methods
are normally used.
Wetting
If a series of liquids with increasing surface tension γL are brought into contact
with a polymer film, complete wetting will occur below a critical surface tension γC
and partial wetting (that is droplet formation) will be observed above this value (see
Fig. 3-14). The critical surface tension γC is a characteristic of the polymer film and a
measure of its surface energy. Films with a high γC are easy to wet, those with a low
γC value can only be wetted with difficulty.
Fig. 3-14 Determination of

the critical surface energy γC
of polymer films using the
Zisman method (θ is the
contact angle).
Wetting is quantified by measuring the contact angle, which is the angle subtend-
ed by the drop at the point of contact to the film. A contact angle of 0° reflects com-
plete wetting. In contrast, a value of 180° represents complete non-wetting (see
Fig. 3-14). The contact angle is measured either by image analysis (sessile drop
method) or by using a Wilhelmy balance [4, 30].
In the Wilhelmy balance method, the polymer film is suspended vertically from
the balance and then lowered slowly until it is in contact with the liquid. If the sur-
face tension at the liquid-air interface is known, the contact angle can be calculated
from the difference in sample weight when in and out of contact with the liquid.
The Wilhelmy method can also be used to investigate dynamic wetting processes
by recording the formation of the liquid lamella in time or by immersing and with-
drawing the polymer film into and from the liquid at constant rate. Time-dependent
measurements are also useful for examining cases in which liquid is taken up after
the polymer film has been wetted or, conversely, in which the liquid dissolves film
components such as emulsifiers.
In addition to their use in determining the critical surface energy γC, contact angle
measurements can also provide information on the polarity of the film surface. In
this case the measurements are conducted with a series of liquids of different polar-
ity (for example isopropanol-water mixtures). For evaluating the data a number
of procedures have been published (see for example the Good-Girifalco-Fowkes
method [30, 31]).
Swelling, dissolution and permeation

The usual means of characterizing swelling and dissolution processes involves
storing weighed films in the solvent of interest (for example water or tetrahydrofu-
ran). After a defined period of immersion (for example 24 h), the film is removed
from the liquid, liquid adhering to the surface of the film is removed and the sample
is weighed in its wet and dry state.
The percentage increase of the wet film relative to its initial weight prior to im-
mersion is known as the solvent or water uptake. The weight loss of the dried film
compared to the initial sample weight specifies the extraction loss and is due to the
partial dissolution (leaching) of film components in the liquid. Soluble and insoluble
film parts are frequently referred to as the sol and gel fractions. Measurements con-
ducted for different storage periods provide information on the kinetics of the sorp-
tion and dissolution processes. The speed with which the wet film dries may also be
of significance for certain applications. Further parameters of interest are the vol-
ume changes that accompany the swelling and the subsequent drying.
Interparticle crosslinking (that is crosslinking after film formation) reduces the
swelling and dissolution of the polymer film strongly. Quantifying the solvent up-
take and extraction loss is therefore a simple means for characterizing this type of
crosslinking. In a crosslinked film, the mean molecular weight Mc between two
crosslinking sites can be calculated from by the degree of swelling in a particular sol-
vent using the Flory-Huggins equation [32]:
ρVS (Q 5/ 3 − Q / 2)
Mc = (3-9)
0.5 − χ
where Q is the swelling ratio by volume, ρ is the polymer density, VS the molar vol-
ume of the solvent and χ the Flory-Huggins interaction parameter for the polymer-
solvent pair (see also Eq. 3-8).
Sorption and dissolution measurements on polymer films in various solvents are
also the basis for determining the solubility parameters of a polymer [33], which are
a measure of its solvent compatibility. In many applications, what is sought is the
greatest possible compatibility or incompatibility between a polymer film and a par-
ticular solvent. In the case of a crosslinked polymer film, the greater the swelling the
better the compatibility. In the case of a non-crosslinked polymer film, the greatest
level of compatibility is achieved at the maximum solution viscosity.
Many of the methods used for the characterization of the emulsion polymer
macromolecules (see Sect. 3.3.3) require the polymer film to be dissolved in a sol-
vent. Full dissolution is hindered if a gel fraction is present. The gel fraction is the re-
sult not only of covalent crosslinking between polymer chains, but also of the physi-
cal entanglement of the chains in these high-molecular-weight emulsion polymers.
The gel fraction is often higher in polymer films which have been subjected to longer
drying times as the chain segments then have the opportunity for greater interdiffu-
sion.
Swelling – particularly due to the uptake of water – often creates opacity within the
film (whitening) which is undesirable in many applications. This phenomenon is
caused by refractive index inhomogeneities created in the film when water pene-
trates the interstitial regions between the particles. Characterization of film whiten-
ing can be done with conventional techniques as discussed above.
The permeation of a polymer film by a liquid can be investigated by filling the liq-
uid into a container whose base is made of the polymer film under test. The loss of
liquid is then recorded gravimetrically as a function of time. Such measurements are

only reproducible if pore-free films can be produced. Films can be tested for the ab-
sence of pores by examining their gas tightness.
Gas permeation
The permeability of polymer films to vapors can be measured gravimetrically in anal-
ogy to liquid permeability (above), with the difference that the film now acts as the lid
rather than the base of a container partially filled with the liquid forming the vapor.
If, rather than being filled with a liquid, the container is filled with a material which
acts as a strong absorber for a particular gas (for example sodium dihydrogen phos-
phate for water vapor or sodium hydroxide for carbon dioxide), gas permeation into
the container can also be monitored. As an alternative to these gravimetric methods,
conventional gas analytical techniques may be used to examine permeability, for in-
stance by monitoring the pressure drop across the film or by the specific determina-
tion of a gas component that permeates the film. As in the liquid permeation studies,
the film samples examined must be free of pores.
3.3.3
Microscopic Characterization of Polymers
Macromolecules
Most of the methods used for the microscopic characterization of emulsion poly-
mers in terms of their macromolecular composition, molecular weight and
crosslinking require the removal of water. For this reason the investigations are per-
formed on the dry polymer film or on freeze-dried samples. The methods employed
are the standard techniques of polymer characterization [34–36].
Some of the measurements are performed on solutions of the polymer in organic
solvents such as tetrahydrofuran or dimethylformamide. Because of their high mo-
lecular weight and their partial crosslinking, complete dissolution of an emulsion
polymer is often difficult (see Sect. 3.3.2), and the information that can be provided
by these methods is in such cases rather limited.
Chemical composition
The chemical composition of an emulsion polymer sample can for instance be de-
termined by Fourier transform infrared (FTIR) spectroscopy [37]. The measurement
is performed on a polymer film. Quantitative analysis involves comparison of the
spectra obtained with those of standard calibration substances.
An alternative or complementary method is pyrolysis gas chromatography. In this
technique the polymer is rapidly heated causing depolymerization or decomposition
and the products are separated and detected gas chromatographically [34].
Polymer composition can also be determined by 1H and 13C NMR [38] on dilute
samples of the polymer in an organic solvent. NMR analysis also enables end group
analysis and to a limited extent monomer sequence studies (for example in terms of
triad distributions).
In recent years there has been increased interest in using gradient HPLC tech-
niques, such as gradient polymer elution chromatography (GPEC [39]), for deter-
mining the compositional distribution of copolymers. The solubility gradient is cre-
ated by mixing a solvent in which the polymer dissolves well with one in which it
does not dissolve (the so-called non-solvent). The copolymer is dissolved in the good
solvent and then injected into the LC column with the non-solvent as eluent, with the
result that the copolymer precipitates at the entrance of the column. During gradient
elution, the amount of the good solvent in the eluent is gradually raised which leads
to the re-dissolution and fractionation of the copolymer.
Molecular weight
The determination of the molecular weight of the polymer is also carried out in or-
ganic solution. A simple method is to measure the intrinsic viscosity [η] of the solu-
tion [34]. The measurement is normally made using a capillary viscometer and in-
volves recording the solution viscosity as a function of polymer concentration c and
then extrapolating the data to zero concentration (see ISO 1628-1). The dependence
of the intrinsic viscosity and the molecular weight, M, is given by the Mark-Houwink
equation:
 1 η( c ) − η0  α
[η ] = lim   = AM (3-10)
c →0  c
 η0 
where c is the polymer concentration, η0 the solvent viscosity and A and α are quan-
tities which are constant at specified temperature for the solvent-polymer pair. Nor-
mally, the c → 0 extrapolation is too involved for routine measurements. In such cas-
es viscosity is only measured at one particular (low) concentration and used as a rel-
ative measure for the molecular weight of the investigated polymer.
The Mark-Houwink equation (Eq. 3-10) assumes that the polymer in solution is
present in the form of random statistical coils. For a given molecular weight, branch-
ing and crosslinking in the macromolecule lead to a lower viscosity. In doubtful cas-
es, alternative methods of absolute molecular weight characterization (static light
scattering, density gradient analysis in an analytical ultracentrifuge, membrane os-
mometry, end-group analysis, and so forth) should be used for comparison purpos-
es [34–36]. A modern alternative is that of matrix-assisted laser desorption ionization
mass spectrometry (MALDI MS [40]). In this technique the polymers are embedded
in a matrix made of a strong UV absorber which enables the unfragmented ioniza-
tion of the macromolecules by a UV laser pulse. Absolute molecular weight determi-
nation is achieved in this mass spectrometer by time-of-flight measurement.
Because emulsion polymers are prepared by a radical polymerization process, the
molecular weight distribution (MWD) is generally quite broad. MWD is usually char-
acterized by gel permeation chromatography (GPC, also referred to as SEC, size ex-
clusion chromatography). GPC fractionates a polymer solution according to coil size
by passing it through a micro-porous gel with a defined pore size distribution [34]. In
addition to simple UV and refractive index detectors, other techniques such as FTIR
spectrometry and light scattering are now used to characterize the individual frac-
tions as they elute from the column. The latter two detectors enable both the chemi-
cal composition and the molecular weight of the individual polymer fractions to be
accessed directly.
Crosslinking
Internally crosslinked polymer particles (“micro-gels”) can be characterized by com-
paring hydrodynamic volumes and molecular weight. High molecular weights cou-
pled with small hydrodynamic volumes indicate extensive crosslinking. The hydro-
dynamic volume is best accessed by viscosity measurements or dynamic light scat-
tering, while molecular weight can be determined by the density gradient analysis in
an analytical ultracentrifuge or by static light scattering.
Micro-gel fractions are a common feature of emulsion polymers because of intra-
particle crosslinking. On the other hand, interparticle crosslinking, which occurs af-
ter film formation, significantly reduces the solubility of the polymer film. In this lat-
ter case, crosslinking is characterized by performing swelling experiments in organ-
ic solvents.
Film and particle morphology

Polymer particles can be produced in a number of morphologies. Figure 3-15 shows
examples of structures that have been observed.
Fig. 3-15 Morphologies of polymer particles.
The morphology of the film, directly after its formation, will be determined by the
structure of the particles, but a significant restructuring of the phases can occur as a
function of time (leading for example to larger domains). The major technique used
to characterize particle and film morphology is transmission electron microscopy
(TEM), which is described below.
Other techniques are small angle X-ray and neutron scattering (SAXS [41] and
SANS [42]), atomic force microscopy (AFM, [43, 44]) and NMR spin-diffusion and
spin-relaxation techniques [45]. However these methods are not in widespread use
and their ability to characterize the composition, size, shape and superstructure of
the domains is somewhat limited. The reader is referred to the literature for further
details.
Transmission electron microscopy

In transmission electron microscopy [46] the dry sample has to be transferred into
ultrahigh vacuum and is illuminated by a high-energy beam of electrons (for exam-
ple 100 keV). In an ideal case, a lateral resolution of around 1 nm is achievable.
Since sample preparation is rather involved, TEM is not a routine technique. In or-
der to examine individual particles, they have to be placed separately on a suitable
substrate under conditions which prevent film formation (that means high dilution
of the sample and drying below the minimum film formation temperature). For the
TEM inspection of a polymer film a thin section containing only one particle layer is
required (typical thickness <100 nm). The thin-cut can only be done at a temperature
below the glass transition temperature of the polymer. Sometimes it is also possible
to directly deposit a particle monolayer on a substrate by drying the dispersion at the
right dilution.
Transmission electron micrographs directly show the size and shape of the indi-
vidual polymer particles. However, to draw any reliable conclusions on the distribu-
tion of particle size or shape the laborious counting of a large number of particles is
required (>1000!).
A fundamental problem of using electron microscopy to analyze polymer samples
is their low electron density, which causes low contrast in the images. Improved con-
trast can be achieved by staining the polymer with heavy-metal compounds such as
RuO4, OsO4 or uranyl acetate. These compounds are incorporated into the polymer
network directly or via a suitable coupling agent.
Staining agents which exhibit high selectivity for certain polymers also form the
basis of morphology studies. For example, polystyrene and polybutadiene can be se-
lectively stained with RuO4. Acrylates, on the other hand, require treatment with hy-
drazine and OsO4. A core-shell particle with a polystyrene core and an acrylate shell
can thus be characterized by staining the core with RuO4. In the same way a possible
phase restructuring taking place in the film of these particles can be studied.
An alternative to the above preparation methods, albeit a rather involved one, is
the freeze-fracture technique, in which the dispersion is shock frozen by being
poured into liquid nitrogen. The freezing process has to be fast enough to avoid crys-
tallization of the water phase. The sample is then cryo-transferred to the electron mi-
croscope where it is fractured. The fracture surfaces can then be imaged using, for
example, replica techniques.
Acknowledgments
I wish to thank Dr J. Lamprecht, Dr W. Mächtle, Dr A. Zosel, Dr H. Nissler,
Dr R. Baumstark, H.-J. Heiter, and S. Krause for their assistance in the preparation
of the manuscript.
72
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4
Applications in the Paper Industry
Jürgen Schmidt-Thümmes, Elmar Schwarzenbach, and Do Ik Lee
4.1
Introduction
In 1998, the world demand for emulsion polymers (dry) was 7.4 million metric tons
and is forecasted to increase to 8.8 million metric tons in 2003 with an annual
growth rate of 3.6 % [1]. Of this 1998 world demand, about 35 % and 32 % were con-
sumed in North America and Western Europe, respectively, while about 23 % was
for paper and paperboard coatings. If the world-wide uses of emulsion polymers for
both paper and paperboard coatings and paints and coatings are combined, they will
account for about half of the world consumption of emulsion polymers. For this rea-
son, the industry for paper and paperboard coatings is a core market for emulsion
polymers, along with the industry for paints and coatings. The world demand for
emulsion polymers in 1998 is shown by market and region in Fig. 4-1, while Fig. 4-2
shows the demand forecast in 2003 [1].
Other Markets
(18%) Other Regions
Paints & Coatings
(21%) North America
(26%)
Carpet Backing (35%)
(11%) Japan
(12%)
Adhesives Paper & Paperboard

(22%) (23%) Western Europe
(32%)
By market By region
The 1998 World Emulsion Polymer Demand:

7.4 Million Metric Tons
Fig. 4-1 The 1998 world demand for emulsion polymers by market and region.
76 4 Applications in the Paper Industry
Other Markets
(17%) Paints & Coatings Other Regions
(26%) (24%) North America
Carpet Backing (34%)
(10%)
Japan
(11%)
Adhesives Paper & Paperboard
(23%) (24%) Western Europe
(31%)
By market By region
The 2003 World Emulsion Polymer Demand Forecast:

8.8 Million Metric Tons
Fig. 4-2 The 2003 world demand forecast for emulsion polymers by market
and region.
This chapter will cover the applications of emulsion polymers in the paper indus-
try, especially in surface sizing and paper coating. Since information on the break-
down in the uses of emulsion polymers for surface sizing and paper coating is not
readily available in the world markets, it is hoped that information available on the
Western Europe market would provide some perspectives on their relative uses of
emulsion polymers. Table 4-1 shows the amounts of emulsion polymers used for
these applications in Western Europe: 3 % and 97 %, respectively [2].
Tab. 4-1 The Western European market for emulsion polymers in the
paper industry [2].
Market segment Amount of polymer dispersions in metric tons

and percent (1997)
Surface sizing 35 000 ( ~3 %)

Paper coating 1 150 000 (~97 %)
Total 1 185 000
4.2
The Paper Industry
4.2.1
History
The precursors of paper were papyrus and parchment, which were used for writing
as early as 3000 BC in Egypt. In China, strips of bamboo or wood were used for writ-
ing and drawing before the discovery of paper. The invention of paper has been at-
tributed to Ts’ai Lun in AD 105, who produced a uniform writing-material paper
from felted plant fibers [3]. The original paper was made in China from rags, bark
4.2 The Paper Industry 77
fiber, and bamboo. The plants were crushed in mortars and water was added to cre-
ate a homogeneous fiber pulp. By dipping a hand wire screen into the suspension, a
thin layer of the pulp was removed and then dried. Even today, these are still the fun-
damental steps in the papermaking process. The art of papermaking finally reached
Central Asia by AD 751 and Baghdad by 793, and by the 14th century there were
paper mills in several parts of Europe [4]. Later, it landed in the New Continent.
With the invention of the printing press by J. Gutenberg in the middle of the
fifteenth century, paper assumed a previously unimagined importance and there
was a massive increase in the demand for paper. As a result of further discoveries,
increasing levels of trade and for other reasons, the level of paper consumption con-
tinued to rise. Numerous raw materials were used for paper manufacture and there
were rapid developments in industrial papermaking with the first papermaking ma-
chine being built in 1799. Nicholas-Louis Robert constructed the first papermaking
machine. Using a moving screen belt, paper was made one sheet at a time by dip-
ping a frame or mold with a screen bottom into a vat of pulp. A few years later, the
brothers Henry and Sealy Fourdrinier improved Robert’s machine, and in 1809 John
Dickinson invented the first cylinder machine [4].
4.2.2
The Paper Industry Today
In 1998, the world production of paper and paperboard excluding newsprint and tis-
sue totaled approximately 240 million metric tons and is expected to grow to approx-
imately 290 million metric tons in 2003 with an annual growth rate of 4 % [1].
The main raw material used to make paper is wood. Both softwoods (long fiber)
and quick-growing hardwoods (short fiber) are processed.
The intermediate stage between the raw materials and the finished paper is so-
called half stuff (pulp). Typically, this is:
– Cellulose from which lignin, resins, and incrustations have been removed by the
refining process to leave high-grade cellulose fiber that is particularly well suited to
paper manufacture.
– Mechanical pulp, which is produced from wood that has been ground or refined
by mechanical means. This type of pulp is less well suited for paper manufacture,
as the incrustations are still present to a large extent and the properties of the pulp
are determined by fiber bunches and fragments inevitably present.
– Paper made of pure cellulose is designated as “wood-free” paper, whereas that
made from mechanical wood is called “wood-containing” paper.
In an effort to protect wood resources, large amounts of recycled papers are also
used in today’s papermaking industry. Modern technology combined with appropri-
ate process chemicals enables this secondary raw material to be used not only for pa-
perboard, but also for high-quality paper.
The proportion of the chemical additives used as fillers in both paper and coatings
is about 3 %, a surprisingly small amount compared to the other constituents such
as recycled paper, cellulose, and pigments. Of this 3 %, synthetic additives comprise
only about one third so that overall synthetic additives make up only about 1 % of the
Chemical additives
Chemical pulp
43% Synthetic
1.0% chemical
additives
0.5% Alum
3%
8%
Starch
1.5%
35%
11%
Waste paper
Mechanical pulp
Pigment/Filler
Fig. 4-3The proportion of chemical additives relative to the total global

raw material demand of the paper industry in 1996.
total content (Fig. 4-3). The two most important groups of the synthetic additives are
the synthetic binders (50 %) and the sizing agents (25 %), as shown in Fig. 4-4. While
synthetic binders are composed of emulsion polymers, sizing agents can be
monomeric or polymeric. In the latter case, they are in the form of polymer disper-
sions.
Additives relevant to paper Additives relevant to

properties manufacturing process
(Functional chemicals) (Process chemicals)
Synthetic binders 1% Biocides
(Paper 50%
Defoamers,
coating) 1% deaerators
1% Dispersants,
cleaners
8%
Retention drainage
3% 5% aids, curing agents,
6% flocculants,etc.
Sizing agents 25% 8%

Wet strength resins
Bleaching chemicals
Dyes, OBA
Fig. 4-4 Process chemicals used in the papermaking.
The pulp is prepared for the paper machine in an upstream unit. In this unit, the
wood is ground, washed, and sorted, and then fiber concentration and consistency
are adjusted to the desired levels.
The paper machine itself is a single continuous production line with a length that
today may exceed 200 m and comprises the following main sections: headbox, wire
section, pressing section, drying section, and finishing section.
4.3 Surface Sizing 79
In the headbox, the pulp suspension is spread across the entire width of the web
and passed onto the wire mesh at the correct speed. The sheet is formed as the water
drains from the mesh and the fibers are fixed into their final orientation while still in
the wet mat stage. In the pressing section, water is driven out of the wet mat by ap-
plying pressure to the web. The web enters the pressing section with a dry content of
about 20 % which increases to 40–50 % as the web leaves this section of the machine.
On passing through the drying section, the web is dried to a final moisture content
that is in equilibrium with the ambient air. The drying section is often equipped with
additional devices which improve the surface properties of the paper or board. Ex-
amples of such devices are the size press, the machine calendering cylinder, various
types of calenders, and coating equipment. The paper or board web is wound onto rolls
in the finishing section which also contains roll handling and wrapping equipment.
The size of today’s paper production lines is enormous. The state-of-the-art paper-
making and finishing machines are up to 10 m wide in web widths and up to
2000 m min–1 (120 km h–1) in production speeds. A wide range of production and
finishing processes guarantees that even the most demanding quality requirements
can be met.
The largest part of the papers produced today is for printing, also known as graph-
ic arts, i.e. for printing paper and board. The requirements that these materials must
meet include:
– high degree of uniformity and smoothness
– good optical properties of which brightness and gloss are the most important
– high opacity and high strength
In short, the physical characteristics of the paper or board must ensure both good
processability and good printability.
To meet these demands, the following two processing stages are incorporated into
the drying section of the papermaking line:
– surface sizing
– paper coating
The use of emulsion polymers in the paper industry is essentially restricted to
these two processes which are described in more detail in the following sections.
4.3
Surface Sizing
Surface sizing means a pigment-free application of hydrophobicizing substances,

the surface sizing agents, in combination with starch. The application will be on-line
to the paper machine by either a size press or a film press. In relation to the paper
mass usually 3 to 5 % (w/w) of starch and 0.1 to 0.25 % (w/w) of sizing agents, each
calculated as solid, will be applied. So in a size press formulation starch clearly dom-
inates with more than 95 % of the solids content. Starch enhances the strength of the
paper, the surface sizing agent hydrophobicizes the paper sheet, thereby reducing
the absorbency of the paper. Thus, the penetration and spreading of print colors are
controlled and the loss of strength in the wet state is reduced.
An alternative to surface sizing is internal sizing, the addition of a sizing agent to

the wet end before the formation of the paper sheet. In this process step, however,
exclusively low molecular weight sizing agents like rosin acids or alkyl ketene dimers
(AKD) are applied.
For surface sizing, mostly polymeric sizing agents are used. The most important
product classes are acrylic copolymer dispersions stabilized by protective colloids.
The particles of the sizing agent consist of a hydrophobic polymer core and a hy-
drophilic shell formed out of the protective colloid (Fig. 4-5).
+ Charged hydrophilic
+ +
+
protective colloid
+
+
+
+
+
Hydrophobic core
+
+
+
+ +
+
Charged hydrophilic
protective colloid
70 - 200 nm
Fig. 4-5 Structure of a polymer-based sizing agent.
The composition of the polymeric core influences hydrophobicity, glass transition

temperature, viscous flow, and binding strength of the polymer. The hydrophilic
shell is highly swollen in water and normally carries either an anionic or cationic
charge. It renders stability to the dispersions during storage and against the high
shear stress during application. It also plays an important role in the interaction be-
tween starch and sizing agent. The hydrophobic effect of surface sizing stems from
the formation of a stable coherent film at the paper surface providing a halftone-like
screen (raster) formed from well defined hydrophobic barriers and areas of hy-
drophilic character (Fig. 4-6). Polymer particles sitting at the interphase between
starch film and fiber surface support the fixation of the starch film to the fiber. Poly-
mer particles in the interior improve the wet strength and delay the dissolution of
starch and the flow of aqueous media within the starch layer. Polymer particles at the
surface reduce the wettability of the surface. Only dispersions stabilized by protective
colloids are able to form such a coherent hydrophilic/hydrophobic raster. The pro-
tective colloid tightly fixed to the polymer core acts as a compatibilizer between
starch and hydrophobic polymer core, preventing a rupture of the film during drying
and shrinking of the starch.
Starch
Polymer protective colloid
Polymer core
Hydrophilic Hydrophobic
Fiber
Fig. 4-6 Formation of a starch-polymer film.
The hydrophilic/hydrophobic balance of the surface can be individually controlled

by:
– the ratio between starch and hydrophobic polymer
– properties of the starch-like film formation, swelling, and water uptake
– hydrophobicity, average particle size, and viscous flow of the polymer particles
Also, in special paper applications like photocopy and ink jet papers, the addition
of polymer dispersions to surface sizing formulations can lead to positive effects.
The interaction between hydrophobic toner and polymer particle enhances the toner
adhesion in case of photocopy papers. This proves to be very helpful in cases where
the process conditions in the copier are insufficient to guarantee complete melting
of the toner on the paper surface.
Applied to ink jet papers, a hydrophilic/hydrophobic raster on the paper surface
results in a highly accurate fixation of the dye right to the spot at the paper surface.
Whereas the hydrophilic areas allow a fast dewatering of the printing ink, mostly to
the interior of the paper sheet, the hydrophobic points prevent a spreading parallel to
the paper surface. Additional modification of the starch/polymer film by cationic
groups results in an additional fixation of the anionic dyes by ionic interaction.
Thereby, color density and outline sharpness can be further improved.
4.4
Paper Coating
Paper coating is the most important surface finishing process for paper in terms of
both the amount of paper that is coated and the quantity of emulsion polymers con-
sumed in the coating process. The method involves coating the surface of the paper
with a water-based pigmented coating color. The emulsion polymer used in the coat-
ing color formulation binds the individual pigment particles together and helps the
entire pigment layer to adhere to the surface of the paper. Furthermore, emulsion
polymers are also added to improve the processability and/or runnability of the coat-
ing color. Coating is typically applied onto paper and board for printing or packaging
applications. Other specialty kinds of paper that undergo coating are labels, wallpa-
per, and non-printed silicone papers which act as the backing sheets for self-adhesive
labels.
Coating paper or board increases the homogeneity of the surface and considerably
improves its optical characteristics such as gloss, smoothness, brightness, and opac-
ity. The properties of the pulp severely limit the surface homogeneity achievable with
uncoated papers. The surface of an uncoated paper will contain fibers which are ap-
proximately 1–3 mm (1000–3000 µm) long and approximately 10 µm thick. If this pa-
per is printed by the halftone process using a 50 lines/cm screen, the dots (200 µm)
are smaller than the dimensions of the fiber. The fibers are thus the limiting factor
dictating image definition. In contrast, the pigments used in the coating color can be
easily ground to a particle size of less than 1 µm. While the surface of an uncoated
paper comprises numerous individual fibers of varying degrees of hardness, the
surface of a coated paper is, by contrast, uniform and homogeneous in structure.
Figures 4-7 and 4-8 demonstrate clearly the differences in the quality of offset and
rotogravure printing on coated and uncoated paper surfaces, respectively.
Uncoated grade,
supercalendered
Coated grade,
supercalendered
Fig. 4-7 Effect of coated paper on offset printing.
For the reasons given above, coated paper exhibits more uniform ink receptivity
and better holdout than uncoated papers. Coating also produces a much smoother
paper surface that is particularly a significant factor when printing individual dots,
especially when using a rotogravure process (Fig. 4-9).
Low basis-weight papers require a high degree of opacity if show-through (i.e.,
when the printing on one side of the paper can be seen from the other side) is to be
prevented. The opacity of an uncoated paper is determined by the cellulose fibers
and any fillers it contains. While fillers are naturally better than cellulose in increas-
ing opacity, they are unable to provide the opacity levels attainable by coating. The
crucial factor determining opacity is the volume of the coating, since this determines
Coated
gravure
paper
Uncoated
gravure
paper
Fig. 4-8 Effect of coated paper on rotogravure printing.
typical dotsize
critical area for

missing dots
Fig. 4-9 Result of printing paper of insufficient smoothness by the

rotogravure printing process.
the area of the pigment–air interface (within the coating layer) at which the scatter-
ing of incident light occurs.
Gloss is a critical property when assessing the quality of printing. Calendering is

only able to improve the gloss of an uncoated paper surface to a limited extent. The
gloss of a coated paper surface can be varied over a wide range, either by purely me-
chanical means (calendering), by the coating process itself, or by controlled addition
of gloss-imparting pigments. In this way, a full range of coated papers from high-
gloss to semi-gloss to matte are easily obtained.
The degree of brightness can be controlled by selecting appropriate pigments, but
can also be adjusted by the use of optical brighteners or toning dyes or both. The
brightness of a coated paper also depends strongly on that of the base paper. If the
base paper is of low brightness (e.g., unbleached), opacifying pigments such as tita-
nium dioxide (TiO2) and special techniques such as double or triple coating are used.
4.4.1
Coating Techniques
A number of different coating machines exist for applying the coating color onto the
base paper. Figures 4-10a–c illustrate the common coating methods, along with the
range of coating weights that can be achieved, the required level of solid content, and
the viscosity of the coating colors.
Stiff blades are more commonly used in North America, while bent blades are
more widely used in Europe.
It is apparent that the various coating methods place different demands on the
rheological properties of the coating color. These requirements must be taken into
account when formulating a coating color for a particular application.
The major components of a coating color are:
– inorganic pigments to cover the surface of the base paper
– co-binder and thickener for controlling the processing properties
– binder (water-soluble or disperse systems or a combination of the two)
Fig. 4-10 Coating equipment. (A) Stiff blade, bent blade, and roll blade;
(B) Air-knife; (C) Pre-metered size press.
Quantitatively, pigments are the principal constituent of any coating color, binders
being used in relatively small amounts. For every 100 parts pigment, there are typi-
cally about 5–20 parts binder and 0.1–3 parts of other additives. Coating color com-
positions common in both North America and Europe for sheet-fed offset and ro-
togravure printing processes are listed in Tab. 4-2.
The quantities given here always refer to the amount of active ingredient required.
A more detailed description of the constituents of a coating color is presented in
Sects 4.4.2–4.4.4.
Once coated, the paper is smoothed as part of the calendering process. Calender-
ing involves subjecting the paper surfaces to high temperatures and pressures in or-
Tab. 4-2 Typical coating color compositions for sheet-fed offset and rotogravure printing process-
es in both North America and Europe.
Sheet-fed offset Rotogravure
North American formulation North American formulation

75 parts fine kaolin clay 85 parts delaminated clay
25 parts fine ground calcium carbonate 15 parts talc
12 parts emulsion polymer 5 parts emulsion polymer
3 parts starch 2 parts starch
0.5 parts calcium stearate 0.5 parts calcium stearate
European formulation European formulation

80 parts fine ground calcium carbonate 50 parts talc
20 parts fine kaolin clay (high gloss clay) 50 parts kaolin clay (coarse or high aspect ratio)
12 parts emulsion polymer 5 parts rotogravure sole binder
0.5 parts co-binder 0.75 parts calcium stearate
0.5 parts curing agent
0.5 parts optical brightener
der to create a smooth, glossy surface. A distinction is made between soft-nip calen-
dered and supercalendered papers. In the soft-nip calender process, the number of
nips is kept low, and higher temperatures and lower pressures are used, compared to
the supercalender process. The advantages of the soft-nip calendering are that it can
be performed “on-line”, i.e., immediately after the coating process and that the bulk
of the paper does not decrease as much as in supercalendering. By varying tempera-
ture and pressure in a controlled manner, a very broad range of gloss levels can be
achieved. In the supercalender, the number of nips used to smooth the paper is
greater, with typically twelve rolls in a supercalender stack. The smoothest and
glossiest paper surfaces are achieved by supercalendering.
4.4.2
Pigments used in Coating Colors
The main constituents of a coating color formulation are the inorganic pigments,
which serve to cover the surface of the base paper and thus to improve its optical
properties.
Coating pigments must therefore satisfy the following requirements:
– high purity
– high brightness and opacity
– high refractive index
– good dispersibility and desirable rheological properties
– amount of binder required should be low
The most important pigments are:
– kaolin clay (often referred to simply as china clay)
– calcium carbonate, natural or precipitated
– titanium dioxide
Nearly in all cases, not one but a combination of several pigments is used in coat-
ing color formulations. Kaolin clay and calcium carbonate are the most commonly
used pigments. There are a great number of different types in each of the two pig-
ment groups: the calcium carbonate grades being distinguished mainly by particle
size, while the plate-like kaolin clays are classified according to their so-called aspect
ratio (ratio of surface diameter to thickness) and particle size.
In the recent years, the use of ground calcium carbonate pigments in North Amer-
ica has been steadily increased so that the differences in coating color formulations
between North America and Europe are being narrowed.
The pigments used in the preparation of coating colors are prepared as slurries.
These are aqueous dispersions which by using dispersing agents such as tetrasodi-
um pyrophosphate or sodium polyacrylate can have a solid pigment content of
greater than 70 %.
The different pigments require different amounts of binder in order to ensure ad-
equate adhesion of the coating to the surface of the paper and sufficient binding be-
tween the pigment particles. For this reason, it is important to keep the specified
binder-to-pigment ratios when formulating coating colors. The following table
(Tab. 4-3) lists the amount of binder required by various pigments to achieve a given
level of binding strength (pick strength) for sheet-fed offset printing paper.
Tab. 4-3 Amount of binder in coating colors as a function

of pigment type.
Pigment Binder demand (%)
Paper Board
Kaolin clay 12 14
Ground calcium carbonate 11 12
Precipitated calcium carbonate 15 18
Titanium dioxide 14 16
More binder is needed when coating board to ensure good glueability in folded
cardboard boxes.
4.4.3
Co-binders and Thickeners used in Coating Colors
Pumping, transfer, re-circulation, and, most particularly, the actual coating method
require certain rheological properties of the coating colors. Low-shear and high-
shear viscosities (shear rates of 10 to >106 s–1) and water retention values are highly
important parameters. For example, in roll coating applications, the thixotropic be-
havior of the coating color is particularly important, whereas Newtonian or struc-
turally viscous (i.e. pseudoplastic or shear-thinning) flow at high shear rates is im-
portant for all blade coating techniques. Coating colors are characterized by their vis-
cosity, solid content, immobilization point, and water retention capacity.
To adjust these properties to the required level, co-binders and thickeners are
added to coating color formulations. If possible, these additives should be chosen to
have a positive influence on the gloss, smoothness, printability, brightness, binding
strength, and glueability of the paper, and they should certainly not have a detrimen-
tal effect on any of these properties. Typical amounts are 0.1–3 parts of co-binder or
thickener to 100 parts pigment and approximately 12 parts binder. In addition to the
emulsion polymers described in greater detail below, other substances are used as
co-binders and thickeners. These include natural products such as starch and syn-
thetic water-soluble polymers such as polyvinyl alcohol and carboxymethylcellulose.
The chemical composition and the behaviors of co-binders and thickeners with re-
spect to pH are shown in Fig. 4-11.
Dispersion Solution
pH < 7 pH > 7
Hydrophobic Anionic charges

polymer chains - COOH - COO repel each other,
Alkali
in form of polymer chains
small balls stretch and
(dispersion particles) - COOH - COO dissolve
Alkali
MAIN MONOMERS
CH2=CH-COOH Acrylic acid
CH2=C(CH3)-COOH Methacrylic acid
CH2=CH-COO-R Acrylic acid esters
CH2=CH-CN Acrylonitrile
CH2=CH-O-CO-CH3 Vinyl acetate
Fig. 4-11 Chemical structure of synthetic co-binders.
In contrast to the emulsion polymers used as binders, those employed as co-

binders and thickeners contain large fractions of hydrophilic (typically carboxyl-rich)
monomers. This high degree of hydrophilicity means that the particulate nature of
the dispersion is lost when the acidic dispersion (pH < 7) is added to the alkaline en-
vironment of the coating color formulation (pH > 7). The resulting structures, which
range from massively swollen polymer networks to polymer chains dissolved in the
aqueous phase, influence the rheology of the coating color in a complex manner and
are still not fully understood.
Apart from the increase in the viscosity of the aqueous phase due to the dissolved
polymer molecules, which are present as stiff chains at the pH of the coating color
formulation, polymer bridges also form between the pigment particles (Fig. 4-12).
These structures, which are strongly dependent on the state of shear in the coating
color, result in a rise in its low-shear viscosity. If, in addition, one succeeds in incor-
porating hydrophobic side chains into the polymer, the resulting associative interac-
tion between the dissolved chains enables the low-shear viscosity to be increased still
further.
A Dispersion
+ Alkali (pH>7)
Solution
Carboxylate Functional Additional

groups with groups with hydrophobic
anionic charges high polarity side chains
Anionic Adsorption Associative

charges repel on pigment interactions
each other surfaces between polymers
Extended Polymer bridges Additional

polymer chains between network structures
in the aqueous phase pigment particles (micelles)
Viscosity High viscosity at Very high

in the viscosity at
low shear
aqueous phase low shear
Latex particles Extended polymer chains
Bridges between pigments Associative thickening
Fig. 4-12 Thickening mechanisms with ening behaviors of various acrylate copolymers;
various types of alkali-soluble co-binders and (B) Various thickening mechanisms of syn-
thickeners. (A) Alkali solubilization and thick- thetic co-binders and thickeners.
All effects induced by the co-binder and thickener in the coating color are very
strongly dependent on the shape, charge distribution, and size of the pigments used
as well as on the solid content of the formulation. Choosing the right thickener or co-
binder for a coating color which is to be formulated for use in a particular type of
coating machine is a complex task that requires good product knowledge and a con-
siderable degree of practical experience.
4.4.4
Binders used in Coating Colors
Both natural and synthetic binders are used in the paper coating. Binders from natu-
ral sources are used in the form of aqueous solutions and include:
– starch
– soy protein
– cellulose derivatives such as carboxymethylcellulose (CMC).
Synthetic binders, which are prepared as aqueous polymer dispersions, are:
– styrene and butadiene
– styrene and butyl acrylate
– poly(vinyl acetate)
– acrylates
– vinyl ester and acrylic ester
– ethylene and vinyl ester
These synthetic binders commonly known as latexes are mostly modified with
functional monomers such as vinyl acids, amides, acrylonitrile, etc. to improve the
colloidal and rheological properties of coating color formulations and the printing
and/or packaging properties of coated papers and paperboards.
As a water-soluble substance, polyvinyl alcohol represents a special case among
synthetic binders.
When the coating of paper began more than one hundred years ago, animal glues
and gelatin were used as binders. Partly because of their high price, these materials
are no longer used today except in a few specialty applications (e.g., gelatin in the
manufacture of photopaper). The natural products of more lasting significance were
starch (from potatoes, corn, and rice) and casein (from milk). Both are binders
which, like the synthetic sole binders, combine the characteristics of binder and co-
binder. However, unlike the synthetic products, starch and casein cannot be added
directly to the pigments, but must first be pre-processed. Table 4-4 presents a gener-
al comparison of natural and synthetic binders.
The most important natural binder still in use today is starch, though it is now fre-
quently used in combination with synthetic binders. Corn starch is more common in
the USA, whereas potato starch is more prevalent in Europe. Native starch contain-
ing two fractions of amylose (linear chain) and amylopectin (branched chain) is not
suitable for coating paper and board because the amylose fraction tends to undergo
retrogradation and the viscosity of coating colors made with native starch is too
high [5]. For these reasons, only treated (i.e., depolymerized) or chemically modified
starches are used. Most paper mills carry out their own starch preparations in-house.
Tab. 4-4 Comparison of natural binders including polyvinyl alcohol with synthetic binders.
Natural binders and Synthetic binders

polyvinyl alcohol
Sold as Solid (powder) Dispersion

Quality consistency Good to poor Very good
Dissolution/digestion needed Yes No
Concentration in aqueous form Maximum 10–20 % 50 %
Viscosity in aqueous form High Low
Film properties Very hard and brittle Variable, ranging from soft
to hard, thermoplastic, elastic
Tendency to foam Casein yes; starch no Yes
Bacterial decay Yes No
Water retention High Practically none
Binding strength (pick strength) Medium high High-very high
Water resistance Poor Very good
The properties of the starch depend on how it is treated or modified. The best results
are achieved by ethylation. However, the most economical method of modification is
enzymatic degradation to prepare enzyme-converted starches. Also, oxidized starch-
es are widely used in North America. Table 4-5 compares the advantages and disad-
vantages of using starch as a binder.
Tab. 4-5 Evaluation of starch as a binder.
Advantages Disadvantages
Low-price binder Low binding strength compared to synthetic binders

Improves runnability, particularly Highly soluble in water, low wet-pick strength
well-suited for roll coating (thixotropic Not compatible with satin white
coating colors can be prepared) Risk of non-uniform printing in an offset printing
Coating colors with a high solid content Variable quality of commercial products
can be prepared Liable to rot
In addition to starch, another natural binder still used in North America is soy pro-
tein. It is mainly used for recycled board coatings.
Emulsion polymers were first used successfully as coating color binders in the
nineteen forties. The advantages and disadvantages of these synthetic binders are
summarized in Tab. 4-6.
The binder in a coating color formulation must be capable not only of binding the
pigment particles together, but also of securing them at the coating surface and of
anchoring them to the base paper. The pigment particles at the coating surface must
be held sufficiently tightly so that the coated paper can be smoothed in calendering
and subsequently printed. The mechanical stress experienced by the surface of the
paper depends very much on the printing process used and on the tack of the chosen
Tab. 4-6 Advantages and disadvantages of emulsion polymers as binders.
Binder properties can be optimized High transportation costs (50 % water)

to meet requirements of printing process
Does not affect coating color viscosity, Freeze-sensitive

high levels of solid content possible
Water resistance of coating is higher than No acceptor sites for optical brighteners
that achieved with natural binders
Better gloss and smoothness attainable
Simple to use:
– no digestion needed
– feed can be controlled via a flow meter
printing ink. The amount of binder added to the coating color formulation must
therefore be chosen appropriately. Special papers are an exception to this rule be-
cause in these materials the binder not only determines the paper’s printability, but also
performs other functions such as controlling its oil- or water-resistance. Table 4-7
provides a rough guide to the amounts of binder required for the various types of
printing process.
Tab. 4-7 The dependence of binder quantity on printing process.
Printing process Amount of binder per 100 parts of pigment
Letterpress printing 8–15 parts

Sheet-fed offset process 10–20 parts
Web offset process 10–18 parts
Flexographic printing 10–18 parts
Rotogravure process 4–10 parts
The amount of binder in coating colors used to coat board that is to be printed
by rotogravure, flexography, or the sheet-fed offset process is usually somewhat
greater than in coating color formulations for paper. More binder is needed for
coated board in order to meet such additional requirements as folding strength and
glueability.
Using too much binder not only increases the price of a coating color unnecessar-
ily, but also can be detrimental to quality. Large amounts of binder can cause the
porosity of the coating to decrease so much that the printing ink does not transfer
properly to the surface or, in extreme cases, is repelled by the surface. Drying times
increase considerably as a result, causing set-off in the stack (i.e., the transfer of wet
ink from a newly printed sheet to the reverse side of the following sheet).
The binder accounts for approximately 15 to 40 % of the total cost of a coating col-
or, depending on the printing process used.
In addition to the amount of binder used, which is a dominant factor determining

the binding strength, the type of binder is also of crucial significance in determining
the properties that influence the appearance and classification of paper and board.
These important properties are:
– pick resistance (dry pick strength, IGT method, Pruefbau)
– water resistance or wet pick resistance (wet pick strength, IGT method, Pruefbau)
– gloss (specular reflection intensity)
– brightness (reflection of visible light λ = 475 nm)
– opacity (hiding opposite to transparency)
– smoothness (Parker Surface Roughness Test, etc.)
– porosity
– compressibility (rotogravure)
– stiffness (more important for light-weight papers)
– drying/setting of printing inks
– mottling (uneven uptake of ink)
– water absorption capacity (the capacity of the paper to absorb water, thus permit-
ting the transfer of inks to moist surfaces)
– ink absorption capacity (the capacity of the paper to absorb ink and to prevent ink
being transferred from the freshly printed areas to the rubber blanket of the fol-
lowing printing station)
– blistering in web offset process (blister-free printing)
– glueability of board and packaging paper
In Sect. 4.4.5, the most important methods of testing coated papers will be de-
scribed.
The extent to which a coated paper needs to fulfil the various requirements listed
above depends on the printing process to be used. The most exacting requirements
on binder strength must be met by paper grades to be printed by the sheet-fed offset
process. Because an aqueous fountain solution is used in the offset process, the wet
pick strength (i.e. the binding strength of the moist paper) is crucially important. As
the sheet-fed offset process is principally used to create high-quality prints, the de-
mands made on optical parameters (brightness, gloss) and on printability (ink ab-
sorption, absence of mottling) are particularly stringent.
As the printing inks used in a web offset press have less tack than those used in
the sheet-fed offset process, the requirements on the binding strength for paper
printed by the web offset process are not so high. However, the paper must exhibit
high resistance to blistering. Once printed, the paper in a web offset press passes
through a drier in order that the printing ink solvents and any residual water within
the base paper can evaporate. If the porosity of the coating is too low, the water vapor
can become trapped causing blistering and detachment of the coating layer.
The rotogravure process uses inks with a very low viscosity. It therefore has the
lowest requirements in terms of the pick strength of the paper. To guarantee the
even and error-free transfer of the printing inks (i.e. low number of missing dots)
from the rotogravure cells to the paper, requires paper which is both smooth and
compressible.
When choosing or developing a suitable binder for one of the various printing
processes, one generally focuses on those four parameters whose effect on binder
properties is sufficiently well known. These are:
– nature of the constituent monomers
– glass transition temperature
– particle size and particle size distribution
– molecular structure of polymers
As mentioned at the beginning of this section, the binders used in coating color
formulations are based on combinations of different monomers. The most common
combinations are styrene with butadiene or acrylic esters and vinyl acetate combined
with ethylene or acrylic esters. An important difference between styrene-butadiene
binders and styrene-acrylic ester binders is the tendency of the binder to yellow under
the influence of UV radiation or heat. Products containing a butadiene-based binder
are considerably more susceptible to yellowing due to the much greater fraction of
double bonds in the polymer. Acrylic ester copolymers are significantly less prone to
thermal or UV-induced yellowing (as shown clearly in Figs 4-13 and 4-14) and these
are the copolymers of choice for the production of high-quality, long-life prints.
Generally speaking, binders based on polyvinyl acetate or on styrene-acrylate pro-
duce a more porous coating than do binders based on a butadiene copolymer.
The glass transition temperature of a polymer is determined by the amounts of its
different monomer constituents. Paper used in offset printing contains binders
whose glass transition temperature lies between 0 °C and 30 °C. The high smooth-
ness and compressibility required for paper grades used in the rotogravure printing
process are achieved by using binders with a much lower glass transition tempera-
ture (<0 °C). Figure 4-15 shows the typical dependence of dry and wet pick strength,
stiffness, gloss, porosity, and evenness of offset printing on the glass transition tem-
perature.
Fig. 4-13 Thermal yellowing as a function of the chemical composition of

the binder.
Brightness Loss
14
After 8 hours of UV exposure
12
10
0
Base paper Chemical Basis Chemical Basis Chemical Basis
Styrene/Acrylate Styrene/Butadiene/Acrylate Styrene/Butadiene
Fig. 4-14 UV-induced yellowing as a function of the chemical composition

of the binder.
- wet pick
- paper gloss
- porosity
Goal Goal
Fig. 4-15 Dependence - dry pick

of paper properties on - print gloss
- printability
the glass transition
temperature of the
binder. Glass transition temperature (Tg)
Particle size and particle size distribution are influenced by the choice and
amounts of emulsifiers and protective colloids that a polymer dispersion contains.
These components are added to stabilize the dispersion thus making it both process-
able (i.e., enabling it to be conveyed, metered, filtered, etc.) and storable. Variations
in the emulsion polymerization process also have a major effect on the size and size
distribution of the polymer particles. Typically, binders used in the paper coating
process have particle sizes of between 100 and 300nm. Figures 4-16 and 4-17 demon-
strate that both the viscosity of the coating color and the wet pick strength of the
coated paper are strongly dependent on particle size.
In contrast to the other possible monomer components, butadiene possesses two
double bonds both of which can act as polymerization sites. Binders based on a
styrene-butadiene combination therefore have a more cross-linked and branched
polymer structure. The extent of cross-linking affects the dry and wet pick strength,
the print gloss and the degree of blistering, which is a highly significant parameter in
Viscosity, mPas
1200
1000
800
600
400
200
0
50 100 150 200 250 300 350
Particle size (D), nm

Fig. 4-16 Dependence of the viscosity of binder dispersions on particle size.
Wet pick strength
100
50
Wet pick strength of paper
and board coatings improves
with decreasing particle size
0
100 150 200 250
Particle size (D), nm
Fig. 4-17 Dependence of the wet pick strength of binder dispersions
on particle size.
web offset printing. Unfortunately, binding strength and blister resistance tend to
oppose one another and cannot therefore be optimized by the choice of binders
alone (Fig. 4-18).
A very similar dependence is observed with the styrene-acrylate binders (Fig. 4-19).
In this case, binding strength and blister resistance show a mutually opposed de-
pendence on the relative molecular weight of the polymers.
The polymer structure, and thus the desired balance between binding strength
and blister resistance, can be controlled in the two classes of binders by careful
adjustment of the polymerization conditions and by the addition of a so-called chain
transfer agent. Additional information on paper coating can also be found else-
where [6–14].
Blister resistance Pick strength
Pick strength
Blister
resistance
Low % Gel content High

Fig. 4-18 Relationship between blister resistance and binding strength
for styrene-butadiene binders.
Blister resistance Dry pick strength
Fig. 4-19 Relationship

between blister
resistance and binding
strength for styrene-
acrylate binders. Molecular weight of Styrene/Acrylate copolymers
4.4.5
Test Methods
In this section, the most important methods of testing coated papers will be de-
scribed. The printability and the final print quality can often be successfully predict-
ed on the basis of these relatively simple tests.
Coating strength tests

The strength required for a paper surface is to a large part determined by the tack of
the ink used in the printing process. Whether or not the paper is dampened prior to
printing is also of considerable importance, particularly in the offset process. The fol-
lowing tests simulate the stresses experienced by the paper surface during the print-
ing process, in particular ink splitting during the offset process (Fig. 4-20).
Fig. 4-20. Ink splitting

in offset printing.
blanket
printing ink
ink splitting
paper or board
Cylinder
Wet pick test

This is a test to determine the water resistance of a coated paper. After wetting the
test strip at constant speed and uniform pressure to create a precisely defined mois-
ture content, the strip is printed with the testing ink while moving at constant or
increasing speed through the press.
Using a hole template to define ten separate measuring dots (representing
precisely defined strip speeds), the color density of each of the ten dots is measured
using a densitometer and then expressed relative to the full tone of the printed sur-
face. When plotted as a function of printing speed, the color density values are a
measure of the water resistance of the paper strip.
When the paper strip is printed at constant speed, the measuring dots used to
determine color density are chosen randomly.
Dry pick test

This test determines the tensile strength of the coating strip when subjected to ink
splitting during the printing process:
The test strip is printed at a precisely defined plate pressure while being accelerat-
ed through the printing zone. The location of the first picking point and the position
at which picking is visible right across the test strip are determined by inspection and
analyzed quantitatively with the aid of a computer program.
However, since in practice, the paper passes through not one but several printing
presses (4–8 in the offset process), a further test can be performed to examine the
effects of this sequential stressing of the paper surface. This is the so-called offset
test.
Offset test
This test simulates repeated ink splitting caused by contact between the printed area
and the rubber blanket during the printing process.
Ink is transferred to the test strip from a plate at an exactly specified plate pressure
and a constant known printing speed. The printed region is subsequently reprinted
five times at 10-s intervals using the same plate but without re-inking. The number
of passes at which the first signs of picking become apparent is recorded. In North
America, Paper-Ink Stability Test (P&I Test) is widely used [15]. The test measures
the rate of ink setting by calculating the slope of the ink splitting force as a function
of the number of impressions taken at a given time interval. Also, this test measures
the number of passes-to-fail. In general, the faster the rate of ink setting, the lower
the number of passes-to-fail. Therefore, for press runnability, the rate of ink setting
and the number of passes-to-fail must be balanced.
Printability tests
Mottle test
This test determines the evenness of the printing.
Ink is transferred to the test strip from an inked plate at an exactly specified plate
pressure and a defined constant speed, and subsequently split three times by an off-
set rubber blanket-covered cylinder. If the coating on the paper is unevenly distrib-
uted, the printed image may appear cloudy as a result. The inhomogeneity of the
printed image is either ranked visually or with a mottle tester (which measures fluc-
tuations in color density).
Measurement of ink gloss

A test strip is printed using a precisely defined plate pressure and constant printing
speed. Once the test strip is dried, the ink gloss is measured using a gloss meter.
Ink set-off test

This test measures the speed at which the oils in the printing ink penetrate the coat-
ing of the paper during the drying (setting) process: A test strip is printed from an
inked plate applied at a precisely defined pressure and a constant printing speed. A
blank counter strip is pressed against the original strip once every 15 s during the du-
ration of the test (900 s). The counter strip will pick up some of the non-dried print-
ing ink from the original strip. The color density of any ink transferred to the count-
er strip is measured using a densitometer. The Paper-Ink Stability Test mentioned
as an offset test can provide information on ink set-off in terms of the ink setting
rate [15].
Rotogravure test
This test determines the suitability of paper or board for printing by the rotogravure
printing process: To perform this test, a gravure cylinder and blade must be added to
a standard IGT tester. The gravure cylinder is inked and the excess ink removed
from the non-printing areas by the blade. Printing is carried out at a constant speed
and a defined force exerted by the impression cylinder. Each test strip is examined to
determine the length at which 20 missing dots have occurred. This particular test
method is known as Helio test.
4.5
Concluding Remarks
Science and technology in the fields of paper surface sizing and paper coating have
been significantly advanced over the past two decades and will be continued to move
forward to meet the needs in the paper industry. There are many challenges
confronting the paper industry. Some of the challenges are conservation of raw
materials, especially trees as fiber source, by improving the current basis weight
vs. stiffness relationship as well as by using recycled and secondary fibers more
effectively, environmentally friendly papermaking, coating, and finishing processes,
better quality coated paper and paperboard products at lower costs, etc. These
challenges will require us to continuously innovate in papermaking, coating, and
finishing. It will be interesting to see how well the paper industry can succeed in the
21st century.
Acknowledgments
One of the co-authors (DIL) would like to thank his two other co-authors (JS-T and
ES) for letting him contribute to this chapter. This chapter has been based on
an English translation of the Paper Industry portion of Chapter 5 Anwendung in der
Papier- and Graphischen Industrie, by Jürgen Schmidt-Thümmes, Elmar Schwar-
zenbach, and Berhard Prantl in Polymerdispersionen, Dieter Distler (ed.), Wiley-VCH,
1998.
101
References
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(ed.), John Wiley and Sons, 1980, graph Series, 1975, 37, 22–63.
pp. 1–38. 12 T. F. Walsh, L. A. Gaspar, Tappi Mono-
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p. 126. Monograph Series, 1975, 37, 120–136.
5 R. L. Kearney, H. W. Maurer (ed.), Starch 14 R. C. Jezerec, G. P. Cogan, Tappi
and Starch Products in Paper Coating, Monograph Series, 1975, 37, 64–69.
Tappi Press, 1990. 15 N. P. Sandreuter, Tappi Coating Confer-
6 L. Göttsching, Papier in unserer Welt, ence Proc., 211, 1994.
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7 T. W. R Dean, The Essential Guide to
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5
Applications for Printing Inks
Barna Szabo
5.1
Introduction
The major printing processes used worldwide are: lithographic, gravure, flexograph-
ic, screen, letterpress and digital. Flexography is the only printing process that con-
sumes significant quantities of water based (aqueous) ink. Less than 23 000 tons per
year of water based ink are used for gravure printing in the US and less than
14 000 tons in Japan; water based gravure volumes are negligible in Europe and Latin
America. Solvent based ink is used mostly for printing gravure, although it is readily
adaptable to aqueous ink. Oil- and solvent-based ink systems are used in the litho-
graphic and letterpress processes. Lithography is the largest volume printing
process. Letterpress is one of the smallest. Both water and solvent based inks are used
in screen and digital printing; these consume comparatively small volumes of ink.
In the United States, approximately two-thirds of flexographic ink is water based;
one-third is solvent based in an estimated flexographic ink market of 200 000 tons.
The major volume of water based flexo ink consumed in the United States is for
printing corrugated containers. The total US ink market for all six printing process-
es listed above is estimated at over 1.1 million tons for year 2000 or approximately
4.5 billion $US.
In Europe, approximately two-fifths of flexographic ink is water based; three-
fifths is solvent based in an estimated flexographic ink market of 180 000 tons. The
total European ink market for all six printing processes is estimated at over 0.9 mil-
lion tons for year 2000 or approximately 4.4 billion $US.
In Latin America less than one-third of flexographic ink is water; greater than two-
thirds solvent based in an estimated flexographic ink market of 34 000 tons. The total
Latin American ink market for all printing processes is over 125 000 tons for year
2000 or approximately 750 million $US.
The flexo ink market in Japan is very small. Approximately one-half of flexograph-
ic ink consumed is water based; one-half solvent in an estimated flexographic ink
market of 27 000 tons. The total Japanese ink market for all six printing processes is
over 400 000 tons for year 2000 or approximately 1.5 billion $US.
104 5 Applications for Printing Inks
The aqueous ink market in 2000 is summarized in Tab. 5-1.
Tab. 5-1 The aqueous ink market in 2000.
Flexo ink Solvent-based Total flexo ink Total printing ink

Water-based × 103 tons, estimated × 103 tons, estimated
Water and solvent
US 2/3 1/3 200 1100

Europe 2/5 3/5 180 910
Latin America <1/3 >2/3 34 125
Japan 1/2 1/2 27 400
Emulsion polymers are used in flexographic and gravure ink for printing flexible
packages, paperboard cartons, corrugated boxes, multi-wall bags, newspapers, and
other flexible substrates (films) and paper products. Styrene acrylic based emulsion
polymers are most commonly used in printing ink applications. Cost is a key factor
in ink raw material suitability for most ink systems. The level of styrene monomer
used in ink grade emulsion polymers is maximized due to film hardness require-
ments of paper and paperboard materials and its low price.
Prior to the mid 1970s, rosin fumarates (i.e. sodium and amine rosin salts) were
the main resins used in aqueous ink. Aqueous rosin based resin solutions provide
the performance properties similar to use of rosin phenolic and rosin maleic pen-
taerythritol esters in a lithographic printing ink. Rosin based resins have been used
in printing ink since the early days of letterpress printing. They are low cost, give in-
herently good pigment dispersion properties, and are easily modified to vary viscosi-
ty and hardness. When aqueous flexo and gravure printing began displacing solvent
based systems, a wider range in properties than possible with rosin became impor-
tant.
Emulsion polymers provide a wide range in properties and low viscosity. Flexo and
gravure inks are referred to as fluid inks because of their low viscosity. Molecular
weight, Tg (glass transition temperature), and particle size distribution are key prop-
erties that are varied to meet specific ink requirements.
Pigment dispersion stability, room temperature film formation, and ink re-solu-
bility are important properties to consider in the design of emulsion polymers for
printing ink. A “support” resin (Sect. 5.2.2) is used in most ink grade emulsions to
maintain these properties. The “support” resin is a low to medium molecular weight
styrene acrylic or other water soluble resin. It comprises up to 60 % solids content of
the emulsion and replaces up to 90 % of surfactant stabilizers.
5.1.1
Flexographic Ink
A flexo ink is a low viscosity (fluid ink) suitable for transfer from an ink fountain via
anilox roll to the plate cylinder and substrate. It dries by evaporation of the solvent
(water). Most presses are equipped with air circulating dryers. A flexo ink is com-
prised of low boiling point solvents for low temperature evaporation and fast drying.
Fig. 5-1 Flexographic press [1].
The composition and solvency is limited to prevent swelling of rubber or photopoly-

mer-based rolls. Water, alcohols, minimal concentrations of acetates (i.e. ethyl,
isopropyl alcohol), and minor levels of aliphatics such as heptane are mostly used.
Acetates and aliphatics are used to solubilize polyurethane and polyamide resins
used in solvent based laminating ink. Only aqueous ink is discussed in this chapter.
A diagram of a flexographic press is given in Fig. 5-1.
A flexographic printing press consists of:
– An ink fountain roll (rubber). The fountain roll rotates in a reservoir of ink and
transfers a large volume of ink to the anilox roll.
– An Anilox ink metering roll (chrome plated or ceramic coated). The anilox is
engraved with cells (of inverted pyramid shapes) varying in density (size) between
80 to 1000 cells per linear inch (2.5 cm). The anilox supplies a precise volume of
ink to the raised surface (print image) of the printing plate. A reverse angle doctor
blade is used to wipe excess ink.
– A printing plate cylinder (steel). A photopolymer printing plate is attached to the
plate cylinder. The printing plate’s raised surface replicating the image contacts
the substrate to transfer ink.
– An impression cylinder (smooth and polished chrome). A smooth polished chrome
cylinder that holds the substrate in contact with the printing plate.
5.1.2
Gravure Ink
A gravure ink is a low viscosity (fluid ink) with rheological characteristics suitable for
transfer “out of” small cells of an engraved cylinder to the substrate. A gravure ink is
comprised of low boiling point solvents for low temperature evaporation and fast
drying. Gravure utilizes various environmentally compliant solvents as required by
specific printing applications. Only water based ink is discussed in this chapter. A
diagram of a gravure press is given in Fig. 5-2.
Fig. 5-2 Gravure press [2].
A gravure printing press consists of:

– A gravure print cylinder (chrome). The gravure cylinder is engraved with cells of
varying sizes replicating the print image. The cylinder rotates through the ink
fountain. Ink fills the cells. An excess is wiped by a doctor blade. Ink is transferred
directly from cylinder to substrate.
– An impression cylinder. The impression cylinder is a rubber coated cylinder that
keeps the substrate in contact with the print cylinder. Its function is to control ink
transfer. The ink is drawn out of the cells of the print cylinder by means of im-
pression pressure and capillary action. An ESA (electrostatic assist) mechanism is
sometimes used to assist in the capillary action. Ink rheology, electron charge and
surface energy are key variables that effect transfer.
5.2
Ink Composition
An aqueous flexo or gravure printing ink is composed of polymer, pigment, solvent,

wax, surfactant, crosslinker, and additives. The polymer (resin) functions as the
“vehicle” for carrying the pigment. It is also a key component for achieving printing
performance properties. The polymer is the material or compound for dispersing a

pigment and preventing its re-agglomeration. It provides adhesion to the substrate.
The branched network of the polymer provides hold-out on porous substrates. The
smooth surface provides gloss for desirable visual effects. Oxidized or crosslinked
polymer structures provide resistance to “chemicals” that contact printed packages.
It provides resistance to scuffing or rubbing. It provides resistance to environmental
conditions such as: heat and temperature, freeze–thaw, ozone, light, oxidation, mois-
ture, etc. The polymer provides viscosity and rheology characteristics necessary for
transfer of ink from press to substrate.
The pigment provides the color. Organic pigments are used in most cases for
lightfastness and transparency. Colorfastness and lightfastness is important to main-
tain desirable visual effects of printed materials. An average consumer would not
purchase a food item (i.e. box of cereal) with faded or shifted colors. This effect
would convey a message about its lack of freshness. Water (solvent) is used to solu-
bilize the resin or polymer. Water is used mainly in flexo and gravure printing
processes. Other solvents such as ethyl-isopropyl alcohol, ethyl-isopropyl acetate,
toluene, and heptane are also used in flexo and gravure ink, but only aqueous flexo
and gravure inks are discussed in this chapter.
Illustrated in Tab. 5-2 is a generic formulation for an aqueous flexographic or
gravure ink. A printing ink formula is frequently modified to meet exact color repro-
duction specifications and/or a customer’s changing performance requirement.
Tab. 5-2 Generic aqueous flexo or gravure ink formulation.
Aqueous flexographic ink Amount Gravure ink Amount

Component (%, w/w) Component (%, w/w)
Pigment dispersion (Sect. 5.2.1) 35–50

Dispersion varnish 55–70
Organic pigment 30–45
Total 100
Emulsion vehicle (Sect. 5.2.2) 25–35
Solution vehicle (Sect. 5.2.3) 10–20
Amine neutralizer 0.5–1.5
Wax emulsion compound 2–5
Wax powder 0–2
Surfactant 1–1.5
Crosslinking additive 0–2
Silica additive 2–5
Corrosion inhibitor 0–1
Defoamer 0–1
Other additives 0.25–0.5
Total 100
Most commercially manufactured printing inks are made from intermediates

such as: pigment dispersion (Sect. 5.2.1), emulsion vehicle (Sect. 5.2.2), solution ve-
hicle(Sect. 5.2.3), and wax emulsion compound (Sect. 5.2.4). Using intermediates
minimizes the number of raw materials handled at the ink manufacturing or blend-
ing site. It facilitates the production of ink in blending plants with minimal equip-
ment and at locations close to the customer and/or printer. Producing ink from in-
termediates offers flexibility in modifying formulas to meet color reproduction spec-
ifications and changing customer application requirements.
5.2.1
Pigment Dispersion
The pigment dispersion is made from dry pigment (which is surface treated) dis-
persed in an aqueous polymer solution. High speed mixers are used to disperse a
pigment from a dried form or an aqueous slurry. The most common polymers used
to disperse pigments are: low to mid-molecular weight styrene acrylics, SMA
(styrene maleic anhydride), or rosin fumarate ester resins. The degree of stabiliza-
tion of a pigment dispersion (which relates directly to color strength development),
ink viscosity stability, transparency and pH drift are controlled by use of polymers
such as those containing salt groups and hydroxyl functionality. Table 5-3 illustrates
the physical properties of polymers used for dispersing pigments.
Tab. 5-3 Solution polymers used for pigment dispersions.
Softening Glass transition Mw (g mol–1) Acid number

point (°C) temp., Tg (°C) (mg KOH g–1)
Styrene acrylic I 140–170 70–125 12000– 18000 210–240

Styrene acrylic II NA 15– 20 30000– 35000 65– 70
SMA ester NA 45–110 50000–150000 165–285
Rosin fumarate ester 125–145 80– 90 2000– 10000 115–200
The stabilization of organic pigment dispersions is achieved by use of polymeric

anionic surfactants that provide strong adsorption on the polar surface of the pig-
ment and hydroxyl groups for interaction with the aqueous phase. Non-polar inter-
mediate sections of a polymeric anion add adsorbed layer thickness [3].
A typical organic pigment particle size ranges between 0.02 to 100 µm (aggregate
size). The particle size distribution of particles in a pigment dispersion are typically
0.5 to 1.5 µm. Most emulsion polymers used in printing ink vary between 20 nm to
200 nm. Because of a pigments relatively large particle size and its wide range in par-
ticle size distribution, the smaller emulsion polymer particles are not suitable for
forming stable dispersions of organic pigment particles and agglomerates. They do
not have sufficient mobility to wet the surface area.
Pigments used in aqueous flexo and gravure ink are supplied as a presscake, in dry
form, or as chips. A presscake is a high solids dispersion of pigment in water. A
presscake is dried by various drying processes to yield pigment agglomerates in a
large range of particle sizes, between 0.02 to 100 µm. Chips are a dry form of dis-
persed pigment particles in a polymer.
Most pigments used in pigment dispersions for printing ink are surface treated
with a resin or polymer compatible with the pigment surface chemistry. The poly-
mer is added as a dissolved aqueous solution during the “pigment striking” step. It
adheres to the pigment surface via physical and/or chemical attraction. Surface treat-
ed pigments are known as “resinated” pigments. A pigment is surface treated or
“resinated” as part of the pigment manufacturing process. A resinated pigment min-
imizes agglomeration, contributes to increased color value and improves the effi-
ciency of the dispersion process. An explanation about the type of resins and poly-
mers used for surface treatment of pigment is a separate segment of ink-pigment
technology that is not covered in this chapter.
It is important that resins or polymers used in the surface treatment of pigment,
are compatible and do not react with the resins and polymers used in the pigment
dispersion. Furthermore, they must be compatible with the emulsion and solution
vehicles of the ink. Incompatibility between these components may cause: pigment
re-agglomeration (resulting in a loss of color strength), increased low shear viscosity
(known as “thixotropy”) leading to a change in ink rheology, and poor printability
(e.g. variable ink transfer) performance.
In addition there are various hybrid resins in use to disperse a pigment. They are
used to achieve specific ink application properties not obtainable by the convention-
al resins and polymers discussed above. For example, a glycerol ester of fumarated
rosin is further esterified with a styrene-allyl alcohol as taught in Westvaco Chemical
Corporation’s patent – Rosin-Based Grind Resins for Aqueous Printing Ink. This
type of resin has high softening point and gives relatively stable low viscosity ink [4].
A fumarated rosin polyamine condensation resin is explained in a second Westvaco
patent – Modified Rosin Resins for Waterbased Inks. The condensation reaction
product of polyamines with certain rosin-based polycarboxylic acids results in an ef-
ficient pigment dispersion resin and gives a stable viscosity over a wide range in pH,
between 8.5 to 10.5 [5]. These resins and others not discussed provide alternatives for
dispersing pigments.
5.2.2
Emulsion Vehicle
The emulsion vehicle provides the “workhorse” performance characteristics of an

ink (i.e. adhesion, gloss, low viscosity, printability, re-solubility in water, heat, and
chemical resistance at low cost). Most printing ink emulsion vehicles are polymer
dispersions composed of styrene acrylics, terpolymers of styrene-α-methylstyrene
and other acrylate monomers (i.e., ethyl acrylate, methyl methacrylate, butyl acrylate,
2-ethylhexyl acrylate, methacrylic acid, acrylic acid, 2 hydroxyethyl acrylate, amino
acrylate). Higher levels of styrene give higher Tg. Higher levels of butyl and 2-ethyl-
hexyl acrylate give lower Tg, thus more flexible polymers. Compared to other poly-
mers (i.e. polyurethanes) styrene acrylics do not give good alkali resistance, chemical
resistance, or adhesion to films and lamination ink (cohesive) bond strength.
Emulsion vehicles are prepared by emulsion polymerization in water in the pres-
ence of surfactant stabilizers. Viscosity is not dependent on molecular weight but
only on solids content and particle size distribution. As a result, high molecular
weights (>200 000 g mol–1) are achievable at low viscosity. Emulsions with small par-
ticle sizes impart properties similar to solution resins with advantages of: low viscos-
ity, near Newtonian rheology, pH stability, low polarity, and insolubility after drying
for immediate water resistance.
Most printing ink emulsions are “resin supported”. Printing ink emulsion poly-
mers contain a “support” resin to reduce MFFT (minimum film forming tempera-
ture), and insure film coalescence. A “support resin” also decreases the need for sur-
factants. A support resin provides ink re-wettability, improves compatibility with pig-
ment dispersions, and improves ink transfer and printability. Support resins are typ-
ically styrene acrylic polymers with acid functionality that are amine neutralized.
A rosin fumarate ester can be used as a “support” resin for ink grade emulsions.
According to Westvaco’s US Patent 5 216 064 [6], a fumarated rosin ester offers ad-
vantages such: as improved gloss, absence of residual glycol used in processing a
styrene acrylic, and higher resin solids. A higher solids emulsion gives faster drying.
Rosin based support resins are lower cost. Westvaco’s US Patent 5 656 679 teaches
that a rosin fumarate reacted with an alkanolamine containing at least one secondary
amine and one hydroxyl group is used as a support resin for ink grade emulsions for
providing improved adhesion to films [7].
Polyurethanes are known to give excellent chemical and product resistance prop-
erties but increase cost. A water soluble polyurethane is made by adding acid modi-
fied monomer to the polymer backbone, the polymer is neutralized with amine, then
used as a support resin in ink grade styrene acrylic emulsions. Polyurethane sup-
ported styrene acrylic emulsion polymers may be used to balance the high cost of
polyurethanes and provide improved chemical resistance [8].
Emulsion polymers are supplied in bulk quantities at solids levels between 45
and 60 %. They are produced by emulsion polymer manufacturers such as: SC
Johnson Polymer, Rohm & Haas, Avecia, Air Products, Westvaco, B.F. Goodrich and
others.
Outlined in Tab. 5-4 are: applications, emulsion characteristics, and physical prop-
erties of the styrene acrylic emulsion vehicles used in flexo and gravure ink. An
emulsion vehicle comprises 25 to 35 % of the total ink formula. The table is sorted by
increasing Tg.
For printing inks that require specific properties not obtainable by conventional
styrene acrylic emulsions, an aqueous dispersion of an acid functional polyurethane-
epoxy acrylate hybrid (self crosslinking for improved chemical resistance) [9] patent-
ed by Air Products and Chemicals, Inc. or a self crosslinking styrene acrylic emul-
sion which reacts upon evaporation of water [10] patented by Akzo Nobel Resins BV,
may be used. The Air Products novel dispersion contains a quaternary ammonium
polyurethane acrylic hybrid carboxylate salt and pendant acrylate epoxide that self-
crosslink upon evaporation of water and ammonia. Akzo’s novel polymer contains a
diacetone acrylamide reactive monomer and a bishydrazide. The crosslinking reac-
tion between ketone groups and a bishydrazide proceeds rapidly at room tempera-
ture, after evaporation of water from the ink.
Tab. 5-4 Typical styrene acrylic emulsion vehicles used in flexo and gravure
printing inks sorted by increasing Tg.
Application P.S. S.C. pH Viscosity Mw A.N. Tg MFFT

(nm) (%) (mPa s) (g mol–1) (mg KOH g–1) (°C) (°C)
Surface print 65– 75 47–49 8.2–8.4 700– 900 >200000 35– 50 –30 to 1 < 7
Pre-print corrugated 120–140 20–25 7.9–8.3 2500–6000 70000–100000 120–130 10– 35 <24
Direct print corrugated 160–180 25–40 6.0–7.9 45–2500 ~100000 125– 50 30– 35 <24
Cup, plate, multi-wall bag, gift wrap 40– 50 45–50 8.5–9.5 150– 500 >200000 40– 55 40– 48 >45
Folding carton 55– 65 45–50 7.9–8.5 150– 500 >200000 40– 55 95–105 >60
Flexo news 180–220 48–52 8.2–8.7 150– 500 >200000 40– 55 95–105 >60
P.S., number average particle size distribution in nanometer; S.C., solids content; A.N., acid number; MFFT, minimum film forming temperature
5.2 Ink Composition
111
5.2.3
Solution Vehicle
Solution vehicles consist of water soluble polymers not manufactured by emulsion

polymerization. The solution vehicle is an alkali soluble polymer in aqueous solution
or a blend of polymers with combined properties into a single waterborne varnish.
Soluble polymers are made by free radical polymerization in a processing solvent or
as addition or condensation products with heat reaching temperatures up to 265 °C.
Solution vehicles are mixtures of soluble resins unlike emulsion polymers. A solu-
tion vehicle is used to increase adhesion to film and improve ink printability or trans-
fer to meet specific performance requirements. The solution vehicle provides pig-
ment dispersion stabilization, transparency, low film forming temperature, gloss
and re-solubility. An alkali soluble resin is a carboxylic acid functional polymer neu-
tralized (solubilized) with ammonia, amine or sodium hydroxide. The acid numbers
are generally above 100. Ammonia or volatile amines are used in most aqueous inks
except for news print inks. After evaporation of the amine, the resin becomes insolu-
ble and resistant to water spray or other water contact. The ink is re-solubilized with
alkaline water for the clean-up cycle. For news print ink, the polymers are solubilized
with sodium hydroxide to maintain re-solubility (open time) of the ink on the press.
News print ink pressman prefer unlimited open time and fewer clean-up cycles. Wa-
ter resistance is not required since ink penetrates the news print paper fibers.
The key solution polymers (resins) used in printing ink are styrene or rosin based.
Styrene-α-methylstyrene monomer and acid functional co-monomers (i.e. acrylic or
methacrylic acid) comprise the bulk of styrene acrylic solution vehicles used in print-
ing ink. Rosin acid reacted with fumaric acid gives a tri-functional “adduct”. The
“adduct” is partially esterified with polyols such as pentaerythritol, glycerin, diethyl-
ene glycol, etc. to achieve a range of acidity, viscosity, Tg and molecular weight.
The viscosity of aqueous polymer solutions is strongly dependant on molecular
weight. High performance characteristics such as rub resistance and heat resistance
are compromised since low ink viscosity is required for flexo and gravure fluid ink
printing. The volatile amines used to neutralize acid functionality results in pH
shifts, unstable viscosity, reduced pigment dispersion stability, and poor alkali re-
sistance.
Water soluble styrene acrylics are processed via free radical polymerization in gly-
col ether solvents. The solvent is stripped by conventional or proprietary processes.
Rosin based resins are processed molten at high temperatures up to 265 °C. These
materials are flaked or pelletized and packaged in bags or bulk storage for further
conversion.
There are various hybrid polymers and co-polymers in use to achieve specific ink
application properties not obtainable by conventional resins and polymers. Water
soluble fatty acid epoxy esters provide improved heat resistance. For example, an
aqueous fatty acid-acrylic acid epoxy ester patented by Reichold Chemical, which
crosslinks via heat and auto-oxidation is used to provide water and heat resist-
ance [11].
Typical solution polymers are listed in Tab. 5-5.
Tab. 5-5 Typical solution polymers.
Resin/Polymer Softening Tg Mw Acid

point (°C) (°C) (g mol–1) number
Surface print Styrene acrylic resin 145 73 4500– 7500 108–213

Folding carton
Direct print corrugated
Pre-print corrugated
Alternative folding carton Rosin fumarate
Direct print corrugated ester resin 125–145 80–90 2000–10000 115–200
Pre-print corrugated
Multi-wall bags and
gift wrap
Milk carton Fatty acid (Castor oil)/ >125 >100 30000–40000 50–60
Cup and plate acrylic epoxy ester
Towel and tissue Styrene acrylic 75–100 6000–10000 200–230
Water and amine
neutralizer
5.2.4
Waterborne Wax Emulsions and Powders
Both natural and synthetic waxes are used in ink. Waxes provide increased block,
rub, scuff and/or water resistance. Waterborne wax emulsions are produced in a
range of particle sizes between 35 to 175 nm (number average particle size distribu-
tion) by Michelman, Shamrock Wax, and others. Polyethylene and Fischer-Tropsch
emulsions improve the rub and scuff resistance of an ink. Carnauba paraffin and
polypropylene emulsions are used to prevent blocking and improve water resistance
of an ink.
Certain waxes are micro-pulverized to yield particle sizes smaller than a dispersed
pigment particle. A micro-pulverized wax is “stirred” into ink as a powder. Recycled
PTFE (Teflon) is supplied in small particle powder form.
5.2.5
Ink Additives
An amine neutralizer is added to solubilize resins containing carboxylic acid func-

tionality. The amine reacts with the resin carboxylic acid to form a water soluble salt.
Volatile amines such as dimethylaminoethanol (DMAE), morpholine or ammonia
are used to insure that a printed product becomes water resistant upon drying or
evaporation of the amine. The type of amine used is selected based on press speed,
pH requirement and evaporation rate and press drying capacity. Sodium hydroxide
is commonly used in news print ink to maintain re-solubility (“open time”) of the ink
on the press.
A crosslinking compound is added to provide covalent branching to a polymer for
enhanced printed film tensile strength and chemical resistance characteristics. Com-
pounds such as zinc ammonium complexes or zinc oxide react with available car-
boxylic acid functionality. Self crosslinking emulsion polymers may be used as ex-
plained in Sect. 5.2.2.
A surfactant is added to reduce the surface tension to give increased ink spreading
and substrate wetting particularly when printing untreated or partially treated films.
The surface tension of water is approximately 72 dynes cm–1 whereas a polyethylene
film is approximately 30–40 dynes cm–1 after surface treatment. Surfactants increase
the foaming tendency of an ink. Therefore levels of surfactant and defoamer are
carefully balanced.
A defoamer is added to reduce foaming. A fine particle size silica powder is added
to increase the viscosity and modify print film slip or abrasion properties.
A corrosion inhibitor is added to prevent corrosion of press parts made of steel.
5.3
Physical Properties and Test Methods
Viscosity, pH and color strength are the main properties that relate to press per-
formance and print quality. Viscosity is critical for satisfactory ink transfer or print-
ability. A gravure ink has slightly lower viscosity than a flexo ink. The pH is con-
trolled since it effects viscosity, viscosity stability and compatibility with other com-
ponents. The viscosity changes with change in pH, but is readily adjusted by adding
amine or water.
Color accuracy (ink color strength) is important for achieving satisfactory print col-
or and to maximize profitability. The color strength of a pigment dispersion inter-
mediate is carefully controlled to narrow tolerances. Therefore, color adjustments in
the ink manufacturing step are minimized.
5.3.1
Typical Properties
The typical properties or specifications of aqueous flexo and gravure ink are:
Viscosity, Zahn efflux cup (ref. ASTM D4212-99) @ 25 °C:
Flexo ink shipping viscosity, Zahn #3 25–30 s
Gravure ink shipping viscosity, Zahn #3 21–25 s
Flexo ink printing viscosity, Zahn #3 18–22 s
Gravure ink printing viscosity, Zahn #2 18–22 s
Zahn #3 8–10 s
pH 9.0–9.5
Color accuracy (ASTM D2244-93) <2.0 Delta E* (CIELAB total color
difference) versus standard
Fineness of grind, (ASTM D1316-93) <2.0
Residue (ref. ASTM F311-97) <15 mg per 100 g ink
5.3 Physical Properties and Test Methods 115
5.3.2
Application Tests
Application specific pass/fail tests are specified to guarantee that an ink shipment
gives satisfactory performance. The application properties are measured relative to a
standard sample. The results are reported as pass or fail versus the standard. The fol-
lowing application tests are performed on aqueous flexo and gravure ink:
– Abrasion resistance, dry/wet rub resistance, Sutherland Rub Tester
– Adhesion at surface tension of 38–44 dynes cm–1, Scotch 610 Tape Test
– Block resistance
– COF (coefficient of friction), ink to ink, static at 26.6° slide angle
– COF (coefficient of friction), ink to ink, kinetic at 19.3° slide angle
– Crinkle resistance at room temperature or that of ice water
– Drying with a 1 millimicron or 2 mil fineness of grind gauge
– Freeze-thaw resistance, two cycles
– Heat resistance, 98 °C
– Milk carton wet rub
– Product resistance – acid, fertilizer, limestone, wood oil
– Re-wetting
– Rub test – metal corrugator
– Surface tension of film
– Viscosity, Zahn efflux cup
– Water resistance, 24 h, immersion at 25 °C
5.3.3
Test Method Abstracts
– Abrasion resistance – Sutherland Rub Tester: A test strip (18.8 cm) is rubbed by a
four pound test block with a 15 cm × 7.5 cm strip affixed. The test is run either:
ink-to-ink or unprinted paper-to-ink, 20 to 40 rub cycles according to specifications.
A subjective comparison is made to a photograph standard or control sample that is
tested subsequently. This test method simulates scuffing that may occur during
in-line filling, handling or transporting of a package. Wax emulsions or micro-pul-
verized powders are added to adjust the abrasion resistance properties of an ink.
For heated abrasion resistance, the four pound test block is held in an oven for
twenty minutes at a temperature specified. The test simulates scuffing that may occur
on hot filling lines or under high friction conditions.
For wet-rub resistance (approximately twelve drops) water is applied to a 18.8 cm
test strip with a pipette. Un-printed paper is used to test paper or board substrates. A
swatch of cotton material is used to test film substrates.
The test simulates rubbing of a package by cotton clothing.
– Adhesion/Scotch 610 Tape Test: A 2.5 cm wide 3-M 610 tape is attached to the ink
and pulled off at an angle of 180 degrees. Ink removal of greater than 10 % is a fail-
ure. This test is performed to flag unusual problems associated with poorly treated
films or ink composition errors
– Block resistance – wet/dry – ink to ink and ink to substrate: The exposure time,
pressure, and temperature are specified by the end use requirement (i.e. 3 min at
1034 bar, 50 °C for surface print ink (5.4) – The ink surface’s resistance to heat and
pressure is subjectively measured. Ink properties that effect blocking results are:
“hardness”, adhesion, cohesion, and slip. The polymer glass transition tempera-
ture (Tg), molecular weight, and surface compatibility effect the block resistance
test.
– Coefficient of friction measurement, TMI slip and friction tester: The peak angle
(static) and average force (kinetic) are measured. An emulsion polymer with low
glass transition temperature is required for high slide angles.
– Crinkle resistance test at room temperature or at the temperature of ice water: The
print is immersed in ice water for one hour (re-ice water crinkle). Two surfaces of
ink are rubbed ink to ink for 10 cycles. Perform a subjective comparison between a
test sample and a standard.
– Drying test with a 1.0 mil (25 µm) or 2.0 mil (50 µm) fineness of grind gauge: Dry-
ing time is measured subjectively by finger tapping and a stopwatch. A polymer’s
glass transition temperature, MFFT and emulsion particle size distribution effect
drying.
– Freeze–thaw test: A sample of ink is placed in a freezer at –15 °C for 4 h. Changes
in viscosity, homogeneity, and seeding tendency are observed.
– Heat resistance test at 100 °C – Sentinel heat seal tester: Set-up a Sentinel heat
sealer according to heat pressure and time interval specified. A one by three inch
(2.5 cm × 7.5 cm) print sample is folded ink surface-to-ink surface and placed be-
tween the sealer bars. The heat sealer is operated. After the sample has been
cooled, the sheets are separated and a subjective comparison is made for cling, ink
transfer and picking. The polymer glass transition temperature (Tg), molecular
weight, and surface compatibility affect heat resistance.
– Milk carton wet rub test: A test print is immersed in milk at 1 to 7 °C for 24 h. A
rub resistance test is performed using a Sutherland rub tester (see abrasion resist-
ance). Specific polymers (Sect. 5.6.1) are used to give resistance to milk.
– Product resistance and/or chemical resistance – acid, fertilizer, limestone, wood
oil, etc : Three drops of an appropriate chemical solution is applied using a
3-mL pipette. After a specified time interval, a cotton swab is rubbed through
the drop over the print surface with moderate pressure. A comparison is made for
discoloration, ink removal, or blistering. A polymer composition, branching struc-
ture and crosslinking density have the largest effect on chemical resistance of an
ink.
– Re-wetting test: A #4 Meyer bar drawdown is allowed to dry for 20 min at RT
(room temperature). A drop of water is placed on the ink surface and subsequent-
ly wiped with a cloth. A subjective comparison is made versus a standard sample.
Solution polymers are neutralized with volatile amines (Sect. 5.2.3) to prevent re-
solubilization after the ink print dries.
– Rub test – metal corrugator: For pre-print liner board, this test simulates the ef-
fects of a corrugator. The extent of scuffing/marring is subjectively compared to a
photographed standard. The emulsion polymer’s soft segment, glass transition
5.4 Inks for Flexible Substrates (Films) 117
temperature (Tg), and molecular weight have the largest effect on the rub resist-
ance properties of an ink.
– Surface tension of film: Accudyne level pens or solutions are used to estimate the
surface tension of treated films. A targeted range of 38–42 dynes cm–1 is specified
for most printing applications. The surface tension of most aqueous styrene
acrylic based pigmented inks are greater than 38–42 dynes cm–1.
– Viscosity, Zahn efflux cup (ref. ASTM D4212-99), seconds: A Zahn efflux cup is a
fast and effective instrument for measuring viscosity of flexo and gravure ink. Vis-
cosity is an important property for maintaining printability. For a flexo press, con-
sistency of ink flow into the pan or well of the doctor blade system, ink-transfer to
the anilox roller, and release of ink from anilox roller are largely effected by ink
viscosity. On a gravure press the release of a consistent volume of ink out of the
cylinder cell is effected by viscosity. Viscosity changes due to pH drift or evapora-
tion of solvent (water) should be corrected immediately.
– Water resistance, 24 h, immersion at 25 °C: A Crinkle test is performed. Two sur-
faces of ink are rubbed ink-to-ink for 10 cycles. A subjective comparison is made
between a test sample and a standard.
5.4
Inks for Flexible Substrates (Films)
The ink used for printing flexible substrates (films) contains a soft film forming
emulsion polymer based on styrene and co-monomers such as butyl acrylate, and
2-ethylhexyl acrylate. Solvent based inks have continued use in high performance
printing applications such as packages requiring lamination bonds (i.e. candy wrap-
pers, potato chip bags). Flexo and gravure printing companies have invested in sol-
vent incinerators to remain compliant with environmental regulations. Examples of
materials used for flexible packaging films are:
LDPE Low density polyethylene (i.e. fruit and vegetable produce bags)
MDPE Medium density polyethylene (i.e. department store merchandize bags)
HDPE High density polyethylene (i.e. grocery item bags)
LLDPE Linear low density polyethylene
(i.e. department store merchandize bags)
PP Polypropylene (i.e. salt, fertilizer bags)
PP-EVA Ethylene vinyl acetate modified polypropylene
OPP Oriented polypropylene
PP-NO Non-oriented polypropylene
PP-AC Acrylic coated polypropylene
PP-PVDC Poly(vinylidene chloride)-coated polypropylene
PET Polyethylene terephthalate
PVDC Poly(vinylidene chloride) (Saran)
5.4.1
Surface Print Film
Surface print inks are designed for printing on polyethylene substrates used in utili-
ty bags, department store merchandize bags, grocery bags, and general purpose sur-
face film applications. The films are surface treated via corona discharge increasing
to a surface tension of 38–41 dynes cm–1 before printing. A corona discharge induces
ions and free radicals to oxidize the surface of a film to form polar functionality. This
change in surface chemistry and roughness increases surface energy and improves
wetting of ink on film. A surface print ink is composed of a soft film forming styrene
acrylic emulsion vehicle to provide adhesion. A solution vehicle composed of low
molecular weight styrene acrylic resin is added to adjust printability. Typical proper-
ties of the emulsion polymers and solution resins used in ink for surface print films
are listed in Tabs 5-3 and 5-4.
5.4.2
Lawn and Garden Bags
Lawn and garden bag inks are designed for printing on polyethylene or polypropy-
lene substrates used in fertilizer, salt, mulch, potting soil, manure, feeds and wood
bark bags. Lawn and garden bags require resistance to: weak acids, bases, fertilizers,
limestone dust, wood oils (i.e. cedar, pine), etc.
A typical Lawn and garden bag ink has a similar composition to surface inks. A
crosslinking compound (i.e. zinc oxide, carbodiimide, polyfunctional aziridine) adds
covalent branching, increases modulus and enhanced print film adhesion and re-
sistance to chemicals.
As an alternative, a self crosslinking styrene acrylic emulsion which reacts upon
evaporation of water may be used according to the Akzo Nobel Resins paper present-
ed at the 44th NPIRI Technical Conference [10].
5.5
Inks for Paper Board Substrates
5.5.1
Folding Cartons
Folding carton inks are designed for printing on paper board (or boxboard) sub-
strates used in: fast food carry out packages, pastry cartons, cereal boxes, mail con-
tainers, auto parts boxes, beverage carriers, milk and juice cartons, and other pack-
ages. Folding cartons are made from solid bleached kraft or solid bleached sulfate
(SBS), unbleached kraft, solid unbleached sulfate (SUS), clay coated unbleached
kraft, recycled paperboard, and coated paperboard.
For beverage carriers, one substrate type is used consistently in most of the US
market. Many beverage carriers are over-coated with a clear protective coating layer.
5.5 Inks for Paper Board Substrates 119
A folding carton ink is composed of a hard non-film forming styrene acrylic emul-
sion vehicle and a styrene acrylic solution vehicle. As an alternative, a film forming
styrene acrylic emulsion vehicle and rosin fumarate ester solution vehicle are used.
A plasticizer (i.e. propylene glycol) and solvent (i.e. n-propyl alcohol) are added to
folding carton ink to improve printability and insure coalescence at room temperature.
5.5.2
Direct Print Corrugated Packages
Direct print corrugated inks are designed for printing on standard kraft paper board
substrates. Corrugated board is manufactured by laminating flat sheets of paper to a
corrugated inner layer to give an increased stiffness-to-weight ratio [12].
Direct print corrugated ink is made from styrene acrylic colloids. Colloids are poly-
mers produced by emulsion polymerization followed by neutralization of available
carboxyl functionality. Colloids have molecular weights in the range of 25 000–
100 000 g mol–1. They are used in low cost ink systems for printing on porous sub-
strates such as corrugated paper board. Colloids are also supplied in solid form for
dissolving in water by neutralization with an amine. This results in uncoiling of the
colloidal particle to form a colloid solution. Colloid solutions give a high viscosity.
They are supplied at low solids concentrations typically between 20 % to 40 %.
A direct print corrugated ink is composed of a styrene acrylic emulsion colloid ve-
hicle and a rosin fumarate ester and/or styrene acrylic solution vehicle. As an alter-
native, a mixture of colloid solution with a film forming emulsion provides the over-
all corrugated ink properties.
Direct print corrugated ink specifications:
Residue <15 mg per 100 g ink
Density (g cm–3/lbs gal–1) 1.07–1.11/8.9–9.3
Dry rub 100 rubs/1.8 kg (4 lb) weight
Grind, NPIRI <2
5.5.3
Pre-print Corrugated Packages
Pre-print corrugated inks are designed for printing on standard kraft, bleached kraft,
mottled kraft, clay coated, and SBS coated paper board substrates. Many producers of
corrugated packages have installed flexo presses for pre-printing linerboard before
making the corrugated board. Printing on a smoother surface gives improved print
quality. These inks must withstand heat (175–200 °C), pressure, and marring/scuff-
ing conditions of the subsequent paperboard corrugating process. Most pre-print
packages are coated with a clear, high gloss, heat resistant, and scuff resistant coat-
ing. The coating adds resistance properties and gloss.
A pre-print corrugated ink is composed of a styrene acrylic emulsion colloid vehi-
cle and a rosin fumarate ester resin and/or styrene acrylic resin solution vehicle. The
physical properties of emulsions and resins used in pre-print corrugated ink are list-
ed in Tabs 5.4 and 5.5 for.
Plasticizers (i.e. propylene glycol) and coalescing solvents (i.e. glycol ether) are
added to maintain satisfactory printability and satisfactory MFFT (minimum film
formation temperature).
5.6
Inks for Poly-coated Board
Inks for polymer coated paper board are designed for printing on polyethylene coat-
ed SBS (solid bleached sulfate) paper board substrates used in milk cartons, ice
cream cartons, beverage cups, and paper plates.
A typical ink for coated board is composed of an epoxy ester based pigment dis-
persion, styrene acrylic emulsion vehicle, and an epoxy ester solution vehicle. The
epoxy resin commonly used is an ester of drying or semi-drying fatty acid and acrylic
acid (Sect 5.2.3). The system undergoes oxidation to give moisture and alkali resist-
ance [11]. Alternative polymers that may be used in inks for coated board are: aziri-
dine (ethylene imine) crosslinking styrene acrylic or a VAE (vinyl acetate ethylene)
self crosslinking emulsion polymer.
5.6.1
Milk Cartons
Milk carton ink must have resistance to alkaline detergent based chain lubricants. A
fatty acid acrylic epoxy ester [11] is the key resin used in this type of ink. Special pig-
ment dispersions are used based on the same epoxy ester since conventional styrene
acrylic based pigment dispersions are not stable in epoxy ester based systems.
5.6.2
Cup and Plate
Cup and plate inks must have tolerance for hot wax coatings and resistance to hot
and cold fluids. They should meet the requirements for general purpose paper plate
use. A hard non-film forming styrene acrylic emulsion combined with hot-air drying
(by oxidation) fatty acid-acrylic epoxy ester [11] provide the resistance requirements.
5.7
Inks for Paper Products
A typical ink used for printing multiple wall bags, gift wrap, and envelopes are com-
posed of a hard non-film forming styrene acrylic emulsion combined with a solution
vehicle comprising a rosin fumarate ester to balance printability and coalescence. A
polymer with high molecular weight and Tg fast drying via fast: resin-solvent (water)
separation, penetration of paper and brightness of color via “holdout” of pigment
particles on the paper surface.
5.7 Inks for Paper Products 121
5.7.1
Multiple Wall Bags
Inks for Multiple Wall bags are designed for printing on kraft: brown, or bleached,
mottled (compressed thin layers of bleached pulp on top of brown pulp), clay coated,
and uncoated paper substrates. Flexographic printing is the most used process for
multi-wall bags.
Multi-wall and other paper bags are made of one or more walls of paper glued to-
gether and treated to provide moisture resistance. Heavy duty bags used as shipping
sacks have three or more plies. Bags used for packaging consumer products (i.e. pet
food, sugar, flower) have two plies. The paper used in bags for packaging consumer
products has been upgraded in recent years to bleached kraft and clay coated.
5.7.2
Gift Wrap and Envelopes
Gift wrap is used for seasonal gifts, retail wrapping, liquor boxes, candy and other
products. The substrates used are 90 % paper and 10 % foil [12].
Inks for Gift Wrap are composed of a hard non-film-forming styrene acrylic emul-
sion combined with a solution vehicle to adjust printability and balance coalescence.
Gravure is the most used process for printing gift wrap.
Envelope ink is made from the same mix of polymers as gift wrap ink.
5.7.3
Newspapers
Newspapers were originally printed by the letterpress printing process. Low cost
black ink was mostly used. A letterpress black ink is composed of carbon black dis-
persed in high boiling point aliphatic petroleum solvent (ink oil). By 1995 the major-
ity of newspapers converted to the offset lithographic printing process. Offset news
ink is composed of carbon black or organic pigments dispersed in high boiling point
aliphatic petroleum solvent based vehicles. The vehicles are resin solutions in ink oil
and/or vegetable oils (i.e. soybean oil). During the 1980’s the remaining letterpress
printers began to switch to the flexographic process and water based ink. Aqueous
flexo news ink is based on higher cost emulsion polymers than typical petroleum hy-
drocarbon resin based offset inks. Therefore it was necessary to target certain news-
paper market segments with higher value products. Flexographic newspaper print-
ing introduced brighter colors to comics and advertising, and overall increased color
coverage per newspaper. A flexographic news ink contains a high molecular weight,
styrene acrylic emulsion with high Tg (glass transition temperature) to provide fast
drying.
A typical flexographic news ink is composed of a hard semi-film-forming styrene
acrylic emulsion vehicle.
5.7.4
Towel and Tissue
The same styrene acrylic emulsions used for sizing tissue paper to provide wet
strength are used in the ink. The colorants used are mostly dyes or pigments that are
not dermatological irritants. The resin should give a waterproof bond and be low
cost. The components of a towel and tissue ink are re-pulpable for ease in recovery of
waste and/or off-grade material to achieve satisfactory economies of paper towel tis-
sue converting.
References
1 Western Michigan University Web Site: 8 Biggerstaff, J. A., Reuther, P. C., Jack-
http://www.wmich.edu/ppse/flexo/, son, K., Westvaco Chemical Division,
Flexographic Process A Comparison of Water-borne Chemical
2 Western Michigan University Web Site: Resistant Technologies and the Variables
http://www.wmich.edu/ppse/gravure/, that Affect their Performance, 43rd
Gravure Process, NPIRI Technical Conference, Septem-
3 Wicks, Z. W. Jr., Jones, F. N., Pappas, ber 15–17, 1999.
S.P., Dispersions in Aqueous Media, in: 9 Tien, C., Mao, C., Snyder, J. M., Beck,
Organic Coatings, Science and Technology, A., Air Products and Chemicals, Inc.,
2nd edn, Wiley-Interscience, 1999, US Patent 5,977,215, Low Temperature
Chapter 20.3, p. 395. Self-Crosslinking, Aqueous Disper-
4 Schilling, P. Westvaco Corporation, sions of Urethane–Vinyl Polymers for
US Patent: 5,208,319, Rosin-Based Coating Applications.
Grind Resins for Aqueous Printing Ink. 10 de Krom, A., Mulder, H., Mestach, D.,
5 Zuraw, P. J., Westvaco Corporation , Akzo Nobel Resins BV, Self-Crosslink-
US Patent: 5,166,245, Modified Rosin ing Acrylic Dispersions Outperform Con-
Resins for Waterbased Inks, 1992. ventional Solventborne Liquid Inks, 44th
6 Rivera, M. A.; Zuraw, P. J., Westvaco NPIRI Technical Conference, October
Corporation, US Patent: 5,216,064, 18–20, 2000.
Rosin-Based Resin-Fortified Emulsion 11 Meeske, C. J., Van der Tuin, E. H.,
Polymers Racey, M. J., Reichold Chemicals, US
7 Hutter, G. F., Westvaco Corporation, Patent 4,166,054, Water Dispersible
US Patent: 5,656,679, Rosin Ester-Amide Epoxy resin Copolymers and Methods
Support Resins for Acrylic Latexes. of Making Same, 1979.
12 Eldred, R. N., Ph.D., Package Printing,
Jelmar Publishing, 1993.
6
Applications for Decorative and Protective Coatings
Brough Richey and Mary Burch
6.1
Introduction
Decorative and protective coatings are used in a great variety of applications, ranging
from the familiar such as coatings for buildings, furniture, automobiles, and large
industrial structures, to less well known applications such as removable coatings, pa-
per coatings, and specialized coatings for optical fibers and electronic components.
Most coating applications have historically utilized solution polymers as the binder
component. However, concerns over pollution, the toxicity of solvents, and ease of
use and clean-up have driven the development of new emulsion polymer technolo-
gies to meet the needs of the coatings industry. The use of emulsion polymers for
coating applications has increased tremendously over the past fifty years and they are
now represented in nearly every segment of the industry. In fact, coatings based on
emulsion polymers frequently set the performance standards and lead the market in
many areas.
The objective of this chapter is to give the reader an overview of the use of emul-
sion polymers in decorative and protective coatings. Because of the great variety of
specific applications, it will not be possible to address them all, and we have chosen
instead to focus on selected application areas which we believe will provide the read-
er with a useful foundation in a variety of coating applications.
6.1.1
Market Overview
The development, manufacture, sale and application of decorative and protective

coatings comprise a large business and we estimate that approximately 20 billion
liters of decorative and protective coatings are manufactured and applied each year,
representing world wide sales of about $60 billion US [1]. Annual growth is typically
the range of 1–3 % world wide, and is generally linked to the combined gross do-
mestic product of the major industrialized and developing nations. Growth rates for
124 6 Applications for Decorative and Protective Coatings
water based coatings have been higher, in the 3–6 % range, with most of the extra
growth due to the switch from solvent based coatings.
We can obtain an estimate for the annual world wide production of emulsion poly-
mers for decorative and protective coatings as follows. If we assume that water based
coatings make up about 50 % of the total world wide volume, then approximately
10 billion liters of water based paint are manufactured each year. To estimate the
amount of emulsion polymer manufactured to yield this amount of coating material,
we can estimate an “average” water based paint has about 30 % volume solids, with
the dry volume of binder representing about 50 % of this value. This yields an esti-
mated 1.5 billion liters of solid emulsion polymer produced per year. Assuming an
average polymer dry density of 1.1 kg L–1 and an average emulsion solids level of
50 % by weight, it follows that the world wide production of emulsion polymer for
coating applications is about 3 billion wet kg (6–7 billion wet pounds) per year. While
this is admittedly a rough estimate, it nevertheless serves to illustrate the enormous
size of the water based coatings market and the large amount of polymer emulsion
needed to supply it.
6.1.2
Coating Industry Trends
The most significant trend in the decorative and protective coatings markets has
been the move to more environmentally friendly coating materials. The shift away
from traditional solvent borne technologies to newer technologies based on water-
borne emulsion polymers, high solids coatings, and powder coatings is a key conse-
quence of this trend. This change has been driven by a variety of regulatory pressures
aimed at reducing air pollution by lowering the volatile organic content (VOC) of
coating materials. Related to these pollution concerns is the desire to increase the
safety of the end use application process, particularly in the area of decorative coat-
ings for homes and offices. Again, this has caused a shift away from traditional sol-
vent borne technologies toward newer technologies with improved health and safety
profiles. Finally, world wide economic conditions have led to consolidation in the
paint manufacturing industry, and its associated raw material suppliers [2]. These
economic factors have created a strong movement towards cost reduction and in-
creases in production and distribution efficiency across the coatings industry. In our
view, the combination of continued technical innovation with improved cost effi-
ciency presents the central challenge to the coatings industry as we move into the
twenty-first century.
6.1.3
Coatings Provide Decoration and Protection
It is common to divide the general class of coatings into two subclasses: decorative
and protective coatings. While this division can be useful, it can be also be mislead-
ing; the vast majority of coatings systems provide both decoration and protection.
Automotive coatings systems provide a familiar illustration of this dual role: they are
foremost a protective coating, and must protect the automobile body from damage
by weathering and the environment; and yet, the color and appearance of automotive
finishes are vital factors which influence the customer’s purchase decision. Interior
decorative finishes provide an example at the other end of the decorative-protective
continuum. While used primarily for decorative purposes, the stain resistance and
cleanability of interior finishes are important performance characteristics which of-
ten provide differentiation in this competitive market.
6.2
Overview of Coating Formulations
Decorative and protective coatings consist of three main components:

(i) pigment, which provides color and opacity to the coating
(ii) binder, which holds the film together and provides coating integrity; and
(iii) carrier liquid, which provides as the liquid character of the coating while in the
wet state (before drying).
In this chapter, we will focus on coatings utilizing emulsion polymer binders, and
consequently, water will be the carrier liquid. These types of coatings are also com-
monly referred to as latex paints, presumably in reference to the similarities in ap-
pearance between the emulsion polymer binders and unprocessed natural rubber.
Commercial paint formulations are usually complex and typically contain more
than the three main components described above. These formulations usually have
on the order of 10–20 raw material components, the specific nature of which de-
pends on the intended application. A more realistic formulation would include: dis-
persed solids such as pigments and fillers stabilized by a polymeric dispersing agent,
a dispersed emulsion polymer acting as the binder, a thickener to provide proper
rheology, coalescents and co-solvents to promote film formation and optimize the
drying process, surfactants to improve colloidal stability and promote substrate wet-
ting, a biocide to prevent microbial spoilage, a defoamer to reduce foaming during
manufacturing and application, and a neutralizing agent to adjust the pH. Many op-
timized formulations contain more than one member of each of these classes. The
primary technical challenge of coatings formulation is to develop cost effective coat-
ing formulations which are stable indefinitely in the wet state, apply correctly to the
substrate, dry into defect free films, and meet the appearance and performance re-
quirements of the intended application.
6.2.1
Volume Solids and Pigment Volume Content
The relative ratios between the volumes of different formulation components control
many of the key appearance and performance properties of a coating [3, 4]. Volume
solids is the simplest of these relationships; it is the ratio between the volume of sol-
id components in a coating and the total volume of the wet coating. It typically is re-
ported as a percentage. Volume solids is a useful quantity because it allows one to
calculate the thickness of a dried coating from the applied wet paint thickness, or
from the spread rate (the volume of wet coating applied per unit of area). It can also
be used to estimate the quality of a coating when comparing coating formulations of
a given class. Since water is an inexpensive raw material, formulations high in water
content (and low in volume solids) tend to have lower raw material costs. Typical
emulsion polymer coatings for decorative and protective applications have volume
solids in the range of 25–45 %, with values ranging up to 60 % for some specialty ap-
plications.
The pigment volume content (PVC) is another useful volume relationship which
is frequently used in coatings formulation development. It is the ratio of pigment
and extender solids to the total coating solids (pigment, extender, and binder solids),
and like volume solids, is usually reported as a percentage. Coatings with low PVCs
have a high binder content, and coatings with high PVCs have a low binder content
with higher levels of pigment and extender. It is important to recognize that PVC
represents a property of the dry film, rather than the wet coating.
PVC is an important quantity because it relates to many of the performance prop-
erties of a dry paint film. If several versions of a particular formulation are prepared
with different PVCs, ranging from lower to higher values, a transition point will be
observed at which many performance features of the coatings change abruptly. This
point is termed the critical PVC, or CPVC, and, in conceptual terms, represents the
PVC where the polymeric components of a film no longer form a continuous phase
surrounding the pigment and extender particles. Above CPVC, the dry coating be-
gins to develop small voids between the solid components of the film, leading to an
abrupt change in the performance features of the coating. The value of CPVC for a
coating depends somewhat on the property used to measure it, and thus it is not a
truly fundamental characteristic of a film. Nevertheless, it has proven to be a useful
and practical conceptual tool for coatings formulation development.
Figure 6-1 is a scanning electron micrograph which provides a vivid illustration of
the differences between above and below CPVC coatings: Figure 6-1A shows the
smooth, polymer rich surface which is typical of a water based enamel formulated
significantly below CPVC; the white spots are TiO2 particles sticking through the
surface of the gray polymer matrix. Figure 6-1B shows the surface of a highly ex-
tended, above critical, flat ceiling coating at the same magnification. Note the high
porosity and variety of extenders in the above CPVC coating. The differences in the
surface features of these two emulsion polymer coatings are striking, and suggest
that these two types of coatings would have very different performance profiles.
The value of the CPVC for a particular formulation will depend on the chemical
and physical nature of the pigments, extenders and the binder. To illustrate this, we
consider two paints formulated with the same total volume of pigment and binder
(equal PVC). In one case the paint is formulated with a smaller particle size (PS) pig-
ment, and in the other case the paint is formulated with a larger PS version of the
same pigment. The CPVC of the paint with the smaller PS pigment would be lower
than the CPVC of the paint with the larger PS pigment. This is because the higher
surface area of the smaller PS pigment will require a higher level of polymer to uni-
formly cover the pigment surfaces. This results in a higher binder demand, and low-
Fig. 6-1 Field Emission Scanning Electron the surface image obtained from a flat ceiling
Micrographs of Below and Above CPVC Coat- coating which has been formulated significantly
ings. (A) shows the surface image obtained above CPVC. Note the porosity and variety of
from a gloss enamel coating which has been extenders present in the coating formulated
formulated significantly below CPVC. (B) shows above CPVC.
ers the PVC at which CPVC is reached. Comparing the actual PVC of a coating to the
CPVC can provide useful information regarding a coating’s physical properties and
suitability for a particular application. Coatings formulated at PVCs below CPVC
tend to have higher gloss, lower porosity, better flexibility and better barrier proper-
ties. Coatings formulated above CPVC generally have lower gloss, higher porosity,
lower flexibility and lower total cost. Since PVC level is usually adjusted upward by
increasing the levels of low cost extenders, PVC can provide a useful gauge of for-
mulation cost (and quality). This measure is most useful for coatings formulated
above CPVC. PVC is a less useful measure of quality in coatings formulated below
CPVC, since these coatings contain little or no low cost extenders and consist prima-
rily of higher cost resins and pigments.
6.2.2
Polymer Matrix
The polymer or binder component holds the coating together and provides many of
the performance features needed for specific coating applications. A high molecular
weight polymeric material is generally used as the binder in order to provide the
toughness and resistance properties needed to protect the substrate and ensure a
durable coating. In practical systems the minimum molecular weight of thermoplas-
tic polymers targeted for coating applications is around 50 000 g mol–1 [5–7]. Poly-
mers with molecular weight below this value generally do not have the required
toughness properties needed for coating applications: lower molecular weight crys-
talline materials are generally too brittle and can chip or flake, while non-crystalline
materials such as amorphous waxes do not have high enough moduli to provide the
film integrity needed for most coating applications.
Decorative and protective coatings are generally designed to perform their func-
tion over the temperature range of –20 °C to +45 °C. The polymers used for coating
applications are usually random copolymers or terpolymers with monomer compo-

sitions such that the polymer glass transitions, Tg, fall in the middle to upper end of
this range. Polymers with glass transition temperatures below 0 °C are not useful in
most coating applications because their films are tacky and weak under normal
ambient temperature conditions. Polymers with Tg significantly above 50 °C tend to
be brittle and inflexible under normal ambient conditions and are less commonly
used in coating applications. These generalizations are most applicable to thermo-
plastic polymers, but the concepts can also be applied in a less formalized way to
thermoset coatings (temperature dependent reactive polymerization systems).
6.2.3
Film Formation
Coatings based on emulsion polymers exist as stabilized colloidal dispersions while

in the wet state. Upon application to the substrate, water evaporates and the film
dries and cures into the final coating. Properly designed and formulated, the wet
paint is stable indefinitely; however, the drying and film formation processes are ef-
fectively irreversible and result in a final film which is a tough, pigment-polymer
composite. The irreversibility of the film formation process is a key technical factor
underlying the successful utilization of emulsion based polymers for decorative and
protective coating applications. If film formation were reversible, then dried coatings
could be degraded by contact with liquid water; the ubiquity of water in our environ-
ment would make the utility of such coatings very limited.
Film formation from emulsion polymers is a complex process but for simplicity
it can be taken to consist of three phases. In the first step, water evaporates from
the continuous phase of the liquid coating and the polymer and pigment particles
begin to crowd together. The effective volume solids of the coating rises significant-
ly. In the second phase, the latex and pigment particles begin to pack together
to create a contiguous film. In the third and final phase, interstitial water diffuses
out of the film and the emulsion polymer particles coalesce into a continuous,
inter-particle polymer network. The detailed physics and chemistry of the film
formation process are still not completely understood and are affected by many
factors [8–10]. Empirically, it has been observed that if the polymer Tg is higher
than the ambient film formation temperature, the final coalescence step of the
process may break down, resulting in a poor quality film with diminished integrity.
The minimum temperature at which an emulsion polymer will form a good film is
referred to as the MFFT (minimum film formation temperature) and is generally
a few degrees lower than the polymer Tg. It should not be a surprise that there
is a general relationship between the polymer Tg and the MFFT. Since film forma-
tion involves the interpenetration of polymer chains between adjacent polymer
particles, a reasonable amount of chain mobility must exist for this process to
proceed. However, the MFFT of an emulsion polymer is not a precisely defined
physical quantity and its value can depend on several factors in addition to Tg
including polymer molecular weight and composition, as well as the drying rate
of the applied coating. Hence, MFFTs are usually determined empirically by moni-
toring film formation as a function of temperature under a set of standardized dry-

ing conditions.
Most coatings are applied under ambient temperature conditions (either on a job
site or in a factory) with typical application temperatures between 10 and 40 °C. To
ensure good film formation at the lower end of this range, polymer Tg values would
need to be in the 10–15 °C range. In practice, it has been found that polymers with
higher Tg are usually needed to provide optimized performance in many coating ap-
plications, particularly for coatings formulated at lower PVCs where the binder con-
tent is high. This presents a problem: polymers with desirable dry film performance
frequently have Tg which are too high to form a good film under typical drying con-
ditions. To circumvent this problem, coatings formulators temporarily lower poly-
mer Tg and MFFTs by use of coalescing agent. Coalescents work by partitioning into
the emulsion polymer particles, disrupting the packing of the polymer chains, and
thus lowering the effective polymer Tg. After the film is applied, the coalescent will
slowly diffuse to the film surface and evaporate, allowing the effective Tg to rise and
yielding a tougher, more useful coating. To be effective, the coalescent must be rea-
sonably compatible with the polymer phase and relatively low in molecular weight in
order to partition into the polymer matrix. It should also have a moderate vapor pres-
sure: the coalescent needs to remain in the film long enough to optimize film for-
mation, but should also evaporate from the film reasonably quickly in order to allow
performance properties to develop. The choice of a coalescent depends on the poly-
mer composition, the coating formulation and the intended application. Oxygenated
solvents of moderate polarity are commonly used for this purpose; these include var-
ious ether-esters of propylene and ethylene glycols, and ester-alcohols.
6.2.4
Typical Polymer Compositions
A variety of polymer compositions are used as binders in decorative and protective

coating applications. By definition, emulsion polymers are based on vinyl mono-
mers, but even with this restriction there are a number of different polymer classes
which can be used for a given application. The choice of polymer system depends on
many factors, which we will highlight below in the context of specific examples of
coating applications. In this section we give an overview of the major emulsion poly-
mer classes and discuss their general performance characteristics.
Styrene-butadiene copolymers
Historically, styrene-butadiene copolymers were the first emulsion polymers to be used
for coating applications. These polymers were based on technology developed for syn-
thetic rubber production during WW II. Typical polymer compositions were 65 %
styrene with 35 % butadiene. While paints based on styrene-butadiene emulsion
polymers opened the door for the development of synthetic latex paints, their cost-per-
formance profiles were not particularly competitive with the solvent borne coatings
present at that time or with the other emulsion polymer technologies which would be
developed later. They now occupy only a very small segment of the coatings market.
Vinyl acetate copolymers

Vinyl acetate (VA) homopolymers were also used in early latex paints, and like
styrene-butadiene polymers, were also not particularly successful in the market. The
main problems were that the high Tg of VA homopolymers made it difficult for these
coatings to form strong, high quality films, and the mottling and loss of film integri-
ty caused by hydrolysis of VA when applied over masonry (alkaline) substrates.
However, vinyl acetate can be copolymerized with butyl acrylate (BA) in an emulsion
polymerization process, resulting in internally plasticized copolymers with MFFTs
in the ambient temperature range and improved resistance to hydrolysis. When
large quantities of BA monomer became commercially available in the 1960s, the
use of VA-BA emulsion polymers in coating applications increased substantially.
Typical vinyl acetate-butyl acrylate copolymers compositions are 80 % VA with 20 %
BA by weight. Because of their relatively low cost, VA-BA copolymers have proven to
be very successful in interior decorative paint applications. While more resistant
than VA homopolymers, VA-BA copolymers can still be degraded by alkaline hydrol-
ysis and their polar character can yield films which are relatively water sensitive.
These factors can limit the use of VA-BA copolymers in demanding exterior applica-
tions, although they are often used for less demanding exterior coatings when low
raw material costs are a primary formulation factor.
Vinyl acetate can also be copolymerized with ethylene (E) in an emulsion polymer-
ization process. Again, ethylene serves as an internal plasticizer for VA, lowering the
Tg of the copolymer into the useful ambient temperature range. Since ethylene is a
gas at ambient temperature, VAE emulsion copolymers need to be manufactured in
specialized reactors, designed for high pressure use. Typical VAE copolymers used
in coating applications are about 90 % VA with 10 % ethylene by weight. While eth-
ylene is a low cost monomer, the cost advantage relative to BA can be lost because of
the higher manufacturing costs associated the use of pressurized reactor systems.
The performance profiles of VAEs are similar to that of VA-BAs; like VA-BA copoly-
mers, VAEs have been most successful in interior decorative coatings.
Styrene acrylic copolymers

Homopolymer styrene has a high Tg (100 °C) and thus needs to be copolymerized
with a soft monomer for use in coating applications. Most frequently, butyl acrylate
is chosen for this purpose, and styrene-butyl acrylate copolymers used in coating ap-
plications typically have a composition of around 50 % styrene with 50 % butyl acry-
late by weight. Styrene is a relatively low cost monomer (although styrene costs have
fluctuated widely over the years) which is produced widely around the world. Be-
cause styrene is relatively hydrophobic, paints based on styrene acrylic polymers
tend to be resistant to water transport and provide good barrier properties, particu-
larly in comparison to vinyl acetate polymers. However, styrene has a strong absorp-
tion band in the near UV region of the electromagnetic spectrum, and photons of
this wavelength are energetic enough to induce photochemical processes which ulti-
mately lead to polymer degradation and reduced exterior durability. In spite of this
drawback, the exterior durability of styrene acrylics is often adequate to meet the per-
formance requirements for many exterior applications, particularly those where low
formulation cost is a primary consideration. Their barrier properties and resistance

to alkaline hydrolysis make styrene acrylics particularly popular in coatings for ma-
sonry applications, and often for stain blocking primers. Styrene acrylics are also
commonly used in industrial maintenance applications, where their good barrier
properties help provide effective corrosion resistance when applied over ferrous sub-
strates.
Acrylic copolymers
Homopolymers of methyl methacrylate have a high Tg (100 °C) and, like styrene and
VA, are too hard for typical coating applications. Again, butyl acrylate is commonly
used to provide internal plasticization, and to bring the Tg of acrylic copolymers
down into the ambient temperature range. Typical acrylic compositions for coating
applications are around 50 % methyl methacrylate and 50 % butyl acrylate by weight.
Unlike styrene, acrylic polymers do not absorb light in the near UV region, and thus
they are resistant to photochemically induced polymer degradation processes. As a
class, acrylics generally exhibit the best exterior durability of emulsion polymers
commonly used in coating applications. However, methyl methacrylate is a higher
cost monomer than VA or styrene, and coatings based on acrylic binders tend to have
higher raw material costs. Acrylic copolymers are used in a wide variety of coating
applications; they are most popular in exterior applications and can be engineered to
provide cost-effective performance features for interior applications as well.
Specialty monomers
Most emulsion polymers used in coating applications are based on the general
copolymer compositions outlined above. However, commercial polymers usually uti-
lize small amounts of specialty monomers to provide added performance features
desirable for specific applications.
In the wet state, emulsion polymer coatings exist in the form of a densely crowded
colloidal dispersion. Good colloidal stability (resistance to particle–particle aggrega-
tion processes) is required in order to provide long term storage stability and to de-
liver the intended performance features.
Colloidal stability can be enhanced by utilizing coulombic or steric stabilization
methodologies. Coulombic stabilization is the most commonly used method, and in-
volves including a small amount of ionizable species (<10 %) in the polymer compo-
sition. Usually an acidic monomer such as acrylic or methacrylic acid is used, which
upon neutralization with a suitable base, provides a layer of net negative charge on
the particle surface. The coulombic repulsion between these negatively charged par-
ticles can provide an effective barrier to thermally induced aggregation processes.
Most anionic surfactants associate with the surface of dispersed emulsion particles,
and they can also be used to increase coulombic stability in emulsion polymer sys-
tems.
Steric stabilization is based on attaching low molecular weight, water soluble poly-
mers to the particle surface. This layer of soluble polymers on the particle surface
provides an entropically based repulsive interaction between particles, thus confer-
ring additional colloidal stability. Both coulombic and steric stabilization inhibit un-
desired particle aggregation in the wet coating and this enhances storage and shear
stability, as well as helping to optimize the film formation process.
A wide variety of other specialty monomers are also used to provide specialized
performance properties for coating applications. For example, amine functional
monomers can be used to improve adhesion to aged alkyd substrates. Specialized
monomers can also be used to improve exterior durability, for example VEOVA
(vinyl ester of vesatic acid) monomers can improve the hydrolysis resistance of vinyl
acetate polymers, and n-butyl methacrylate can be used to enhance the durability of
BA-MMA acrylics. Polymer hydrophobicity can be fine tuned by varying the levels of
hydrophobic and hydrophilic monomers in the composition and styrene or ethyl
hexyl acrylate are used to increase film hydrophobicity and reduce water permeabili-
ty in BA-MMA systems. Specialty monomers are also used to provide specific chem-
ical functionality to polymer compositions. For example, hydroxyethyl methacrylate
can be used to provide hydroxyl functionality to acrylic resins, allowing these poly-
mers to be used in cross-linkable thermoset coatings which cure via melamine
chemistry. While specialty monomers are used at relatively low levels in polymer
compositions, they frequently provide the performance features needed for the suc-
cessful application of emulsion polymers in many coating areas.
6.2.5
Pigments, Extenders, and Additives
While the polymeric binder is usually a major component of a coating formulation,

it is important to recognize that the other components (pigments, extenders, and ad-
ditives) also play a vital role in ensuring a coating will meet the desired cost and per-
formance targets. In this section we will give a brief overview of these other compo-
nents, with the aim of providing the reader with a background sufficient to under-
stand the formulations and examples discussed later in this chapter.
Pigments provide the color and hiding properties of a coating. They can be either
organic materials, such as phthalocyanine blue and carbon black, or inorganic mate-
rials such as titanium dioxide (TiO2) and iron oxide [11]. For coatings based on emul-
sion polymers, pigments usually exists as a colloidal dispersion of sub-micron or mi-
cron sized particles. Pigments are dispersed into a liquid by a high shear rate grind-
ing processes, usually in the presence of specific dispersing agents (specialized sur-
factants or low molecular weight polyacid resins) which provide colloidal stability
and help optimize color efficiency. It is the selective absorption and scattering of vis-
ible light by the pigment particles which provides color and opacity to a coating.
TiO2, the most common pigment used in coating applications, gives a white color
and excellent hiding because its high index of refraction and carefully optimized par-
ticle size allow it to uniformly and efficiently scatters light across the visible spec-
trum. Colored pigments function by absorbing a portion of the visible light spec-
trum, and the unabsorbed spectral components are scattered back from the film, giv-
ing rise to its color. Pigments make up a substantial portion of a coating’s total raw
material cost, and they are carefully processed and formulated in order to maximize
their performance.
Extenders provide a low cost way to adjust the solids level of a coating formulation.
For example, coatings formulated above CPVC generally contain high levels of ex-
tenders, because it would be cost prohibitive to raise the PVC this high by use of
TiO2 alone. Extenders are inorganic materials which are processed to yield particle
sizes on the micron scale. Functionally, extenders differ from inorganic pigments
because they do not significantly absorb or scatter visible light. Like the binder and
pigment components, the extenders in an emulsion based coating exist as a stable
dispersion in the water phase. A high shear rate milling process, aided by dispersing
agents, is used to create the dispersion. A variety of extender materials are common-
ly used in coating applications; these include: calcium carbonates, clays, feldspars,
silicas, and talcs [12]. While extenders are relatively inexpensive, they can have a sig-
nificant impact on the performance of a coating. Careful selection of extender com-
ponents is needed in order to optimize the cost-performance balance of a coating for-
mulation.
Dispersants provide enhanced colloidal stability to pigment and extender particles
when formulating coatings based on emulsion polymers. Dispersing resins also fa-
cilitate the wetting and breakdown of pigment and extender agglomerates in the ini-
tial milling and/or grinding process and help to stabilize and reduce the viscosity
of the millbase (the millbase is a concentrated dispersion prepared from the pigment
and extender powders). Dispersants are generally low molecular weight, water solu-
ble, vinyl resins with high levels of acid functionality. They are usually neutralized
with a base such as ammonium hydroxide, sodium hydroxide or potassium hydrox-
ide, and are used at levels of 0.5 to 1.0 % by weight solids on pigment and extender
solids. In coatings based on emulsion polymers, dispersants act by increasing the
coulombic stability of the pigment particles; dispersing resins associate with polar
functional groups on the pigment surface, and the ionized acidic groups on the resin
backbone provide strong anionic stabilization to the particles under neutral or basic
pH conditions.
Thickeners are used to provide emulsion based coatings with the desired applica-
tion rheology. Coatings formulated with emulsion polymers generally have volume
solids in the range of 25–40 %, and in the absence of a thickening system, this range
of volume solids would be too low to provide adequate viscosity for most coating ap-
plications. The proper choice of a thickener and optimizing its level allows the coat-
ing’s rheology to be adjusted to meet the needs of the intended application. There are
three main classes of thickeners or rheology modifiers which are commonly used in
emulsion polymer coatings: Cellulosic (a class of modified natural products, usually
hydroxy ethyl cellulose, or HEC), HASE (a class of synthetic polymers termed hy-
drophobically modified alkali swellable emulsions) and HEUR (a class of synthetic
polymers termed hydrophobically modified ethylene oxide urethanes). Cellulosics
are relatively high molecular weight water soluble polymers which thicken by raising
the viscosity of the water phase of the coating. HEC polymers were one of the origi-
nal materials utilized for thickening water based coatings and they are still in com-
mon use, primarily in low sheen decorative coating applications. HASE thickeners
are high molecular weight emulsion polymers which are activated, or swelled, by
neutralization with a base such as ammonia. In contrast to conventional HEC, the
HASE polymer backbone is modified by pendant hydrophobic functional groups,

which can associate with hydrophobes from other thickener molecules, hydrophobes
from surfactant molecules, and with hydrophobic domains on the surface of the
emulsion polymer particles. This hydrophobic association gives HASE thickeners
improved efficiency, and helps them resist volume exclusion flocculation, an unde-
sirable aggregation process associated with high molecular weight, non-associating
polymers. HASE thickeners are cost effective and they are used in a variety of deco-
rative coating applications. However, the alkali swellable component of their compo-
sition can increase the water sensitivity of a film, and they are not generally preferred
for demanding exterior applications. HEUR thickeners are also hydrophobically
modified synthetic polymers, but they are lower in molecular weight (50 000 g mol–1)
and do not have the alkali swellable component of the HASE thickeners. Because of
their lower molecular weight and associative character, HEUR thickeners make a
positive contribution to the colloidal stability of a coating. They are particularly use-
ful for demanding applications of decorative and protective coatings where higher
gloss, water resistance, and effective barrier properties are needed. Again, coating
manufactures careful optimize the rheology modifier package in order to ensure that
the coating applies correctly, and that it meets the appearance and performance
needs of the intended application.
Opacifying aids are frequently included in coating formulations to enhance the
hiding performance of TiO2. At low TiO2 levels, the opacity or hiding power of a coat-
ing increases linearly with TiO2 content up to about 10 PVC. Above this level, indi-
vidual TiO2 particles begin to crowd or interfere with each other, and while total hid-
ing continues to rise, hiding efficiency (hiding scaled to the amount of TiO2) starts to
fall off. In spite of this decrease in efficiency, coatings manufacturers generally uti-
lize TiO2 levels in the range of 15–25 PVC to provide adequate wet and dry film opac-
ity. Opacifying aids work by improving TiO2 efficiency, and thereby allow coating
manufacturers to reduce formulated raw material costs while maintaining hiding
performance.
Common opacifying aids fall into two main classes: hollow sphere particles and
small particle size extenders. Hollow sphere particles are sub-micron sized hollow
polymer beads which enhance TiO2 hiding in the dry film by bringing a low index of
refraction air void in close proximity to the TiO2 particle. (In the wet state before the
film dries, the central air void is filled with water, and the hiding contribution is sub-
stantially reduced.) The air void effectively increases the difference in refractive index
between the TiO2 scattering centers and their surrounding medium, thereby in-
creasing scattering efficiency and improving hiding. Since TiO2 levels are usually re-
duced when hollow sphere opacifying aids are utilized, hiding efficiency is also im-
proved through a reduction in TiO2 crowding. Hollow sphere particles also make a
direct contribution to hiding, because their central air voids provide a certain amount
of intrinsic scattering to the dry film.
Figure 6-2 presents a transmission electron micrograph of a commercial hollow
sphere opacifying aid. The sample is presented as seen from above, with the polymer
shells appearing as a dark rings and the voids as the lighter cores. The particle size is
quite uniform with particle diameters of roughly 300 nm.
Fig. 6.2 Transmission Elec-

tron Micrograph of a Hollow
Sphere Opacifying Aid. Sample
was prepared by diluting poly-
mer dispersion with water and
then drying a small quantity on
an electron microscope sample
grid. Contrast was increased by
staining with RuO4. Particles
are approximately 300 nm in
diameter. Polymer shells
appear as dark rings, and the
hollow cores appear as the
light areas within the rings.
Small particle size extenders are the other class of opacifying aids; acting as spac-
ers, they increase the average distance between TiO2 particles in a film, thereby re-
ducing crowding effects. The primary particle size of these specialized extenders is
quite small (typically <0.5 µm), and the colloidal components of a coating need to be
properly formulated and stabilized in order for these materials to work effectively.
Biocides protect coatings from attack by microbial organisms. In the wet state, wa-
ter based coatings possess the basic ingredients needed to support microbial growth:
water, a source of carbon and nitrogen, and trace minerals. The use of anti-microbial
agents, or biocides, is generally required to prevent water based paints from spoiling
while being transported and stored. A variety of materials are used as in-can preserv-
atives for water based coatings; in general, preservatives used in these applications
are electrophilic compounds which function by reacting with nucleophilic groups
within the cell or on the cell surface, thereby disrupting the function of vital cellular
components. Isothiazolones, and materials based on formaldehyde are most often
used for this purpose, although other chemistries are used as well. Preservatives are
used at low levels and generally do not affect the performance properties of a coating,
unless they are inactivated and are unable perform their function.
Paint film mildewcides are commonly used in exterior coatings formulations to
prevent defacement of the coating surface by mold and mildew. The surface of an ex-
terior coating can accumulate nutrient compounds from the local environment; they
may leach out from the substrate, or they may be deposited by rain or from the at-
mosphere. These materials, and the coating itself, support microbial growth on the
paint film surface. The microbial growth process can eventually lead to unsightly
mildew and algae growth on the coating surface, seriously affecting decorative per-
formance, and in severe cases, causing deterioration of the film itself. Coatings
based on vinyl emulsion polymers have better resistance to microbial growth than
traditional alkyd coatings, but paint film mildewcides are usually included in exteri-
or formulations to provide additional protection. (Apparently, the natural oil compo-
nents of alkyd resins make them more readily metabolized by microorganisms, lead-
ing to poorer intrinsic mildew resistance.) In the past, paint film mildewcides based
on organomercury compounds provided cost effective protection in emulsion poly-

mer coatings, but environmental and health concerns now strongly limit their use.
Modern organic mildewcides have significantly improved environmental risk pro-
files; they partition strongly into the polymeric domains of the coating, and if they
are released into the environment by the weathering process, they are present at ex-
tremely low concentrations so that they can be broken down and metabolized by mi-
croorganisms in the soil. The most common organic paint film mildewcides in use
today are based on iodopropynylcarbamate, isothiazolone and chlorothalonil
chemistries. Over the life of a film, these biocides slowly diffuse to the coating sur-
face where they act to control microbial growth. Combinations of organic biocides
are sometimes used to provide increased protection against a broad spectrum of mi-
croorganisms, and formulators commonly include zinc oxide in order to provide
longer term protection from mildew growth. Used properly, modern paint film
mildewcides offer a safe and cost effective means to significantly extend the service
life of exterior coatings.
Defoamers are used to prevent or to dissipate foam in coatings based on emulsion
polymers. Small air bubbles can be introduced into the liquid coating during the
manufacturing or application processes. If these bubbles are stabilized or long lived,
they can interfere with the efficiency of manufacturing, or leave unwanted voids in
the dried film. Unfortunately, the surfactants which are used in the manufacture of
emulsion polymers and water based coatings can also act to stabilize foam. De-
foamers are used in a formulation to destabilize and to speed the breakup of foam in
the liquid coating. They are generally hydrocarbon or silicone based dispersions or
emulsions which have limited compatibility with both the water and polymer phases
of the coating. This marginal incompatibility is an important factor in defoamer ef-
fectiveness, and it must be properly balanced or it can result in film defects or loss of
activity. While typically used at low levels (<1 % by weight), defoamers can signifi-
cantly enhance the paint manufacturing process, as well as improving the applica-
tion, appearance and performance characteristics of a coating.
Wetting aids are used to improve the ability of water based coatings to form defect
free films over a variety of substrates. Pure water has a high surface tension,
73 mN m–1 [9], and while the surfactants present in a water based coating can reduce
this to values in the 25–30 mN m–1 range, this may not be adequate to allow proper
wetting (and thus adhesion) to low surface energy substrates such as plastics or cer-
tain re-paint surfaces. Also, surfactants can potentially interact with all the colloidal
materials in a coating formulation (pigments, extenders, thickeners and defoamers)
this can affect the amount of free surfactant available to reduce the surface tension.
The equilibrated surface tension of a formulated coating will ultimately depend on
the complex distribution of surfactants molecules between these colloidal particles,
the water phase and the coating surface, and the judicious use of wetting aids can be
used to supplement colloidal stability and to promote proper wetting of the sub-
strate. Typically wetting aids are surfactants or very low molecular weight oligomeric
polymers. A wide variety of non-ionic and ionic surfactants are used, including hy-
drocarbon and silicone based materials. They are generally selected by a combina-
tion of previous experience and direct testing. Different wetting aids are used to ad-
6.3 Decorative Coatings 137
dress a variety of coating problems, including poor substrate adhesion, poor flow and
leveling and poor color acceptance. While typically used at low levels (<1 %), they can
play a vital role in enabling water based coatings to meet specific appearance and
performance requirements.
6.3
Decorative Coatings
The primary role of decorative coatings is to enhance the esthetic appeal of homes,
offices and other architectural structures by providing color, texture and sheen to
interior and exterior surfaces. Decorative coatings are commonly classified by their
intended application, and these include interior wall, interior trim, exterior wall and
exterior trim. The sheen level of the coating is also commonly characterized, and
these terms include flat, semi-gloss and gloss. These distinctions are not rigid
or comprehensive, and coating manufactures commonly break these classes down
further, or combine them, in order to enhance the marketability of their products.
There are also many kinds of more specialized decorative coatings, such as masonry
finishes, clear and stain finishes for wood, floor paints for masonry and wood, drive-
way sealers and arts and crafts finishes. Space limitations prevent a detailed discus-
sion of these specialized coating applications, but much of the information we pres-
ent here can be easily adapted to these coatings.
6.3.1
Emulsion Polymers in Decorative Coatings
The history of decorative coatings is long one, arguably extending back to prehistoric
times with paintings on the walls of cave dwellings. Focusing on more recent times,
solvent borne drying oils and alkyds were the predominant polymer technologies
used throughout most of the twentieth century. However, rising environmental and
health concerns, coupled with improvements in the performance of emulsion poly-
mer coatings, have allowed water based coatings to move into the leading positions
in the decorative application areas. While emulsion polymers are now the market
leaders in most decorative applications, there are still a variety of technical issues
which remain to be addressed by both raw material suppliers and paint manufactur-
ers. Clearly, regulatory pressure to drive down VOC emissions continues to increase
throughout the world, and the challenges of balancing the often conflicting objec-
tives of product cost, product performance and product differentiation remain.
6.3.2
Polymer Compositions used for Emulsion-based Decorative Coatings
A variety of thermoplastic emulsion polymers are used in decorative coating applica-

tions, with VA-BAs, EVAs, styrene acrylics, and acrylics being most popular. VA-BAs,
EVAs and styrene acrylics are commonly used for interior flat wall coatings, with the
choices between them generally based on regional economic and performance char-
acteristics. Acrylics and styrene acrylics are the preferred chemistries for exterior
applications, again with regional economic factors and performance characteristics
driving specific choices. Acrylics and styrene acrylics are both used for interior and
exterior gloss and semi-gloss applications, while for interior semi-gloss applications,
VA-BAs, acrylics and styrene acrylics are commonly used. These are generalizations,
and the specific choices made by paint formulators are based on a complex mixture
of factors, including regional custom, local availability, raw material cost, and specif-
ic performance needs.
6.3.3
Regional Distinctions in Decorative Coatings
There are significant regional distinctions in the formulation of decorative coatings.

Differences in building materials and, consequently, the substrates to which coat-
ings are commonly applied, underlie many of these distinctions. For example, North
America (NA), Australia – New Zealand (ANZ) and Scandinavia all have relatively
high levels of wood substrates, whereas masonry substrates are more common in
Europe, Latin America (LA) and Asia. Substrate differences are a major factor in the
preference of acrylics for exterior wood applications in NA, ANZ and Scandinavia,
the use of elastomeric wall coatings for masonry applications in Europe, and the
choice of styrene acrylics for masonry applications in LA and Asia.
The availability of supplies of low cost monomers is another important factor af-
fecting the choice of polymer composition; this drives the use of VA-BA polymers for
the low cost interior flat segments of NA and ANZ, and the use of styrene acrylics for
decorative segments in Europe and Asia. In Latin America, decorative paints are
commonly designed for both interior and exterior applications, and styrene acrylics
and VA-BA polymers predominate in these markets. Regional economic factors also
influence the choice of polymer used in coating applications: differences in raw ma-
terial costs, and in labor costs, can affect how end users balance the higher initial
costs associated using a more durable, high performance coating, versus the higher
deferred costs associated with using a less durable coating having a more frequent
re-paint cycle.
6.3.4
Market Size of Decorative Coatings
Decorative coatings, as defined here, account for roughly 40 % of worldwide coatings

production. The ratio can vary from country to country; heavily industrialized coun-
tries have a relatively higher proportion of protective and product finishes, while less
industrialized countries often have a higher proportion of decorative finishes. Start-
ing with the world wide coating production estimate of 20 billion liters per year [1],
and taking the fraction of decorative finishes to be 40 %, would give the total produc-
tion of decorative coatings to be roughly 8 billion liters per year worldwide. Assum-
ing that about 50 % of this is based on emulsion polymer technology leads to an esti-
mated annual production of about 4 billion liters of water-based decorative coatings

world wide. We estimate the North American market to be a third of this value or
about 1.5 billion liters per year. If we estimate the average retail selling price to be
$4–5 US per liter, this gives a total NA market value of $6–8 billion US per year for
decorative coatings. The volume of the European decorative coating market is rough-
ly comparable in size to the North American market. Taking the annual European
production estimate to be also 1.5 billion liters per year, and assuming an average
retail selling price of roughly 4–5 Euros per liter, would give a total European market
value of about 6–8 billion Euros per year for decorative coatings. Again it is impor-
tant to emphasize that these are very rough estimates, and are intended to give the
reader a general picture of market size.
6.4
Interior Decorative Coatings
Interior decorative paints are designed to provide texture, sheen and color to the in-
terior walls and ceilings of homes and offices. Paints based on emulsion polymer
technology now account for most of this segment. The popularity of water based
paints in interior decorative applications is due to many factors, including their ease
of use, low odor, fast dry, good appearance and color stability, and the ease of soap
and water clean-up. Paints for this application are designed for a variety of specific
applications such as kitchen and bath, wall, trim and ceiling; they also provide differ-
ent sheen levels such as flat, satin, semi-gloss and gloss. Coatings manufacturers
produce a wide variety products to meet the different needs of this large market seg-
ment, and this in turn requires a correspondingly large number of formulations and
raw materials. Because of space limitations, we will focus our discussion on two of
the major segments of the interior decorative market, flat interior wall paints and in-
terior trim enamels, and use them to highlight performance and formulation con-
cepts of this market segment.
6.4.1
Key Performance Features
Interior flat wall coatings have a low or “flat” sheen, and they are usually formulated
with an 85° gloss level below about 4 %. Low sheen levels are usually achieved by us-
ing large particle size extenders at relatively high PVCs. While low sheen levels help
to hide defects in the substrate, differences in sheen and color are readily observable
in these coatings, and thus sheen and color uniformity of the applied coating are key
performance attributes. Good application characteristics are important as well; inte-
rior flat wall paints are frequently spray applied in new construction applications,
and are generally applied by roller in re-paint applications. Formulating with asso-
ciative thickeners (typically HASE) can help reduce roller splatter, an important char-
acteristic in re-paint applications. End users expect decorative coating to have good
hiding characteristics, and while true one-coat hiding remains an elusive goal, coat-
ing manufacturers carefully balance hiding performance and cost in these formula-
tions. Interior flat coatings also need to have good cleanability characteristics, since
they are routinely applied to living areas (with higher potential for dirt and stains),
and the coating’s ability to be easily cleaned can add significantly to its service life
and user satisfaction.
Enamel coatings are frequently applied to trim surfaces such as doors, window
frames, decorative moldings around doors and windows, base boards, cupboards
and shelving. These surfaces often have a high level of day to day human contact and
a tougher, more resistant coating is needed to provide substrate protection, film in-
tegrity and optimum appearance characteristics. Trim enamels are frequently brush
applied so good flow and leveling characteristics are important. Enamels are gener-
ally formulated at higher sheen levels, with values for semi-gloss and gloss coatings
ranging from 30–85 % at 60°, respectively. They are applied over a variety of sub-
strates, including aged alkyd, aged water based enamels, primed wood or metal, and
thus they must have good adhesion characteristics. It is also desirable that the coat-
ing’s hardness develop quickly so that objects can be placed on painted surfaces
without marking the film. Trim enamels should also have good block resistance so
that adjacent painted surfaces can be pressed into contact without sticking to each
other. Finally, because they are applied in high use areas such as doors, windows and
kitchen areas, trim enamels need good stain resistance and cleanability.
6.4.2
Interior Decorative Coating Formulations
Flat Interior Wall Coatings

Cost is one of the most important factors for interior flat coatings and drives many of
the choices in formulations and raw materials. Vinyl acetate and styrene based
copolymers are most frequently used as binders for this market and cost considera-
tions also drive the use of relatively high levels of low cost extenders. Thus, PVCs are
generally high, and are usually above CPVC. Opacifying aids are commonly used to
help achieve high hiding levels, and they also help to lower raw material costs by re-
ducing TiO2 levels. Rheology modifiers are chosen to provide the desired rheology
profile, with HASE and cellulosic thickeners being most commonly used. A coalesc-
ing agent is usually included to enhance film formation, although recently developed
binders for interior flat coatings can often be formulated with very little or no added
coalescent. Propylene glycol is commonly used as a pigment grinding aid, and to im-
prove the freeze thaw resistance of the wet paint during storage. Finally, anionic and
non-ionic surfactants are commonly added to optimize colloidal stability and en-
hance color development and uniformity. Table 6-1 provides an example of a typical
interior flat coating formulation.
Interior Enamels
Polymer performance plays a more significant role in the formulation of enamel
coatings than in flat coatings, since the polymer component makes up a higher vol-
ume fraction of the dried film. Acrylic and styrene acrylic emulsion polymers are
Tab. 6-1 Interior decorative flat formulation.
Material Weight % Comments
Grind Prepare in a high speed disperser

Water 13.56
Propylene Glycol 4.07 Grind and freeze-thaw aid
Dispersant 0.52 Polyacid
Defoamer 0.18 Hydrocarbon dispersion
Biocide 0.16 Isothiazolone preservative
Aminomethylpropanol 0.18 Base, grind aid
Titanium Dioxide 10.73 Interior grade
Calcined Clay Extender 13.65
Calcium Carbonate Extender 9.04 Coarse grade
Grind sub-total 52.09
Let down Add to grind with good agitation

VA-BA Emulsion Polymer 19.72 55 % Solids
Hollow Sphere Opacifying Aid 6.84
Coalescent 1.34 Ester alcohol, film formation
Water 16.58
HEUR Thickener 1.72 25 % solids
Ammonia (28 %) 0.18 Base
HASE Thickener 1.36 Emulsion
Total 100.00
Property Value
Total PVC 63 %
Volume Solids 33 %
Weight Solids 47 %
most commonly used in this segment, with vinyl acrylics playing a role in the lower
performance/lower cost end of the market. Performance considerations limit the
PVCs of these coatings, and enamels are formulated significantly below critical PVC,
generally in the range of 15–25 % PVC. Extenders and opacifying aids are not com-
monly used in gloss enamel coatings, and are used to a limited extent in semi-gloss
coatings. HEUR and HASE thickeners are often used as rheology modifiers; they
provide excellent flow and leveling with brush application and generally allow for
higher gloss levels. The harder polymers used in enamel coatings generally require
higher levels of coalescing agents to provide good film formation. Again, anionic and
non-ionic surfactants are commonly added to optimize colloidal stability and en-
hance color development and uniformity. Table 6-2 provides an example of a typical
interior/exterior gloss enamel formulation.
Tab. 6-2 Interior/exterior decorative gloss enamel.

Propylene Glycol 3.36 Grinding aid
Water 2.43
Dispersant 1.12 Hydrophobically modified polyacid
Surfactant 0.10 Non-ionic pigment wetting aid
Defoamer 0.02 Silicone emulsion
Titanium Dioxide 21.28 Universal Grade

Acrylic Emulsion Polymer 50.67 Specialized gloss enamel vehicle
Water 15.16
Diethylene glycol butyl ether 0.58 Co-solvent
Coalescent 2.50 Ester alcohol, film formation
Phosphate Surfactant 0.09 Wetting Aid
HEUR Thickener A 2.36 20 % solids
HEUR Thickener B 0.19 25 % solids
Total 100.00
Property Value
Total PVC 21 %
Volume Solids 32 %
Weight Solids 45 %
6.4.3
Standard Application and Performance Tests
Many specialized tests have been developed to measure the application, appearance
and resistance properties of interior decorative coatings. The reader is referred to
the specific ASTM and ISO test methods given in Tab. 6-3, and the cited refer-
ences [13–14] for a more detailed description of test method protocols. Our objective
in this section, and in the subsequent application and performance test sections, will
be to identify the key performance features and to give the reader an overview of how
these tests are conducted.
Decorative coatings are often stored for long periods of time under sub-optimum
conditions before they are sold or applied. In the warmer regions of the world, coat-
ings are frequently stored in warehouses where temperatures can reach 45 °C for ex-
tended periods of time. In the colder regions of the world, coatings can be subjected
to repeated freeze-thaw cycling when stored at an unheated job site. Heat age and
freeze-thaw stability testing protocols have been developed to assess the storage sta-
bility of coating products. Heat Age Stability is tested by placing the paint in an oven
for a specific time and temperature, and then testing the coating for key performance
Tab. 6-3 Selected coating applications test methods.
Application test ASTM method* ISO method**
Freeze-thaw resistance D2243 1147

Heat age stability D1849
Low temperature film formation D3793
Gloss D523 2813
Color acceptance D5326
Hiding D344, D2805 2814, 6504
Block resistance D4946
Print resistance D2064 3678
Adhesion – qualitative D3359, D6677 2409
Adhesion – quantitative D2297, D4541 4624
Scrub resistance D2486, D4213 11998
Stain removal (top coat) D3450, D4828 4586
Stain blocking (tannin) D6686
Durability – exterior D660, D661, D662, D772, D3719, D4214 4628
Durability – accelerated D4141, G26, G53, G151 4892, 11341
Corrosion – exterior D610, D1014 4628
Corrosion – accelerated D2803, D4587, G85 7253, 11997
Tensile testing D2370
Permeability testing D1653 7783
Early washout (traffic paint) D 1640 – Modified
No pickup test (traffic paint) D711,D713
** ASTM test methods can be obtained from the ASTM web site – http://www.astm.org
** ISO test methods can be obtained from the ISO web site – http://www.iso.ch
properties. Many different time-temperature protocols are used; two common ones
are 10 days at 60 °C or 30 days at 50 °C. Freeze-thaw stability is tested by subjecting
the coating to repeated freeze-thaw cycles, typically 3–5 cycles of temperature
changes between –20 °C and room temperature; changes in viscosity and other key
performance properties are then evaluated.
Decorative coatings are commonly applied by brush, roller, or spray techniques,
and coatings manufacturers generally design their products to perform well when
applied by any of these methods. Testing protocols include laboratory testing under
carefully controlled conditions, and field trials under realistic application conditions.
The objective is to develop a coating which applies correctly, has a rheology profile
which allows good flow and leveling, without excessive sagging, and provides a uni-
form coating to the substrate. Application properties are particularly important with
products designed for professional painters, since these features are vital to reducing
call backs and maintaining high productivity.
Good initial appearance is an important factor in determining customer satisfac-
tion in any coating application, but is particularly vital for decorative finishes. The
applied coating is expected have the right color and the right sheen level. Defects in
the applied coating should be minimal, and easily repairable. A variety of standard-
ized laboratory instruments have been developed to measure sheen, hiding and col-
or development (Tab. 6-3). Also, many specialized tests have been developed to as-
sess appearance properties under specific application conditions. For example the
color rub-up test assesses the color variability of a coating when applied by brush or
roller application techniques. Since large interior wall areas are usually painted by
brush application around the perimeters, and then filled in by roller application to
the center sections, variations in color uniformity can have a significant impact on
end user satisfaction. In laboratory testing of this property, a draw-down of uniform
film thickness is first applied, and then a section of the coating is either rubbed with
the finger or brushed until the coating starts to dry. Color differences between the
low shear rate draw-down region and the high shear rate rub up or brushed region
are then assessed subjectively, or measured quantitatively with a color spectropho-
tometer. Problems in this area are generally related to poor colloidal stability; a light-
ly flocculated pigment dispersion can be temporarily dispersed by the high shear
conditions of brushing, and this can result in a color which appears different from
adjacent areas coated under the lower shear rate of roller application.
Resistance properties
In contrast to the appearance and applications properties of a coating, resistance
properties are not assessed by the user during and immediately after the application,
but rather, they impact user satisfaction by affecting the service life of the coating.
Laboratory testing plays a key role in assessing the resistance properties of coatings,
because it provides a controlled and accelerated measure of performance features
which may take years to become evident in actual end use applications. Adhesion is
a key performance factor and several tests have been developed to measure this pa-
rameter. All adhesion tests follow the general protocol of applying the test coating to
a defined substrate such as chalky or aged alkyd, steel or aluminum, allowing the
coating to dry for a specified time, and then testing the adhesion of the applied coat-
ing by attempting to separate it from the substrate. Adhesion can be tested under wet
or dry conditions (wet adhesion is usually a more severe test than dry adhesion), and
the coating is usually scored or cut in order to minimize the confounding effects of
film integrity. Cohesive failure occurs when the coating remains bound at the
film–substrate interface and separation occurs within the coatings itself, or by de-
struction of the substrate. This is generally indicative of good adhesion performance,
but it can sometimes be misinterpreted when a coating has extremely poor film in-
tegrity (giving a false positive reading). Adhesive failure occurs when the applied
coating separates from the substrate at the interface between the coating and the
substrate. Failures of this type can be assessed via subjective or quantitative meas-
urements, such as using knife peel, cross hatch/tape pull, or a quantitative measure-
ment of the force to peel. While it is desirable to have a coating exhibit cohesive fail-
ure in lab tests, coatings which exhibit adhesive failure often show good adhesion
performance in actual exposure testing. Experience and careful comparisons against
known standards are generally required in order to obtain useful performance pre-
dictions in these cases.
The cleanability of a coating is generally assessed by stain resistance or scrub tests.
In the stain resistance test, the coating is allowed to dry for a specified time (usually
a week) and then common staining materials such as coffee, tea, fruit juice, mustard,
ketchup, pencil, pen or felt tip marker are applied to the surface. After a specified
contact time, the coating is washed with a cleaning formulation and then is rated for
stain removal relative to controls. The scrub test assesses cleanability differently, and
measurers the ability of a coating to resist abrasion by a stiff brush and an abrasive
cleaner, or cleaning solution. A coating of defined thickness is applied to a vinyl
chart and dried for a specified time, usually a week. A specialized scrub testing ma-
chine is used to scrub the coating with a brush and a standardized abrasive medium.
The operator assesses the number of scrub cycles needed to wear through the coat-
ing to the substrate. In another variation of the scrub test, the test coating is placed in
the testing machine for a fixed number of cycles using either the abrasive medium or
a cleaning solution, and then cleaned and dried. Performance is assessed by meas-
uring the weight of coating lost during the scrub process. Both tests are subject to
high levels of variability and carefully controlled experiments are needed to produce
accurate and reproducible results.
Block resistance is a measure of a coating’s ability to resist destructive self adhe-
sion when placed into contact with itself. This is an important feature for coatings
which are applied to windows and doors, since in these components, painted sur-
faces are placed in contact in routine operation. Dry time and contact pressure are
important factors affecting block resistance and are the primary variables which are
controlled in laboratory testing. The coating is cast on a non-rigid substrate such as a
coated paper chart, and allowed to dry under controlled conditions for a specified
time (typically ranging from 8 h to 4 weeks). Small squares of the coated substrate
are then cut out and placed with the coated sides facing together. A defined pressure
(generally in the form of a 0.5 kg weight on a surface area of approximately 5 cm2) is
applied for a specified period of time and temperature (typically 12 h at 25 °C or 4 h
at 50 °C). The test squares are then pulled apart and rated subjectively for self adhe-
sion. Ideally, the two test squares separate with minimal force, leaving no film dam-
age. Failure is noted when the film is visibly damaged upon separation. In a variation
of this test, the coating can be applied to a rigid substrate such as glass or metal, and
these test areas are placed together, under pressure, as described above. The force
necessary to separate the test areas is then measured quantitatively.
The print resistance test measures the ability of a coating to resist permanent im-
printing caused by the placement of heavy objects, such as books or vases, on a hori-
zontal coated surface. In this test, a coating is cast onto a metal substrate, and then a
heavily textured object, such as a rough cloth is placed on the coated surface with a
defined pressure (typically about 1 kg per 5 cm2). The test is allowed to progress for a
specified time and temperature (usually one week at 25 °C, or one day at 50 °C), and
then the coating is evaluated subjectively against controls for its ability to resist per-
manent marking or defacement.
6.5
Exterior Decorative Coatings
Exterior decorative coatings are used to provide aesthetic and protective features to
the exterior walls and trim of houses, apartments and offices. They share many of
the application, appearance and resistance features characterizing interior decorative
coatings, with the obvious and important difference that they are expected to provide
these features while being subjected to the deleterious effects of UV radiation and
weathering. In addition, exterior decorative coatings are expected to protect their
substrates from the harmful effects of weathering for the lifetime of the coating.
Historically, alkyd and oil based coatings were commonly used in exterior decorative
applications, but over the past 30 years coatings based on emulsion polymers have
advanced and are now the preferred technology for this application. The primary
reason for this is the superior durability of acrylic emulsion polymers (and to a lesser
extent vinyl-acrylic and styrene-acrylic polymers) in exterior applications. Alkyd and
oil based coatings rely on oxidative cure processes to develop resistance properties.
While the cure processes are quite efficient, they can eventually lead to film embrit-
tlement and subsequent cracking over dimensionally unstable substrates. Addition-
ally, most alkyd resins are made by the esterification of phthalic anhydride with un-
saturated fatty acids or natural drying oils. The UV absorption characteristics of
these materials make them quite susceptible to UV degradation, leading to poor tint
retention and premature chalking. Finally, the ester linkages of oil and alkyd based
coatings are susceptible to alkaline based hydrolysis, a polymer degradation process
which can be accelerated by the basic pH conditions present in many masonry appli-
cations, particularly over freshly prepared concrete. Acrylic based polymers are more
resistant to these different degradation processes and, consequently, have become
the performance standards for exterior decorative coatings.
6.5.1
Exterior durability is the key factor which differentiates the performance of exterior
decorative coatings. This is primarily manifested in three important areas: tint and
gloss retention – the ability of a coating to maintain its original color and gloss level
during exposure, chalk resistance – the ability of a coating to resist the surface pow-
dering caused by UV and moisture induced polymer degradation, and resistance to
cracking and adhesion loss – the ability of a coating to resist grain cracking and the
subsequent flaking and loss of adhesion when applied over wood substrates. Good
dirt pick-up resistance is also important; the coating should be resistant to darkening
caused by adsorption of dirt and soot from the external environment. Adhesion to a
variety of architectural substrates is also an important performance feature, particu-
larly in re-paint applications where weathered substrates present particular chal-
lenges. Because exterior coatings are generally viewed from a distance, appearance
properties such as flow and leveling are somewhat less important than they are in
many interior applications. Of course, most of the other performance features de-
6.5 Exterior Decorative Coatings 147
scribed above for interior decorative coatings also apply to their exterior counter-
parts.
6.5.2
Exterior Decorative Coating Formulations
Acrylic emulsion polymers are generally preferred for exterior decorative applica-
tions because of their good exterior durability characteristics. Styrene acrylics and
vinyl acrylics are also popular, particularly in regions of the world where lower labor
costs reduce the economic barrier to a more frequent re-paint cycle. In contrast to in-
terior flat paints, exterior flat paints are generally formulated below CPVC in order to
provide improved durability. Because good moisture resistance generally is required
for exterior applications, cellulosic and HEUR thickeners are generally chosen as
rheology modifiers for exterior applications; cellulosics are commonly used in exter-
ior flat formulations, while HEURs are commonly used in gloss and semi-gloss
formulations. Durable grades of TiO2, coated with inorganic materials to provide
improved UV resistance, are generally chosen for exterior applications. The choice of
extenders can also have a significant impact on the performance of exterior coatings.
Based on our experience, the tint retention and chalk resistance of exterior flat coat-
ings can be enhanced by favoring the use of coarse silica or nephiline syenite over
clays. Calcium carbonates generally have good tint retention, but they can degrade in
regions with acid rain, sometimes leading to poor dirt pick-up resistance. Carbonates
can also can show frosting (the appearance of a hard white exudate, visible on tinted
films) in horizontal face down applications. Finally, a paint film mildewcide is gen-
erally included in exterior formulations, particularly in flat and satin formulations, to
minimize mildew growth on the coating after application. A typical formulation for
an exterior flat decorative coating is given in Tab. 6-4.
6.5.3
Exterior exposure testing is the most direct and reliable method to evaluate the dura-
bility of exterior decorative coatings. The most representative and general exposure
protocol is to actually apply the coating to test homes or buildings, and to then evalu-
ate the performance over a long period of time. However, the cost and logistics of
such large scale trials limit their use, and the vast majority of exterior exposure test-
ing is done via controlled exposure experiments carried out at established exposure
sites around the world. Most raw material suppliers and many coating manufactur-
ers have set up their own exposure sites, or use commercial exposure services, to
provide this capability. A typical experimental design for an exposure experiment
would include experimental and control coatings which are applied, in replicate, to
test areas (on the order of 15 cm × 30 cm) over a variety of representative substrates.
The choice of substrates depends on the intended market segment and region, but
normally would include several different types of wood and masonry in both new
and re-paint applications. In the Northern hemisphere, South vertical exposures are
Tab. 6-4 Exterior decorative flat formulation.

Cellulosic Thickener (2.5 %) 10.71 HEC thickener
Water 7.17
KTPP 0.08 Co-dispersant
Non-Ionic Surfactant 0.08 Pigment wetting aid
Mildewcide 0.25 Isothiazolone mildewcide
Titanium Dioxide 21.09 Exterior universal grade
Zinc Oxide 2.11 Mildew protection
Nepheline Syenite Extender 16.87 Coarse grade
Functional Extender 0.42 Thixotropic clay

Acrylic Emulsion Polymer (60 %) 22.86 Enhanced adhesion to alkyd and
chalky re-paint
Ester Alcohol Coalescent 0.83 Film formation
Ethylene Glycol 0.25 Co-solvent and freeze-thaw aid
HEC Thickener 8.07 2.5 % in water
Water 7.17
Total 100.00
Property Value
Total PVC 50 %
Volume Solids 35 %
Weight Solids 54 %
commonly chosen to accentuate failure modes which are linked to UV exposure;

these include gloss loss, grain cracking, chalking and color fading. North vertical ex-
posures are used to evaluate mildew resistance and discoloration by dirt pick up.
Exterior exposure testing is not a rapid process; some failure modes can take sev-
eral years to develop. Exposures at South 45° can be used to accelerate failure modes
linked to UV radiation and moisture; this exposure angle increases the flux of UV
energy incident on the sample, as well as increasing the intensity and duration of
moisture contact brought about by the daily dew cycle and rain. However, 45° expo-
sures are generally uncommon in real world applications, and the data obtained
from these experiments should be interpreted with caution. By using specialized
exposure techniques such as: exposing samples at South 45°, selecting woods with
poor dimensional stability as substrates, and applying thinner layers of coating (one
coat applications), coatings scientists can accelerate the exposure testing process.
However, even with these methods, it can still take 2 years or more to develop a clear
picture of a coating’s durability characteristics.
6.6 Elastomeric Wall Coatings 149
Accelerating the process for assessing the durability of exterior coatings is of obvi-
ous interest to raw material suppliers, coating manufacturers and end users. This is
currently an area of active research and a variety of efforts are under way to improve
the predictive ability of accelerated weathering protocols [15]. While a variety of ex-
posure instruments and devices have been developed, and are commonly used to
provide accelerated exposure information, we have found that these instruments do
not always provide information consistent with exterior exposures. Accelerated expo-
sure devices have proven to be most useful when evaluating specific failure modes,
and comparing the performance of coatings of similar composition, applied over di-
mensionally stable substrates.
6.6
Elastomeric Wall Coatings
Specialized elastomeric wall coatings were first introduced into European markets in
the early 1980s. Their function is to enhance the appearance and durability of exteri-
or masonry surfaces present on large buildings such as apartments, hotels and of-
fices. These types of structures often have large uniform surfaces which can be dis-
figured by small cracks and fractures, caused by uneven thermal expansion and con-
traction. Elastomeric coatings improve the appearance of masonry surfaces by cover-
ing these small cracks with a smooth elastic film, and they enhance the durability of
masonry substrates by preventing the intrusion of water into these defects.
6.6.1
Elastomeric wall coatings are designed provide a high quality decorative and protec-
tive finish for large masonry surfaces. The elastic character of these coatings, along
with the use of thicker applied films, allows them to bridge cracks in the substrate
and to stretch and shrink with thermally driven building movement. Elastomeric
coatings also prevent the penetration of wind driven rain and water into the substrate
by sealing these cracks, thus improving the durability of the underlying masonry ma-
terial. Emulsion polymers used for elastomeric wall coatings generally have low Tg
(typically less than –20 °C) in order to provide the elastic character needed for effec-
tive crack bridging. The use of such soft polymers would normally lead to coatings
with poor dirt pick up resistance and tackiness, but proprietary technologies are usu-
ally employed to address these problems. Elastomeric coatings can significantly en-
hance the durability of many masonry surfaces, and because masonry construction
is widely used around the world, the use of elastomeric wall coatings has grown sig-
nificantly over the past 20 years.
6.6.2
Typical Elastomeric Wall Coating Formulations
Elastomeric coatings are formulated to yield tough films which maintain a balance of
tensile strength and elongation characteristics across a broad temperature range
(–10 to +30 °C). These coatings are generally formulated at relatively low PVCs (typi-
cally in the range of 30–45 %) to provide the dried film with good elasticity and bar-
rier properties. These coatings are formulated with relatively low levels of hiding pig-
ments, since thick coatings are generally utilized. They are usually extended with
fillers such as calcium carbonate. Volume solids are typically high, in the in range of
50 % to 60 %, in order to provide for thicker dried films. For optimum long-term per-
formance, it is recommended that the total dry film thickness be in the range of 300
to 500 µm, much thicker than typically used in architectural applications. Coatings of
this thickness need a carefully optimized rheology profile in order to prevent sagging
during the application and drying processes. Cellulosics, either alone or in combina-
tion with HEUR thickeners, are generally preferred for this application. An effective
paint film mildewcide is also need in order to prevent discoloration of the coating
surface by mildew growth. Elastomeric wall coatings are generally formulated to be
applied by professional painters using either roller or spray application techniques.
A typical elastomeric coating formulation is given in Tab. 6-5.
Tab. 6-5 Elastomeric wall coating formulation.
Grind Prepare with high speed disperser

Water 5.67
Ethylene Glycol 2.75 Grind aid and freeze-thaw
Dispersant 0.44 Polyacid
KTPP 0.09 Co-dispersant
Titanium Dioxide 6.20 Exterior Grade
Calcium Carbonate Extender 26.12 Fine grade
Zinc Oxide 2.21 Mildew protection

Surfactant 0.55 Wetting aid, non-ionic
Acrylic Emulsion Polymer 54.20 Specialized elastomeric vehicle
Mildewcide 0.18 Isothiazolone class
HEC Thickener 0.27 Solid
Water 0.89
Total 100.00
Property Value
Total PVC 31 %
Volume Solids 49 %
Weight Solids 61 %
6.6.3
The tensile and elongation properties of an elastomeric coating are important

performance features which characterize the coating’s ability to bridge cracks in the
substrate. These properties are commonly evaluated in the laboratory at ambient and
below ambient temperatures by use of a tensile testing instrument (Instron type or
equivalent). Testing is performed at a constant rate of jaw separation with load cells
adequate to measure the tensile forces generated. Testing sample dimensions are
usually about 500 µm thick × 2 cm long × 1 cm wide, and samples are cut with a die
from a dried film which was drawn down over a Teflon release plate. The sample is
fastened between the jaws of the tester and is stretched apart at a constant strain rate
until it breaks. Values for the percent elongation and tensile strength at break are
then calculated. These values depend somewhat on the strain rate used; generally,
lower strain rates yield higher values for elongation, coupled with lower values for
tensile strength at break.
The permeability of an elastomeric coating is crucial for determining whether the
coating will allow adequate passage of water vapor through the coating. In the labo-
ratory, permeability is evaluated by sealing a dried paint film of specified thickness
over a cup of water and placing the assembly in a constant temperature and humidi-
ty room. Water loss from the cup, through the film, is measured by mass difference
over the course of one week. Permeability is then calculated from the rate at which
water is lost through the film.
6.7
Primer Coatings
Primer coatings are used to provide a functional boundary layer between the sub-
strate and the topcoat. Coating manufacturers design a variety of specialized primers
to enhance total system performance for a variety of coating applications. Primers
generally provide many or all of the following features:
(i) they promote effective adhesion to a variety of substrates;
(ii) they prevent the transport of a variety of different types of colored stains from
the substrate to the topcoat;
(iii) they enhance corrosion resistance;
(iv) they serve as a flexible linkage between dimensionally unstable substrates and
the topcoat; and
(v) they reduce irregularities and imperfections in the substrate, providing a
smoother and more uniform surface for the topcoat.
Decorative and protective primers generally have demanding performance specifica-
tions, and are usually formulated at relatively low PVCs and high volume solids.
They usually are not designed to provide high hiding or intrinsic weathering resist-
ance, since the topcoat can be independently optimized to provide these and other
performance features.
6.7.1
Primer vehicles based on emulsion polymer technology were introduced in the

1970s and have shown a steady increase in market share over the past 30 years. They
are used in a variety of exterior and interior coating applications. Stain blocking
primers are one of the most popular types, and are used to prevent discoloration of
topcoats by a variety of materials, including tannin stains from wood, children’s
marker stains, water stains and nicotine stains. Water based primers generally block
the transport of stains by two principle mechanisms:
(i) the primer acts as a physical barrier and blocks the migration of stains from the
substrate to the topcoat (this is similar to the way in which solvent based primers
block stain transport); and
(ii) the primer is formulated with specialized ingredients, such as zinc oxide or oth-
er functionalized extenders, which lock (by interacting with) stain molecules into
the film.
While the stain may be visible at the surface of the primer coating after drying, it is
effectively locked into the film and does not lead to discoloration of the topcoat.
Binders for stain blocking primers are usually based on relatively hydrophobic emul-
sion polymers with acrylic or styrene acrylic compositions. Primers are expected to
have excellent adhesion, and water based primers are formulated to adhere to a vari-
ety of substrates including metal, wood, and chalky or aged re-paint surfaces. Since
this level of performance may not be needed, or achievable, in many topcoat formu-
lations, the use of specialized primers offers a flexible and cost effective way to meet
the performance needs of many different coating applications with a limited number
of optimized topcoat products.
6.7.2
Primer Formulations
Primers based on emulsion polymers typically are formulated with PVCs in the
range 25 to 45 % and volume solids in the range 30 to 40 %; lower PVCs and higher
volume solids formulations are preferred because these characteristics provide
tighter and more flexible films. Primer formulations frequently (but not always)
contain some type of reactive pigment or specialized extender to enhance per-
formance features: stain blocking primers frequently utilize functionalized exten-
ders to lock stains while anti-corrosive primers utilize reactive pigments to passivate
ferrous substrates. The performance characteristics of primers can be greatly affect-
ed by the choice of thickener and dispersant; HEUR rheology modifiers along with
relatively hydrophobic dispersants are generally preferred in this application. In gen-
eral, effective primers are formulated with a high degree of colloidal stability and re-
duced levels of water sensitive materials in order to improve performance character-
istics. Table 6-6 illustrates a typical formulation used in stain blocking primer appli-
cations.
Tab. 6-6 Stain blocking decorative primer formulation.

Water 4.90
Titanium Dioxide 14.67 Exterior grade
Dispersant 0.21 Acrylic acid type
Zinc Oxide 1.18 Functional extender – stain blocking

Acrylic Emulsion Polymer 65.16 Specialized primer vehicle
Ester Alcohol Coalescent 1.40 Film formation
Ethylene Glycol 2.73 Co-solvent and freeze-thaw aid
Biocide 0.19 Isothiazolone mildewcide
Thickener B 0.20 HASE (30 %)
Ammonia (28 %) 0.10 pH adjustment
Water 1.24
HEUR Thickener B 1.03 20 % solids
Total 100.00
Property Value
Total PVC 19 %
Volume Solids 37 %
Weight Solids 49 %
6.7.3
Application testing for stain blocking primers is focused on the ability of the primer
to block stains and to provide a suitable substrate for the topcoat. Laboratory testing
for tannin stain resistance is performed by applying the primers, along with a suit-
able topcoat, to wooden panels with high tannin levels such as western red cedar or
redwood. The panels are allowed to dry for a short time and they are then placed in a
high moisture environment such as a fog box or mist chamber. Because of the high
degree of panel to panel variability inherent with a natural substrate such as wood, a
careful experimental design (comparisons on the same panel, replication, etc.) is
needed to obtain meaningful results. After the panels are removed from the fog box
and allowed to dry, the performance is rated by a visual comparison against the con-
trols. Laboratory testing of marker stain resistance is done in a similar manner; the
performance of primer-topcoat combinations are evaluated for their ability to resist

discoloration relative to a set of pass and fail controls. Testing is usually carried out
with several water based and solvent based markers, which are applied to draw-down
charts. The trial primers are then drawn down over the test area, allowed to dry for a
short period (usually 2–4 h) and then coated with a suitable topcoat. Samples dry
overnight and are then rated relative to controls by a visual comparison.
6.8
Protective and Industrial Coatings
The distinctions between protective and decorative coatings are often a matter of de-
gree, and for our purposes, we will define protective and industrial finishes as coat-
ings which are applied to large industrial structures, such as bridges and factories, or
to products produced in an industrial production process. We will not include auto-
motive coatings in our current discussion, since they are covered in Chapter 7 of this
volume. Even with these limitations, there are a great number of different types of
application areas which use protective or industrial coatings; these include coatings
for industrial structures, machinery and equipment, metal containers, wood furni-
ture and flat stock, and more specialized applications such as coil coatings, marine
coatings and traffic marking coatings. The performance requirements of coatings
designed for protective and industrial applications are generally more demanding
than those of decorative coatings. Because of this, and the wide variety of applica-
tions, the shift to coatings based on waterborne emulsion polymers has not been as
pronounced as it has been in the decorative area. Solvent borne coatings are the his-
torical market leaders in protective and industrial coating markets, and they still hold
this position in most applications. However, new developments in polymer design
and formulation technologies have allowed waterborne finishes to make significant
inroads into many areas of protective and industrial coatings. This, coupled with an
increasingly stringent regulatory environment, has led to significant growth in the
use of waterborne coatings for these applications.
6.8.1
Copolymers used in Protective and Industrial Coatings
A variety of synthetic polymer resins are used in coatings for protective and industrial
finishes, with solvent-borne alkyds, acrylics, urethanes, epoxies and polyesters being
most common. Recently, high solids coatings (based on solvent borne polymers
designed for formulation with low levels of solvent) and powder coatings have also
made significant inroads into the protective and industrial coatings areas. In the con-
text of waterborne coatings, acrylic emulsion polymers are the most common com-
positions chosen for these applications, although significant amounts of waterborne
epoxies, polyurethanes and emulsified alkyds are also used. Acrylic emulsion poly-
mers for protective and industrial coating applications are generally designed with Tg
in the range 30 to 60 °C, significantly higher than binders used for decorative appli-
cations. Thermosetting acrylic systems, which utilize melamine or other types of

crosslinking chemistry, are also used in many factory applied, oven bake applica-
tions. Since most protective and industrial finishes are applied to dimensionally sta-
ble substrates, polymers with harder compositions can be utilized in order to provide
improved performance characteristics, without suffering the drawbacks usually as-
sociated with using higher Tg polymers in many decorative applications.
6.8.2
Market Size
Based on the analysis presented in the earlier sections of this chapter, coatings used
in protective and industrial (non-decorative) applications represent about 60 % of an-
nual world wide production, or roughly 12 billion liters per year. Assuming that au-
tomotive and other applications outside the traditional finish applications represent
roughly a third of this value, we estimate the world wide annual production to be ap-
proximately 8 billion liters per year for protective and industrial finishes, as we have
defined them. North American production is estimated to be about 1/4 to 1/3 of this
value, or roughly 2 to 3 billion liters per year. The penetration of waterborne coatings
has been less in these markets than in decorative areas; assuming a value of 25 %
yields an estimated annual production rate for waterborne protective and industrial
finishes to be on the order of 2 billion liters world wide, and 0.5–0.7 billion liters per
year in North America. Again, we emphasize the approximate nature of these esti-
mates and provide them to give the reader a general idea of market size.
6.8.3
Industrial Maintenance Coatings
Industrial maintenance coatings are designed to provide corrosion control and ex-
tend the service life of large metal and concrete structures associated with manufac-
turing, chemical processing and transportation. Typical applications include bridges,
storage towers, water tanks, chemical plants, oil refineries, water treatment plants,
and electrical power plants. Solvent borne coatings predominate in this high per-
formance application, with alkyds historically holding the largest share, and epoxies
and urethanes showing very good growth in recent decades due to their strong per-
formance profiles. The use of waterborne coatings in the light and medium duty
segments of this market has grown significantly over recent years, and we estimate
they now account for approximately 20 % of these segments in North America.
6.8.4
Early water based coatings for industrial maintenance applications utilized polymers
developed for exterior decorative coatings. Although these polymers provided good
gloss and tint retention in exterior applications, they were not optimized to provide
good corrosion or chemical resistance. Better barrier properties were needed to im-
prove these performance features, and specialized maintenance binders were devel-
oped by reducing polymer molecular weight (to promote improved film formation)
and utilizing more hydrophobic compositions (to provide better resistance to water
and ion transport). A properly balanced composition is needed for optimum per-
formance in maintenance applications; all acrylic polymers provide excellent dura-
bility characteristics, but are generally supplemented with more hydrophobic
monomers such as styrene or ethylhexyl acrylate in order to provide improved barri-
er properties and corrosion resistance. Acrylonitrile is sometimes incorporated in
order to improve chemical resistance, particularly in applications where resistance to
gasoline and aromatic solvents is desirable. Good colloidal stability is particularly
important in maintenance coatings; these coatings are often formulated with reac-
tive pigments which can be difficult to stabilize, resulting in reduced gloss, or poor
storage characteristics. In addition to these features, industrial maintenance coat-
ings should show good adhesion to metal substrates, good hardness development
and enamel-like resistance to marking and abrasion.
6.8.5
Formulation Characteristics for Industrial Maintenance Coatings
Industrial maintenance coatings are usually enamels, and are formulated in a man-
ner similar to decorative gloss enamels: they are formulated significantly below crit-
ical PVC in order to enhance gloss, barrier properties and toughness. Urethane rhe-
ology modifiers are generally used to provide a more Newtonian rheology profile
(good flow and leveling) as well as to avoid the weak flocculation and water sensitiv-
ity associated with cellulosic and HASE thickeners, respectively. A wide variety of
reactive pigments are often used to enhance corrosion resistance, particularly in
primer formulations. Many of these materials are inorganic salts, based on zinc,
calcium or barium cations with anions of phosphate, borate, or metaborate. Effective
coalescing agents are needed, since harder polymer compositions are generally used,
and a combination of two or more coalescing agents is often used to optimize film
formation, drying time and wetting characteristics. Finally, a variety of additives are
commonly included in these formulations; like decorative enamels, these can in-
clude dispersants and surfactants for pigment incorporation and stabilization, de-
foamers, mar aids to increase abrasion resistance and glycols for improved pigment
grinding and freeze-thaw stability. Table 6-7 illustrates a typical formulation used in
industrial maintenance applications.
6.8.6
Industrial maintenance coatings are evaluated by many of the standard stability, ap-
plication and resistance tests used for decorative coatings. Like decorative finishes,
they are applied in the field and need to have good heat-age and freeze-thaw stability.
They should also have good appearance and application properties, and are general-
ly evaluated for performance in spray, roller and brush application, as well as for
Tab. 6-7 Yellow industrial maintenance coating.

Water 5.34
Surfactant 0.21 Pigment wetting aid, non-ionic
Titanium Dioxide 6.94 Universal grade
Yellow Pigment 6.94 Yellow iron oxide
Premix Mix the following with good agitation

Styrene Acrylic Emulsion Polymer 68.51 Specialized maintenance vehicle
Ammonia (15 %) 0.32
Let down
Add the grind to the above premix,
then add the following ingredients Add with good agitation
Coalescent 4.48 Alkyl acetate ester
Propylene Glycol 1.07 Co-solvent, freeze-thaw aid
Methanol 3.73 Co-solvent, freeze-thaw aid
Sodium Nitrite (15 %) 0.96 Flash rust inhibitor
Thickener 0.25 HEUR (25 %)
Total 100.00
Property Value
Total PVC 11 %
Volume Solids 35 %
Weight Solids 44 %
gloss, and color uniformity. Like exterior decorative finishes, the exterior durability
of industrial maintenance coatings are commonly evaluated by exterior exposure
testing, with particular emphasis being placed on corrosion resistance, gloss reten-
tion and color retention. In contrast to most decorative finishes, industrial mainte-
nance coatings are also evaluated in the laboratory for corrosion resistance. Salt
spray and prohesion testing are commonly used and both of these techniques use
aqueous salt solutions and high humidity to accelerate the corrosion of steel test pan-
els. Samples are prepared by coating steel test panels with a film of defined thickness
and then drying for a specific time under controlled temperature and humidity con-
ditions. The test panels are then scribed to expose bare steel beneath a portion of the
coating, placed in the test chamber, and evaluated at periodic time intervals. Panels
are subjectively rated, relative to controls, for blistering and corrosion on the face and
at the scribe.
Salt spray and prohesion testing both suffer from the general problem discussed
above in regard to accelerated exposure testing: corrosion resistance in laboratory
tests does not always correlate well with performance in real world applications.
Laboratory corrosion tests use a combination of aqueous salt spray and high humid-
ity conditions to speed corrosion processes, and there is some question regarding
whether they actually accelerate corrosion processes present under normal use con-
ditions. Salt spray testing uses a high salt concentration (5 % NaCl by weight) and
100 % humidity at elevated temperature (35 °C) to provide a more aggressive testing
environment. Prohesion testing utilizes lower salt levels (0.35 % ammonium sulfate
and 0.05 % NaCl), and alternating cycles of salt spray and drying, at ambient tem-
perature and 35 °C, respectively, to provide a somewhat more realistic, but slower
evaluation. In spite of the simplicity and speed of these tests, it is generally acknowl-
edged that realistic exterior exposures, preferably in the form of trials on actual metal
structures such as bridges or storage tanks, are the best way to obtain useful infor-
mation regarding the corrosion resistance of industrial maintenance coatings.
6.9
Traffic Marking Paints
Traffic marking paints are used to control the flow of vehicle and pedestrian traffic
on a variety of surfaces such as roadways, parking lots, walkways and airport run-
ways. Since the late 1980s, waterborne traffic markings have enjoyed strong growth
in the United States and in parts of Europe and Asia. This is due not only to in-
creased environmental sensitivity, but also is due to improved performance features
which have been incorporated into waterborne acrylic emulsion polymers for traffic
marking paints. We estimate the total world wide market for traffic marking paints
to be around 400 million liters per year, with the North American market represent-
ing about 120 million liters of this total. Most of the traffic paint market in North
America has shifted over to waterborne technology and the share of water based traf-
fic coatings is now estimated to be greater than 80 %.
6.9.1
Description of Traffic Paint Market
Road-marking paints have been in use since the 1920s; however, traffic paint tech-
nologies have changed dramatically over this period. Early paints were based on oil-
modified phenol-formaldehyde resins, which were later replaced by alkyds or chlori-
nated rubber blends. In the early 1990s, the technology shifted toward more envi-
ronmentally friendly and higher performing waterborne acrylic systems. The en-
abling technology which allowed for the widespread use of waterborne traffic paints
was the development of fast drying acrylic emulsion polymers in the late 1980s.
These products use proprietary technology to provide waterborne traffic paints with
the ability to dry rapidly under a wide range of relative humidity and airflow condi-
tions. Due to their acrylic compositions, they also offer improved glass bead reten-
6.9 Traffic Marking Paints 159
tion, which leads to better retention of retro-reflectivity (the ability of a material to re-
flect light back towards the source from a variety of incidence angles) and nighttime
visibility.
6.9.2
The success or failure of road-marking paints depends on their ability to:

(i) dry quickly enough to prevent damage by traffic following the striping truck;
(ii) adhere to the road surface (concrete or asphalt) during the expected lifetime of
the coating; and
(iii) retain a large percentage of the glass beads applied to the coating surface for
nighttime visibility.
In addition, various governmental agencies can mandate specific requirements for
viscosity, color, VOC content, percent solids, opacity, etc.
6.9.3
Typical Traffic Paint Formulation
Formulations for waterborne traffic markings differ substantially from those of dec-
orative coatings. The volume solids of waterborne traffic paints are quite high,
around 60 %, in order to minimize the amount of water, and to thereby speed the
drying process. Traffic paints are also formulated near or above CPVC, in the range
of 55–60 %, to provide higher porosity and increased drying speed. They contain
many of the components found in the waterborne coatings discussed previously,
such as dispersants, defoamers, and rheology modifiers. As with any paint, these
components must be chosen with care so as to not detract from the desired perform-
ance characteristics. Table 6-8 illustrates a typical formulation for paint used in traf-
fic marking applications.
6.9.4
Fast drying is an important characteristic for traffic marking paints, and a modifica-
tion of the standard coating dry-through test (also called the early washout test) is
used to evaluate the time needed for a traffic paint to become resistant to washing off
with water (presumably rain). In this test, a draw-down with a film thickness of
330 µm wet is placed in a humidity chamber maintained at 90 % relative humidity
with negligible air flow. The dry-through time is defined as the time required for
there to be no surface deformation when the test operator’s thumb is twisted
through an arc of 90° with minimal pressure on the paint film. While the coating has
not dried in the conventional sense by this time (all moisture has not yet left the
film), the values obtained in the dry-through test provide a useful measure of the
time needed for a coating to become resistant to being washed away by rain.
Tab. 6-8 Traffic marking paint.

Acrylic Traffic Paint Emulsion 32.40 Utilizes rapid set technology
Dispersant 0.36 Ammonia neutralized, polyacid
Wetting Agent 0.20
Defoamer 0.21
Titanium Dioxide 7.11 White pigment
Let down Mix grind for 15 minutes, and add

with good agitation
Methanol 2.13 Co-solvent
Coalescent 1.31 Ester-alcohol, film formation
Defoamer 0.18 Hydrocarbon type
HEC Thickener 0.68 2.5 % in water.
Water 1.34
Total 100.00
Property Value
Total PVC: 60 %
Volume Solids: 61 %
Weight Solids: 78 %
A traffic marking paint also needs to quickly become resistant to tire pickup after
application to the roadway. This property is commonly evaluated in the laboratory by
the no-pick-up test. In this test, a steel cylinder, outfitted with rubber O-rings, is
rolled over the surface of the drying paint film at specified times. The no-pick-up
time is defined as the point at which paint does not adhere to the rubber rings when
the cylinder is rolled across the film. The auto-no-track test is a complementary field
evaluation method which also measures the time for a traffic marking paint to be-
come resistant to tire pickup. This test is carried out by passing a moving automobile
over a freshly applied transverse or diagonal marking line, and determining the min-
imum time required for there to be no indication of pick-up and re-deposition of the
line by an observer standing at a distance of 15 m.
Retro-reflectance is a quantitative measure of a traffic marking’s nighttime visibil-
ity. The retention of retro-reflectance is determined in the field, and is related to the
ability of a traffic marking paint to retain small, reflective glass beads which are
dropped onto the coating surface during the coating application process. It is meas-
ured either by a portable or truck-mounted retro-reflectomer. Often, specifications
will call for initial minimum values as well as some minimum throughout the life-
time of the marking. Requirements can vary, but typical initial values for white
markings are on the order of 250 mcd m–2 lux–1 while yellow markings are somewhat
less (ca. 150 mcd m–2 lux–1) owing to their lower TiO2 content.
161
References
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7
Applications for Automotive Coatings
Sunitha Grandhee
7.1
Introduction
The automotive coatings industry is faced with new challenges as we enter into the
new millennium. Environment legislation, cost and quality in addition to globaliza-
tion and market constraints are driving new developments. Increasingly stringent
environmental legislation and tougher market conditions require that modern coat-
ing systems must bring, not just enhanced product performance but also reduced
overall production costs to paint producers. Daimler-Chrysler, Ford and General Mo-
tors in the United States, has formed a consortium, the United States Council for
Automotive Research (USCAR) which now is the umbrella for 11 other research con-
sortia including the Low Emissions Paint Consortium (LEPC). LEPC is tackling the
technical challenge of developing paint-related technologies to reduce or eliminate
VOC from automotive coatings.
The movement towards lower to zero VOC involves many types of coatings tech-
nologies. Need to reduce VOC has led to change in many raw materials that were tra-
ditionally used in coatings. Furthermore, manufacturers often want their coatings
modified so that they can be used at faster production rates, baked at lower tempera-
tures, or changed in color.
An approach to this problem is by the appropriate modification of acrylic primary
dispersions to suit automotive coating requirements or solvent-free secondary dis-
persions of conventional resin types like epoxies, polyesters, polyurethanes. Today,
the latest water-borne coatings are much more robust in terms of usage or applica-
tion friendliness and require significantly less heating or air-conditioning than two
decades ago. They still require some additional dehydration or special kinds of flash-
es before going into ovens to help remove the water.
The biggest manufacturing industry in the world today is the auto industry, with
over seventy separate companies or subsidiaries, employing 4 million people. In the
United States over 15 million cars are produced annually. It is estimated that motor
vehicle production on a global basis will rise from 54.9 million in 1998 to some
59.3 million by 2003 [1].
164 7 Applications for Automotive Coatings
Europe
$8.9 B
Asia
$3.1 B
Africa, Middle East,

Latin America
$1.6 B
North America
$7.5 B
Fig. 7-1 Original equipment manufacturers (OEM) coatings demand

1999.
Demand for motor vehicle coatings is forecast to rise by 1.8 % per year to 2.0 mil-
lion metric tons by 2003, with OEM coatings posting 1.5 % growth per year to
1.2 million metric tons.
In 1999, Europe was the largest market for coatings for OEM end markets at
$8.9 billion. North America was second having used $7.5 billion in OEM end mar-
kets. Asia, with faster economic growth than Europe or North America, last year
spent $3.1 billion on OEM coatings (Fig. 7-1). The rest of the world, which includes
Africa, the Middle East, and Latin America, consumes $1.6 billion in OEM coatings,
according to P.G. Phillips. The market for automotive OEM coatings alone is growing
at 3.2 % per year [2].
7.1.1
History of Automotive Coating
The history of automotive paint dates back to the beginning of the 20th century,
when the mass production of automobiles started [3, 4]. Mixtures of ground pig-
ments and linseed oil – like old wood coatings used for carriages and stagecoaches –
were brushed on the surface and allowed to dry. The coating was then sanded
smooth and refinished in the same manner. These products were not colorful. Hen-
ry Ford always said, “You can have a car any color you like as long as it is black.” In
the 1920s nitrocellulose-based enamels were applied, offering a wider range of color
choices to the market.
During the early 30s the auto industry started using “stoving enamels” based on
alkyd resins. These enamels were selected to improve gloss and gloss retention. The
introduction of the spray gun technique made automotive coating much faster than
using the brush method. It minimized sanding between coatings and applied the
product evenly. Alkyds as a whole proved to be more durable and faster drying than
nitrocellulose enamels. This product and process was the system of choice for most
vehicle manufacturers until the 1950s [3, 4].
In the mid 1950s the next great technology leap happened. Acrylic lacquer, while
not markedly better in terms of performance qualities over alkyd enamels, did pos-
sess one outstanding trait: it was incredibly fast drying as compared to enamels of
the time. Automobile companies such as General Motors immediately saw the pro-
duction time savings as a real plus. The coating was applied to the vehicle surface
with a spray gun. At that point the product, still wet, contained a large amount of sol-
vents. Baking the vehicle in a large oven caused the solvents to evaporate and the
product to flow to a uniform smooth finish.
In 1960 the Ford Motor Company went back to the stoving methods. They did this
after realizing that consumers made a vehicle purchase using mainly their eyes:
“shiny sells”. Ford also decided that they liked many of the properties that the early
acrylic resins provided. They went to work with yet another new group of suppliers to
create “acrylic stoving enamels”. This product was also applied with a spray gun. It
had a very high gloss, was durable and was oven cured to produce a hard and color-
ful surface. Using polyisocyanates dramatically magnified and improved acrylic
enamel’s performance qualities like gloss, hardness, durability [3, 4].
Throughout the 50s and 60s, corrosion was the major cause limiting automobile’s
life span. Cationic electrodeposition of a protective coating was the major invention
in the late 1960s, eliminating corrosion as a major cause of automotive failure [5]. In
this process electrically charged paint particles are deposited from aqueous solution
onto metallic substrates by application of an electrical field. Today, 99 % of all vehi-
cles manufactured use some type of electrocoat process.
During the 1970s Japanese and European major paint companies developed the
next technology change, the application of two-coat acrylic painting systems:
basecoat/clearcoat. They were also successful at providing the consumer with
metallics or metal flake paints. German automakers influenced this change with
their color-plus-clear combinations on such premium vehicles as Mercedes Benz.
The technology is a one-stage acrylic flat basecoat followed immediately by a high
gloss urethane crosslinked clearcoat. This results in excellent durability to corrosion
and stone chips, and very high gloss [3, 4].
In the late 80s and early 90s new laws were enacted that governed the content and
application of paints. The amounts of volatile organic compounds (VOC) were low-
ered using water-borne binder systems. Automotive paint systems are now well
within VOC limits and comply with EPA standards for emissions. Today approxi-
mately 14 million vehicles are coated with water-borne technology each year. Out of
the 99 North American assembly plants, 33 plants are using water-borne based
coats [6]. The main suppliers of OEM coatings are PPG, Dupont, BASF, Nippon and
Kansai Paint company.
Another approach to VOC reduction is the use of powder coatings, however, there
is a lot of cost in converting existing spray booths to suit powder application. Hence,
a variation on this theme is to use slurries of powder in water as automotive
clearcoats. A new clearcoat system has been introduced, that offers zero emissions,
is powder dispersed, and is stabilized in water [7]. This method is used commercial-
ly by Daimler-Chrysler in Europe.
Bayer recently won the Presidential Green Chemistry Challenge Award for its two-
component water-borne polyurethane system. Generally, isocyanates, one of the raw
materials for polyurethanes, are unstable in water. Trying to make water the carrier
for isocyanates was no easy task. Bayer modified isocyanate molecules to stabilize
them in water, so customers can apply them together with polyols, just prior to paint-
ing, to make polyurethane coatings [8].
7.2
Automotive Coating Layers
Current automotive coatings are made up of a number of distinct layers (Fig. 7-2),
the coatings are either spray applied or electrodeposited.
Clearcoat
Basecoat
Primer
Electrocoat
(+) ( -)
Fig. 7-2 Automotive OEM

coating layers.
7.2.1
Spray Coating
OEM automotive coatings are those used for painting trucks and cars on fast moving
assembly lines. Stringent conditions are established for surface preparation, applica-
tion and curing. Typically the clearcoat, basecoat and primer are spray applied while
the electrocoat is electro-deposited by dip application. Drying and curing usually in-
volves energy input such as heat and UV radiation to produce coatings of higher
toughness, solvent resistance and uniformity of appearance. The layers should cure
to a desired finish and should have a wide tolerance for bake conditions. Low bake
temperatures are desired to save energy cost.
The various coating layers, with their thickness and functions, are shown in
Tab. 7-1.
Automobile bodies are generally fabricated from steel [9–11], therefore corrosion
protection is one of the most important functions of automotive coatings. After the
fabrication of the car body, the surface is coated (phosphate coating) by dipping into
Tab. 7-1 Function and typical thickness of automotive coating layers.
Layer Thickness Function
Clearcoat 40 µm Withstand solar radiation, atmospheric

pollution (acid rain, bird droppings,
aggressive chemicals like road salts and
caustic detergents)
Basecoat 15 µm Optimum appearance and long lasting color
Primer 35 µm Good adhesion and resistance to chipping
Electrocoat 20 µm Long-term corrosion protection
an aqueous solution containing primary zinc phosphate Zn2(H2PO4)2 as the major

component. For parts of the exterior, plastic and rubber components are used, which
in some cases are completely coated before assembly. The use of plastics as a substi-
tute for metals began accelerating in the 1970s to achieve a weight reduction in order
to improve fuel economy.
Polymers used as binder

Table 7-2 shows the emulsion polymers most often used in the various automotive
layers.
Tab. 7-2 Water-borne binders used for automotive coatings.
Coating Resin chemistry Dispersion Type
Electrocoat Epoxy-amine Secondary Cationic

Primer Polyesters Secondary Anionic
Basecoat Polyacrylics Secondary Anionic
Basecoat Polyacrylics Primary Anionic
Basecoat Polyesters Secondary Anionic
Basecoat Polyurethanes Secondary Anionic/nonionic
Basecoat Polyurethane-acrylics Secondary Anionic
Water-borne emulsion polymers are used in formulating automotive coatings for

electrocoat, primers and basecoats. Clearcoat polymers are primarily still solvent-
borne. A powder dispersed in water (powder slurry) has been developed as a binder
for clearcoats [7].
For the purpose of this chapter’s discussion, electrocoat, is not referred to as
primer since an additional layer is present before the vehicle is top coated. Most cur-
rent automotive passenger cars are coated with four coating layers in addition to the
phosphate coating, as shown in Fig. 7-2 and Tab. 7-1. Furthermore basecoat here, in
this chapter is referred to an independent layer, even though basecoat is considered
as part of the automotive topcoat system.
Automotive OEM coatings are thermosetting coatings, i.e. a chemically
crosslinked matrix is formed between the main resin molecules. This matrix cannot
be returned to its original form by use of solvent or heat.
Aqueous polymer dispersions used in automotive water-borne coatings are classi-

fied as:
– primary dispersions: polymerization is carried out in the presence of water by emul-
sion or mini emulsion polymerization.
– secondary dispersions: the polymer is synthesized in an organic solvent and later dis-
persed in water.
Based on the nature of the solubilizing group, the polymer is classified as anionic,
cationic or nonionic. The higher the concentration of the polar groups, the greater is
the solubility of the polymer. Incorporation of functional groups in the polymer
skeleton is necessary for stabilization in aqueous phase [12].
Formulation ingredients
The amounts of main ingredients present in a water-borne automotive coating for-
mulation are shown in Tab. 7-3; the functions of these ingredients are summarized
in Tab. 7-4.
Tab. 7-3 Main ingredients (%) of for automotive coatings, RCA: rheology control agent.
E-coat Primer Base coat

Metallic Solid color
Solids (resins, crosslinker(s), pigments) 17–24 35–45 23–25 25–30

Solvents 2– 3 5– 7 10–15 10–15
Additives (RCA, defoamer, wetting agents) 1– 2 2– 3 2– 3 2– 3
Water 71–80 45–58 57–65 52–63
Tab. 7-4 Function of ingredients in an automotive coating formulation.
Ingredient Function
Aqueous polymer dispersion Film formation, mechanical properties

Crosslinker Reacts with functional groups on main resin to form
crosslinked matrix
Pigment dispersion Provides color, hiding
Flake pigments Provides appearance effect
Solvents Reduces viscosity, controls rate of drying and film formation
UV absorber Inhibits degradation of film by sunlight
Catalyst Drives crosslinking reaction
Secondary resins Pigment dispersion, adhesion promotion
Antifoamer/defoamer Decrease foaming tendencies
Rheology control agents (RCA) Control leveling, sag, aligns aluminum flakes
(metallic basecoats)
Other additives Improve substrate wetting, flow, pop tolerance, etc.
Standard test methods

The standard test methods for automotive water-borne coatings are summarized in
Tab. 7-5.
Tab. 7-5 Test methods for automotive coatings.
Test Method Description
E-coat Stomer ASTM D562 Viscosity

Basecoat, primer ICI cone/plate ASTM D4287 Viscosity
Basecoat, primer Brookfield ASTM D2196 Viscosity
Basecoat, primer Ford viscosity ASTM D1200 Viscosity
Basecoat, primer Dip type ASTM 4212 Viscosity
E-coat, primer, Film build ASTM D1186, Thickness
basecoat ISO 7253,
ISO 4623
E-coat Salt spray resistance ASTM B117, Corrosion, J2334 preferred to
SAE J2334, B117
DIN 53167
E-coat, primer Gravelometer J 400 Chip resistance testing,
testing coating flexibility,
adhesion and overall
resistance to chipping
damage by stones
E-coat Hardness (pencil) ASTM D3363 Hardness
E-coat Impact (Gardner) ASTM D5420 Hardness
E-coat, primer, Humidity ASTM D1735, Adhesion and appearance.
basecoat ASTM D2247, Condensing humidity (D2247)
ASTM D4585, and water soak (D1735)
DIN 53209
Topcoat, primer UV SAE J2020 Appearance (gloss, cracking ,
chalking) Weathering test
Topcoat, primer Xenon lamp SAE J1960 Accelerated test to check
for gloss loss
Topcoat, primer Sunshine/ ASTM G 152 Accelerated test to check
carbon arc for gloss loss
Topcoat, primer Tape test ASTM D3359 Adhesion
Topcoat, primer Exposure SAE J 951 Durability, Florida exposure
Topcoat, primer Exposure SAE J 1976 Outdoor weathering of exterior
materials
The J tests were developed by the Society of Automotive engineers, USA (www.SAE.org)
The test methods for automotive layers are designed to stimulate conditions likely
to occur in the field and are of two types – appearance and performance. Appearance
includes gloss, distinctness of image, mottle, orange peel. Performance properties
include physical properties of hardness, flexibility, impact resistance, adhesion,
stone-chip resistance, cold crack resistance i.e. stability to extremes of temperature
and humidity, curing efficiency.
Polymer dispersions are applied as coating binder mainly in three of the four
layers: electrocoat, primer and basecoat. These layers are now described in more
detail.
7.2.2
Electrocoat
Electrocoat or e-coat or Elpo is the first pigmented coating layer, which is applied
over the phosphate coating of the fabricated car steel body. It serves as a bridge
between the metal and the overlaying coating layers. This coating layer is applied
in a dip application by cathodic electrodeposition to the steel automobile body. Dip
application has the advantage to fill the smallest recessed areas of the automobile
body. This complete coverage ensures excellent corrosion protection to the automo-
bile.
Cationic electrocoat applied by dipping process is used worldwide for coating au-
tobodies and its adoption in 1970s and 1980s led to major improvement in the corro-
sion resistance of cars. Until mid 1970, electrocoat was of the anodic type [13–15]. In
1976, PPG introduced the first cathodic primer, and this technology, with continu-
ous improvement, has become the standard of the automotive industry worldwide.
Combined with the more recent introduction of galvanized sheet metal, car manu-
facturers are now able to offer ten years warranties against corrosion.
Requirements
Current systems are characterized by excellent corrosion protection, good throwing
power and good filling properties at film thickness of ca. 20 µm.
Polymers used
The resins used in electrocoat, must have excellent hydrolytic stability and resistance
to salt accelerated corrosion and the chemical composition of the resin also allows
for excellent adhesion of the next coating layer. Most current cathodic systems are
based on modified epoxy resins containing amino groups. These are dispersed in
water by neutralizing the amino groups with organic acids such as formic, acetic or
lactic acid. Bisphenol A epoxy resins are reacted with polyamines to yield a resin with
amine and hydroxyl groups. The resulting polymer is reacted with a polyisocyanate,
which is partially blocked with an alcohol (e.g. 2-ethylhexyl alcohol). Salts are formed
with the amine groups with a low molecular weight carboxylic acid. The epoxy back-
bone is made flexible by various ways by incorporation of polyester and polyether
diols [16], acrylic grafts [17]; low-Tg aliphatic epoxies [18]; fatty acids [19] and fatty
monoepoxies [20].
The resins are crosslinked by blocked isocyanates, Mannich reactions or re-esteri-
fication. Blocked isocyanates which are used as crosslinking agent are stable in the
slightly acidic water system, whereas melamine formaldehyde resins are not. During
baking, the blocked isocyanate reacts with a hydroxyl group to form a urethane
crosslink. Amine-substituted resin binders provide greater corrosion protection for
steel, perhaps owing to strong interaction between the amine groups and the sub-
strate surface that increases wet adhesion, which is the most critical factor for corro-
sion protection.
Cationic polyurethane dispersions are obtained by incorporating tertiary amine
functionality into the backbone, either by introducing tertiary amine groups in the
diol, instead of a carboxylic group, followed by quaternization with an alkylating

agent or protonation with a suitable acid [21].
Other coating systems contain cationically modified copolymers obtained by poly-
merization of acrylic monomers in presence of unsaturated polyurethane macro-
monomer [22], and water-dilutable dispersions of cationically modified and urethane
modified methacrylic copolymers obtained by solution polymerization [23].
Composition
Most of the commercial cathodic electrocoat formulas are two-pack formulas
consisting of a pigment dispersion intermediate and the principal resin compo-
nents [24].
Pigment dispersion:
Aqueous dispersion resin (epoxy amine isocyanate adduct) 10–15 %
Extenders 20–30 %
Anticorrosive pigments 3–7 %
Organometallic oxides 1–2 %
Deionized water 65–46 %
Principal resin component:

Epoxy amine adduct 20–25 %
Crosslinker 10–12 %
Organic acid 0.5–1.0 %
Organic solvent 1–3 %
Deionized water 68–69 %
Pigments commonly used are titanium dioxide and extender pigments. Special
lead-containing pigments e.g. silicates are used as anticorrosive agents. Lead also cat-
alyzes the curing reaction, however the trend nowadays is eliminate lead from elec-
trocoat. Solvent content is low (typically less than 2 % based on total volume). The
solids content is ca. 20 %.
The application technique allows coating of complicated shapes and even internal
areas. A coating of uniform thickness is obtained after baking at 150–180 °C for ca.
20 min.
Application
The car body is coated on a production line by immersing the body in a tank con-
taining the aqueous primer dispersion and subjecting it to a direct current charge.
The applied voltage causes the dispersed particles and pigments to migrate to the car
body. As they are deposited, the consequent transfer of electrons provides an electri-
cally neutral film deposit. During the process electroendoosmosis occurs, squeezing
the water out of the deposited coating and leaving it in a firm state. With this process,
improved uniform coverage is achieved in recessed areas and on sharp edges as well
as on flat surfaces. The body is baked to coalesce and cure the primer film with much
less sagging occurring.
Electrocoat bath:
Coatings stable at a pH a little below 7 are preferred.
Viscosity: 20–50 mPa s at 25 °C
Bath solids: 15–25 % (1 h at 110 °C)
Water: 64 % Deionized water
Solvents: 1–4 % Organic solvent
Bath pH: 5.0–6.0
Bath conductivity (20 °C): 0.8–1.5 mS cm–1
Cure schedule at metal temperature: 165–170 °C for 20 min
7.2.3
Primer
Primer or primer surfacer is spray applied over the electrocoat before applying the
basecoat. The main function is to minimize surface roughness and improve adhe-
sion of the basecoat. The uniform thickness provided by the e-coat, makes it smooth
and glossy which makes the adhesion to basecoat very difficult. The primer also pro-
tects the light sensitive cathodic electrodeposition layer from exposure to light.
Historically the basic function for spray primers has been corrosion resistance and
preparation of a surface to receive a top coat. With the advent of electrocoat in the au-
tomotive industry corrosion resistance has become less of a issue for spray primers.
The corrosion function of spray primers has centered around protecting against
sanding cut throughs (sanding to bare metal) on the electrocoat primer. Presently
the main purpose of spray primer is the preparation of a surface to receive a top coat
(basecoat/clearcoat). Other properties that are presently of great concern for spray
primers are yellowing, adhesion, chip resistance, sandability, leveling, UV durability
and smoothness of the coating with respect to the surrounding coatings (electrocoat
and topcoat).
A current trend is to use color key primers; the colors are picked for use under a
group of top coats with related colors. A chip-resistant primer called anti-chip is fre-
quently applied over the electrocoat on the lower parts of the car body. It is designed
to be especially resistant to impact by stones thrown up from a road against the car
body.
Requirements
The primer must have good chip resistance and exterior durability. Weakness in the
layer will lead to UV radiation degradation causing loss of adhesion of primer to
basecoat/clearcoat and ultimately delamination.
Polymers used
The development of chip resistant water-borne primer-surfacers has benefited from
the use of predominantly water-borne polyester and polyester-polyurethane resins.
Polyesters which are dissolved or dispersed in water by neutralizing acid groups
with amines are crosslinked with a suitable melamine resin. Aqueous polyurethane
or acrylic modified polyurethane systems are also slowly entering the primer market.
Water-borne polyesters used for automotive coatings have both hydroxyl and car-
boxylic groups as terminal groups. Usual acid numbers are in the range of 35–60 mg
KOH g–1 resin, to give amine salt solutions in solvent that can be diluted with water
to give reasonable stable dispersions of aggregates of resin molecules swollen with
water and solvent. To give acid functionality, 2,2,-bis(hydroxymethyl)propionic acid
is used as one of the diol components. Hydrolytic stability is also affected by the
choice of the polyol. In addition to the steric effect, it has been shown that polyols
with low water solubility give polyesters that are more stable against hydrolysis
under basic conditions than those with higher water solubility, presumably because
the polymers are more hydrophobic.
Since many of the polymers are hydroxyl functional, they are cured with various
melamines and blocked isocyanates. The polymers are mainly stabilized in the water
phase by neutralization of anionic groups with amines which are volatile (di-
methylethanolamine, 2-amino-2-methyl-1-propanol).
To avoid emulsifiers, the polyesters are copolymerized with hydrophilic mono-
mers. In the case of linear high molecular weight polyesters, often sodium 5-sul-
foisophthalic acid, polyethylene glycol are copolymerized. However, the copolymer-
ization increases the melt viscosity and decreases water resistance and adhesion. Wa-
ter-borne polyesters which are of the acrylics-grafted type form stable aqueous dis-
persion. They consist of “core-shell” particles with a core of high molecular weight
polyester. Small particle diameters were obtained by use of polyesters having the
largest amount of unsaturated bonds unless gelation occurs [24–30]. Thermosetting
water based polyester resin coating composition prepared from polyalkadienediol
may be directly applied to wet electrodeposited coating [31].
Composition of primer
Primers are highly pigmented systems, containing titanium dioxide in combination
with extender pigments such as silicates or barium sulfate, carefully selected to im-
prove the paint attributes (leveling, sanding, humidity resistance). UV absorbers and
HALS stabilizers can be added to improve UV resistance. The pH of the system is
maintained between 7 and 8.
Application and testing

Primer coating are spray applied onto the electrocoated substrate. Typical wet phase
testing includes seed check, gloss, weight per gallon, viscosity, appearance, humidity
sensitivity, settling , impact resistance, topcoat adhesion, solvent resistance, filter-
ability and sand scratch telegraph. For the anti-chip-appearance, weight per gallon,
viscosity, solids, sag and solvent pop and gravelometer-chip resistance test are
used.
7.2.4
Basecoat
Basecoat is the layer which contains the color pigments. This layer is covered by the
transparent coating (clearcoat).
Basecoats – along with the clearcoat also called the topcoat system – form protec-
tive layers over the car body surface and are very important as decoration. They have
the characteristics of:
– full and deep gloss
– highly brilliant solid or metallic color effects
– long-lasting resistance against weather and chemical influences
– easy to repair and polish
In terms of appearance, a significant trend in automotive original equipment fin-
ishes has been influenced the dramatic growth in the use of basecoat-clearcoat fin-
ishes to replace single-stage pigmented topcoats. Basecoat-clearcoat finishes provide
a “wet” appearance, previously associated with European vehicles, in that the appear-
ance of the basecoat is enhanced by the transparent clearcoat. Because of the
smoothness of the surface and clarity of the film of the clearcoats, the gloss and dis-
tinctness of the image of these multi-stage finishes has been widely accepted as the
standard of appearance in both the automotive original equipment and refinish coat-
ings markets.
The basecoat/clearcoat system consists of a colored layer (basecoat) which is
overcoated after a brief flash off time with a protective layer of clearcoat. Both layers
are cured together at about 120–140 °C. The basecoat contains pigments which pro-
vide solid (straight) shades or metallic finishes. In order to reduce the emissions of
VOC, water-borne basecoats have been developed, which may contain only up to
20 % co-solvents.
Composition of basecoat
The pH of the system is maintained between 7.0 and 8.0. Approximately 10–15 % by
weight is comprised of solvents. The trend nowadays is to go with HAPS (Hazardous
Air PollutantS) compliant solvents like monoethers of propylene glycol. Solvents
help in achieving good flow and leveling of the coating after it is sprayed. They also
help in proper alignment of the metal flakes of a metallic coating. A UV absorber in
the top coat that strongly absorbs UV in the wavelength range of 290–380 nm also
helps to protect the primer from degradation. HALS stabilizers are added to improve
UV resistance. Water-borne basecoats contain crosslinker building a polymer net-
work and ensuring film stability and durability. Water-borne basecoats also contain
rheology modifiers e.g. polyurethane thickeners [32], polyacrylic acids [33] and pig-
ment like additives (metasilicates, colloidal silicon dioxide).
Metallic pigments are frequently incorporated into the basecoat to provide the ap-
pearance phenomenon known as the geometric metamerism or “color-travel”. Coat-
ings with geometric metamerism display different hue and brightness when viewed
at different angles. This effect is used by automotive stylists who specify metallic
basecoat–clearcoat finishes to draw viewers eye the subtle contrast in hue and bright-
ness found in styling lines and curvatures in the vehicle.
Even though, water-borne coatings have been the most popular approach to VOC
reduction and there has been a substantial reduction of solvents on going from
solvent-borne systems to water-borne systems, the trend now is to eliminate solvents
Solvent-borne basecoats Water-borne basecoats

Resin 22%
Resins 23%
Pigment
2% Pigment 2%
Organic
Solvent 12%
Water 63%
Organic Solvent 76%
Fig. 7-3 Solvent and water-borne basecoat compositions.
almost completely. Fig. 7-3 shows the differences in composition between solvent-
borne basecoats and water-borne basecoats.
Binders used
Anionic coatings systems for water-borne topcoats are emulsion polymers,
miniemulsion polymers, polyurethane dispersions, different types of dispersions of
acrylic resins in water and amino resins, water-borne polyesters, polyurethanes.
Many of the polymers are hydroxyl containing and cured with various melamines
and blocked isocyanates. The polymers are mainly stabilized in the water phase by
neutralization of anionic groups with volatile amines (2-amino-2-methyl-1-propanol).
Cross-linkers like aminoplast resins, alkoxy silanes, blocked epoxy resins, carbodi-
imides can be used.
Application and testing

Typically, line speeds for spray application of basecoats are lower in Europe com-
pared to United States. Furthermore, turbine pumps are used for circulation of wa-
ter-borne basecoats in United States, while piston pumps are used in Europe.
The main tests for basecoats paints are: solids content, viscosity, stability at room
temperature/hot box 43 °C/56 °C. Basecoat–clearcoat testing depends strongly upon
customer requirements, e.g. film failures (popping, cratering, seeding), flow and lev-
eling, color matching, gloss and effect (in case of metallic systems). There are differ-
ent stability tests: mechanical stability (hardness and flexibility) and stability against
environmental influences (rain, humidity, light, higher temperature). To test the sta-
bility of topcoats against the effects of weather (mainly sunlight, humidity, tempera-
ture and fallout against pollution) coated panels are exposed for several years in spe-
cial places (Florida, Arizona, Okinava, a southern Japanese isle and Alunga in north-
ern Australia). For trials, there is the possibility to run shorter test times in accelerat-
ed weather machines (weather-o-meter) which try to model the natural conditions.
There are many other requirements including: resistance to car brushes, bird drop-
pings, acid rain, sudden thunder showers on a car that has been sitting in the hot
sun, the impact of pieces of gravel striking the car, gasoline spillage and so on.
7.3
Properties of Water-borne Binders used for Automotive Coatings
7.3.1
Emulsion Polymers
Emulsion polymers are binders of choice for automotive water-borne basecoats ap-
plications, because of their low cost and processing requirements. A particularly
valuable element of acrylic emulsion polymer chemistry is the ability to incorporate
a broad range of functional chemical groups into the polymer chain via ester, amide
carbamate, derivatives of acrylic or methacrylic acid. These functional groups can
provide sites for crosslinking, adhesion, compatibility with other polymers, post-
polymerization reactions, biochemical activity, etc. Acrylic latexes are increasingly
becoming popular for basecoat automotive applications, because of their resistance
to photodegradation and low cost, in addition to their well-known features including
safe handling, low toxicity, low odor, and easy clean-up. A number of patents exist in
the literature, wherein core shell polymers have been suggested to be used for water-
borne basecoats. To achieve good flow properties, a low minimum film-forming
temperature, good stability to agitation and good adhesion to other coating layers,
multiphase emulsion polymers are used, where the latex particles are small in size,
the core material is hard and the shell is soft and the latter is made of strongly hy-
drophobic monomers and a relatively large proportion of monomers carrying car-
boxyl groups [34–36].
Acrylic core-shell polymers have been used as principal polymers for aqueous metal-
lic basecoat paints [37–40]. The anionic shell allows pseudoplastic flow behavior
which ensures parallel orientation of the aluminium pigments in the wet paint film.
This orientation and the low solids content are responsible for the metallic gloss and
high color flop (change in color observed on varying the viewing angle) of the base-
coats.
For thermoset automotive coatings cross-linkable polymer dispersions are
used [41–47]. Compositions containing methylol(meth)acrylamide can be used for
very low VOC water-borne coatings. Relatively low-Tg polymers that coalesce well
without coalescing solvents are applied and subsequent crosslinking will give the re-
quired film properties. Water-soluble or a water-dispersible alkylated melamine
formaldehyde crosslinking agent or a polymeric partially methylated melamine
formaldehyde resin having a degree of polymerization of approximately 1–3 are used
frequently. Such compositions have been used for automotive quality clear coat
and/or pigmented color coat for automobiles and for an automotive quality primer
composition [48]. Functionalized latexes in baked coatings can be crosslinked with
aminoplast resins, alkoxy silanes, blocked isocyanates, epoxy resins and many other
cross-linkers.
To improve the water resistance, branched vinyl esters with long hydrophobic
chains can be used [49].
Emulsion polymerization is carried out as a semi-continuous batch process [50].
The polymer particle size is between 50 and 500 nm.
7.3.2
Microgels
Microgels are used as rheology control agents (RCA) for solvent-borne basecoats and
clearcoats. They are crosslinked microparticles made by emulsion polymerization
using monomers like ethylene glycol dimethacrylate, allyl methacrylate or divinyl-
benzene. They are insoluble in the aqueous medium and are stable towards gross
flocculation. The chemical composition and degree of crosslinking of the microparti-
cle may be such that it has a Tg below room temperature in which case the mi-
croparticles will be rubbery in nature, alternatively, it may be such that the Tg is
above room temperature, that is to say the particles will be hard and glassy. The poly-
mer micro-particles can be dispersed in the basecoat composition in a state in which,
even at low solids contents, the dispersion contains a few if any multi-particle aggre-
gates. The presence of the crosslinked polymer microparticles in the basecoat com-
position, confers upon the film derived from the latter, the desired ability to with-
stand subsequent application of the topcoat composition without disturbance of the
film or of the pigmentation, in particular metallic pigmentation, which it contains
and without which, therefore a successful basecoat/clearcoat system cannot be
achieved. Microgel dispersions having a pseudoplastic or thixotropic character have
been used for formulating metallic pigments in the basecoat composition. This gives
the advantage of the flip tone effect as well as the gloss to produce the ever popular
metallic finishes for the automotive industry [51].
7.3.3
Miniemulsions
Significant advances have been made in recent years in applying miniemulsions for
making water-borne polymers for the coating industry. Since the introduction of
miniemulsion polymerization in the early 1970s [52] many investigators have stud-
ied the subject and have used many different methods to prepare miniemul-
sions [53–57]. Miniemulsions are routinely prepared using some kind of high shear
device, in most cases this being an ultrasonifier or a microfluidizer [58].
Shork et al. have shown that incorporation of polyester into each acrylic latex parti-
cle, prepared via miniemulsion polymerization, leads to an effective in situ grafting
of the acrylic and polyester systems [59]. The hydrophobic nature of the polyester
resin makes it impossible to be accommodated by traditional emulsion polymeriza-
tion due to mass-transfer limitations in crossing the aqueous phase to micellar nu-
cleation sites. Thus, stable water-based latex coatings can be prepared that also have
the ability to cure (by crosslinking).The above hybrid miniemulsion polymerization
was successfully used to incorporate an oil modified polyurethane in the acrylic
droplets to give stable miniemulsions which were polymerized to give hybrid latex-
es [60, 61]. The hybrid polyurethane modified miniemulsion latexes have been suc-
cessfully used in formulating coatings for basecoats [62–64].
Additionally, miniemulsions made using a mixture of polyurethane and acrylic
monomers were used to make latexes using a semi-continuous feed. This technique
was successfully used to core-shell polymers for use in making water-borne
basecoats [64, 65]. Stable aqueous dispersion of polymeric microparticles containing
cellulose ester, and an acrylic polymer and a surfactant has been used for coating
compositions. These coating compositions have good leveling and flow characteris-
tics and exhibit good humidity resistance, appearance, adhesion and chip resistance
when used in a “low bake repair” process as well as a good automotive quality fin-
ish [66]. These dispersions of microparticles are produced by high stress dispersion
followed by polymerization of the vinyl monomers in the presence of cellulose ester
within the micro-particles.
7.3.4
Selection of Monomers, Initiators, and Surfactants
Glass transition temperature is usually the first design property considered for the
application. Hydrophilicity, hydrophobicity, acid-base properties, crosslinking ability
are other properties [67, 68]. Acrylic acid (AA) or the somewhat less water-soluble
methacrylic aid (MAA) are used in the order of 1–2 % (w/w) of the monomer charge.
The effects of acid monomers on stability and viscosity are maximized when they are
incorporated in the last part of the monomer feed and the polymerization medium is
acidic. Sometimes di- or tri-functional cross-linking monomers are included. To im-
prove acid rain etch resistance, carbamate functional monomers are included,
wherein the carbamate groups crosslink with melamine, used for clearcoats. The
aminoplast cured coating system combines acid resistance with excellent coating
properties providing protection against etching by acid rain [69].
The most common initiators are peroxydisulfate salts, especially ammonium per-
oxydisulfate. Thermal initiation is preferred to redox initiation. Whitening of films
may occur sometimes due to the hydrophilicity of the salts like ferrous thiosulfate. A
water soluble azo initiator 4,4′-azo-bis(cyanovaleric acid) has also been used for mak-
ing acrylic latexes [70].
Chain transfer agents are sometimes added to control the molecular weights and
the distribution. Latexes and coatings are stabilized by biocides or water-miscible sol-
vents to prevent microbiological contamination and deterioration [71]. Choice of sur-
factants are critical for automotive paint application due to their foaming tendency,
ability to impart water sensitivity to paint films and change gloss characteristics. Typ-
ically a low particle size in the range of 50–300 nm is preferred, so in general anion-
ic surfactants are used at levels of 0.5–2 % (w/w) based on polymer. Nonionic sur-
factants may be added in stabilizing the latex against coagulation during freeze-thaw
cycling making it less sensitive to coagulation by salts, less sensitive to changes in
pH. Choice of surfactant can also affect film formation temperature, since some
nonionic surfactants plasticize the latex polymer, leading to lower Tg and hence, a
lower temperature for coalescence. For example, nonylphenylethoxylate nonionic

surfactants with less than nine ethoxy units reduce film formation temperature as
compared to 20 to 40 ethoxylate units, but the higher ethoxylated surfactants are
more effective latex stabilizers [72].
7.3.5
Secondary Acrylic Dispersions
Automotive coatings containing acrylic resins as binders are well known. Organic
solvents used are generally alcohols, glycol ethers and other oxygen-containing
solvents that are soluble or miscible with water. Acrylic resins made in solvents (e.g.
1-(n-propoxy)-2-propanol, 2-butoxyethanol, butyl alcohols) are polymerized by free-
radical mechanisms. Typical monomers used are MMA/BA/BMA. Azo initiators are
typically used. Hydroxy monomers like HEMA, HEA are used, while acrylic acid
monomers are used to impart water solubility. After polymerization the carboxylic
acid groups are neutralized. Typically, these resins have acid numbers of 40–60 (acid
number is determined by titration and is defined as mg of KOH required to neutral-
ize 1 g of resin solids, equivalent weight equals 56 100/acid number). In the low-mo-
lecular-mass range (<6000 g mol–1), the Tg depends on the molecular mass. Subse-
quent cross-linking leads to an increase of Tg which is dependant on the cross-link-
ing density.
The choice of amine is crucial. 2-(dimethylamino)ethanol is widely used [73]. Ther-
moplastic latexes are of higher Tg (upwards of 60 °C) are used for higher toughness,
mar and chemical resistance, since heat is available for film formation. The hydrox-
ylic monomers can be incorporated for cure with melamine and isocyanate resins,
the carboxyl monomers can provide cure with epoxies, aziridines and carbodiimides.
7.3.6
Secondary Polyurethane Dispersions
Another important class of materials used for OEM coatings are aqueous
polyurethanes due to their versatility in their properties [74–80]. Since the introduc-
tion of polyurethane dispersions in 1960s, they have enjoyed considerable interest
and commercial acceptance. Polyurethane dispersions can be classified into three
main groups:
– non-ionic type;
– ionic type; and
– dispersions containing both the non-ionic and the ionic groups.
Anionic PU dispersions
In the first step of the synthesis, a conventional polyether- or polyester-based iso-
cyanate-terminated prepolymer is obtained by condensation polymerization of a diol
and a diol containing a carboxyl function, preferably reacting the hydroxyl groups of
dimethylol propionic acid with isocyanate groups. In the next step, the carboxyl
groups are neutralized with an amine which is subsequently dispersed in water and
chain extended in order to obtain high-molecular-weight materials by reacting with a

diamine in further steps. Aliphatic isocyanates are preferred, because beside confer-
ring good durability, they show lower reactivity with water and carboxylic groups.
Further aliphatic isocyanates favor very rapid reaction with diamines in the chain ex-
tension step. As neutralizing bases, tertiary amines are preferred compared to other
amines to prevent unwanted side reactions with isocyanates. A number of diols, iso-
cyanates and amine raw materials can be used to adjust the mechanical properties,
glass transition temperature and durability.
Non-ionic Dispersions
In the non-ionic types, the hydrophilic centers comprise of polyether chain seg-
ments [75, 81]. The different morphology exhibited by aqueous polyurethanes and
acrylics explains why the minimum film forming temperatures of polyurethane dis-
persions (PUD) are lower than that of acrylics with equal hardness [82]. Polyurethane
particles can exhibit core-shell morphology with the shell having higher molecular
weight and higher urea functionality than the core. This effect was found to be quite
pronounced with isophorone diisocyanate-based polyurethane dispersions [83]. A
two coat one bake coating process which does not give environmental problems has
been developed using aqueous PUD [84, 85].
Water-borne basecoats containing polyurethanes have been produced with a for-
mulation containing less than three pounds per gallon and lower temperatures than
solvent-borne systems [86]. Rapid-drying polyurethanes have been used for industri-
al finishing and automotive refinish with a well-balanced range of properties at low
VOC level. High-performance OEM-clearcoats have been produced with good chem-
ical resistance with excellent mar resistance. Some limitations of using anionic wa-
ter-borne polyurethanes are, volatile amines used to salt these carboxylic acid-func-
tional resins, which leaves during baking, thereby hindering the cure of the strong
acid-catalyzed acrylic-melamine clearcoats, resulting in wrinkled finish and loss of
DOI (Distinctness of image), and the limited rheological stability with metallic for-
mulations which contain certain rheology control agents. In certain formulations,
anionic PU resins have generally not given satisfactory application properties and
paint stability. In response to these limitations, nonionic polyurethane dispersions
were developed [87, 88].
Hybrid systems
The blending of resins is a simple and useful technique for improving paint proper-
ties. While water-borne acrylic resins and polyurethanes have been widely used as
polymers for automotive coatings, both water-borne resins are inferior to correspon-
ding solvent based counterparts because of hydrophilic functional groups or surfac-
tants which are introduced to impart dispersion stability to these resins. Table 7-6
shows some of the advantages and disadvantages of polyurethane and acrylic resins.
The most widely utilized technique for making hybrids is to free radically poly-
merize a combination of monomers in the presence of a pre-formed polymer which
may or may not be intrinsically dispersible. If the preformed polymer is water dis-
persible, it can be used directly as a seed for subsequent free radical polymerization.
7.4 Rheology 181
Tab. 7-6 Advantages and disadvantages of polyurethane and

acrylic resins.
Acrylics Hardness Toughness

Weatherability Mar resistance
Chemical resistance Elongation
Gloss
Affinity for pigments
Cost
Polyurethanes Mar resistance Cost
Elongation
Softness and adhesion
Urethane acrylic aqueous dispersions prepared by an acrylic polymerization in the

presence of an aqueous polyurethane can possess a range of advantages over the cor-
responding blends, e.g. reduced water sensitivity, ability to prepare in the cosolvent
form. Since polyurethanes are generally more hydrophilic than the acrylic copoly-
mer, the polyurethane concentrates at the particle surface. In a well designed system,
the particles coalesce on film formation to give a film with a continuous poly-
urethane phase. “Hybrid” acrylic-urethane latexes have been made by simultaneous
polymerization of acrylic monomers and chain extension of urethane prepolymers
giving structures similar to interpenetrating network polymers, with mechanical
properties exceeding those, if blended [89].
Combination of special emulsions, microgels and water-soluble resins have yield-
ed excellent aqueous binders for various coatings [25].
7.4
Rheology
A major concern in developing water-borne automotive coatings is to achieve a dis-

tinct rheology profile providing good sprayability, sag resistance and leveling proper-
ties, simultaneously. In low solids solvent-borne systems, controlling the rate of sol-
vent loss controls viscosity and sagging and metal flake orientation. In water-borne
systems rheology control agents (RCA) are added to control sag and flake orienta-
tion.
The viscosity of the paint must be very low at the spray gun in order to ensure a
good and uniform atomization. After the paint meets the car body, however its vis-
cosity needs to be very high so as to prevent sagging on vertical surfaces and cloud-
ing. The flow behavior of the aqueous basecoat therefore has to be adjusted by in-
cluding a rheology additive, the thickener, in the formulation. The paint must have a
good intrinsic viscosity, i.e. the viscosity must depend on the shear rate. With a high
shear force, such as is present at the nozzle during the spraying process, the viscosi-
ty needs to be very low. If the paint then meets the car body, it is virtually unaffected
by the shear strength and the viscosity must rise to very high values with almost the
same solids content so that the paint does not sag and the aluminum platelets do not
lose their alignment. A pseudoplastic (“shear thinning”) behavior is ideal for coating
materials. Viscosity is fairly high at low shear rates which avoids settling in the can
and gives good anti-sag properties. At higher shear rates, the viscosity is reduced
which allows easy handling and application of materials.
Interactions between thickener and latex particles in water-borne automotive coat-
ings and the corresponding microstructures were investigated using dynamic me-
chanical spectroscopy, cryo-replication, TEM and analytical ultracentrifuge tech-
niques [90].
Attempts to correlate various rheological parameters to good metallic appearance
have not been found to be successful [91]. However, in the case of four samples with
varying metallic flop index values, it has been observed that higher degree of pseudo-
plasticity led to a better flake orientation when compared to samples with lower
metallic flop index values. (Fig. 7-4)
Steady Shear Viscosity Profile
10000
Sample A
Viscosity [mPas]
Sample B
Sample C
1000
Sample D
100
Fig. 7-4 Viscosity ver-

sus shear rate, metallic
10 flop index values: sam-
1 10 100 1000 ple A 62, sample B 57,
sample C 58, sample
Shear Rate [1/s] D 49.
A Zeiss multiangle goniospectrophotometer MMK-111 with 45° illumination an-

gle was used to measure the lightness values of the basecoat/clearcoat film at differ-
ent angles. The degree of “travel” was estimated using the following mathematical
calculation [92]:
Metallic flop (MF) index = 50(L25 – L70)/L70
where L25 and L70 is the lightness value at 25° and 70° off of specular reflectance.
Specular reflectance is the reflectance of the incident light. When incident light falls
on the coating surface. Values of this parameter for basecoat/clearcoat typically
range from 45 for a coating with poor travel to 70 for a coating with very good metal-
lic flake orientation.
When light strikes a surface, some of the light penetrates where it can then be ab-
sorbed, scattered, or even transmitted if the layer is sufficiently thin. Nevertheless,
because of the change in refractive index between air and most substances, a certain
7.5 Crosslinking 183
proportion of the incident light is reflected directly from the surface. The angular
distribution of this light depends upon the nature of the surface but light that is re-
flected at the opposite angle to the incident light is called specular reflectance. Light
that is reflected by the substance itself is called body reflectance. Instead of examin-
ing the energy that passes through the sample, specular reflectance measures the en-
ergy that is reflected off the surface of a sample or its refractive index. By examining
the frequency bands in which the rate of change in the refractive index is high, users
can make assumptions regarding the absorbency of the sample.
Acrylic microgels have been developed that impart thixotropic flow using swollen
gel particles [52, 93–96]. Thixotropic agents are added to increase the viscosity at low
shear rates to minimize sagging [97, 98]. In the final film, the index of refraction of
the polymer from the microgel is nearly identical with that of the crosslinked acrylic
binder polymer so that light scattering does not interfere with color flop. The effect
of the gel particles depends on the interaction with the low molecular weight resin.
The rheological properties of the systems are discussed elsewhere [99].
7.5
Crosslinking
Thermoset coatings (chemically crosslinked film) play a very important role in the
automotive coatings industry. All coating layers uses resins which need to be
crosslinked. By crosslinking the resin used in the coating, many properties can be
greatly improved, such as hardness, mar resistance and solvent resistance.
Crosslinking reactions became important in the 1950s with the introduction of
acrylic resins in the automotive sector. A further impetus was given by increasingly
stringent environmental legislation. Lower solvent content and the replacement of
conventional solvent-borne paints by water-based paints meant that the molecular
mass of the binders had to be lowered to a range where the required paint properties
(film formation, hardness and flexibility) no longer exist. These properties therefore
had to be obtained by increasing the molecular mass by crosslinking after applica-
tion. Furthermore, the glass transition temperature and film hardness are increased,
the chemical reaction after application also provides advantages of high molecular
mass dispersions.
A widely used method of cross-linking paint films consists of reacting of hydroxyl
containing acrylates or carbamate containing acrylates with melamine-formaldehyde
resins or urea-formaldehyde resins [100–102]. Crosslinking is carried out at
ca.130 °C and is effected by acid catalysis (Fig. 7-5). The paints exhibit outstanding
gloss and durability [103].
The possibility of making cross-linkable latexes by emulsion polymerization in the
presence of etherified melamine-formaldehyde resins has been demonstrated by
Jones et al. [104]. Dynamic mechanical measurements showed that films from
slightly or moderately cross-linked particles behave like homogeneous networks in
the linear viscoelastic range [105]. Melamine formaldehyde cross-linkers have been
used with water-reducible acrylics, water-reducible polyester–polyurethanes and

acrylic latexes [106–109] in automotive water-borne basecoats.
A practical and effective crosslinking mechanism in cathodic electrocoating is
done with polyfunctional blocked isocyanates. The mechanism involves the reaction
of an isocyanate group (NCO) with the hydroxy group of the epoxy backbone and lib-
eration of the blocking group. Other crosslinking mechanisms that have been stud-
ied are use of addition polymers, Mannich bases, Michael adducts [110] sulfonium
stabilized polymers, transesterification reaction of hydroxy, alkoxy, amido and ester
systems with hydroxy functional cathodic backbone (Fig. 7-5) [111–114].
Melamine-Hydroxyl reaction
R'
R'
N OR ROH
+ HO
N O
N N N N
N OR OR
H+ N
R' R'
Alkoxylated Hydroxyl-functional Melamine Ether
Melamine Acrylic
Isocyanate-Hydroxyl reaction
R NCO + HO
R
N O
Isocyanate Hydroxyl-functional
Urethane
Acrylic
Melamine-Carbamate reaction
OCNH2 OCNH2 O
OH
O O C O
N
250 F H
OR N
N N
OR OR
N N N
N N N
N N
N
Fig. 7-5 Crosslink reactions.

7.6 Application Properties 185
7.6
Application Properties
Water-borne coatings initially presented a number of difficulties. Water-borne vis-

cosity characteristics are distinctly different and application, film formation and dry-
ing behavior are dependant on humidity and phase distribution of solvents as well as
the usual factors of solids, temperature and air flow. Water-borne coatings them-
selves vary depending whether they are latexes, dispersion (semi-soluble) resins or a
combination of the two. On account of the viscosity anomaly, water-borne paints
based on water-soluble binders have a relatively low solids content (ca.30–40 %) and
require relatively large amounts of organic solvents (up to 15 %) to ensure water sol-
ubility and film formation. They also have the advantage of a broad drying spectrum
(physical, oven drying).
As a result of the particulate nature of the acrylic latex polymers, only low gloss
and, in some cases, only limited corrosion protection can be obtained. Water-borne
coatings based on dispersions can be applied by spraying, however they are of only
limited use for electrostatic coating and dipping applications due to their rapid dry-
ing properties. Aqueous dispersions generally contain a few per cent of high boiling
solvents which act as temporary plasticizers and lower the minimum film-forming
temperature, thus allowing film formation to occur. A film of sufficient hardness is
obtained only after complete evaporation of solvent, which may take up to several
days. The film may, however be somewhat hydrophilic due to the presence of car-
boxyl groups and emulsifier residues, this reduces its water resistance, gloss and
gloss retention.
Coating films formed from some water-soluble binders tend to be water-sensitive
because of their hydrophilic solubilizing groups. They can be formulated to have a
high gloss due to their good pigment wetting and stabilization. They can also have a
high level of corrosion protection, which depends on the corrosion-inhibiting pig-
ments used and the chemical nature of the binder. The latter determines adhesion to
the substrate and diffusion of water and oxygen through the paint film. In the case of
paints made from emulsion polymers, the required application viscosity of water-
borne emulsion paints is generally obtained by adding a small volume of water. The
evaporation behavior of polymer dispersions is similar to that of conventional sol-
vent-based paints.
In the production and application of water-borne paints, water is used as the sol-
vent or diluent. The physical properties of water and organic solvents differ. Some of
these properties have to be taken into account when water is used as a paint solvent.
The water molecules have a high dipole moment and associate with one another.
This means that water has a high boiling point and high latent heat of evaporation
despite its low molecular mass. This in turn results in fairly long evaporations or in
the need to supply energy in the form of heat to evaporate the water and dry the paint
film. The high dipole moment of water is also responsible for its high surface ten-
sion. With substrates having a low critical surface tension (e.g. plastics or unsatisfac-
torily greased metals) this leads to inadequate wetting, unsatisfactory edge covering,
and crater formation. Critical surface tension (at 20 °C) of water is 72.5 mN m–1.
Circulation studies of water-borne metallic basecoats demonstrate a few reasons

why specular reflectance is lost during circulation. The flow induced stress of circu-
lation reduces flake size and produces cycles in liquid surface tension. Surface ten-
sion in turn controls amount of picture framing and film thickness. If rust is present
in the circulation system, it can react with the paint resins, creating gel lumps which
under circulation trap the metal flake hindering flake alignment. Smaller flakes,
thicker film thickness and poor aluminium alignment all reduce specular re-
flectance within the sprayed basecoat paint film [109–115].
7.6.1
Metallic Effect
Typically in solvent-borne systems, the basecoat requires high solvent or low solids
content in order to achieve perfect orientation of aluminium flakes, which results in
the so-called flip effect. The key factor is the rapid rise in viscosity on the car which
results in the aluminum flakes effectively frozen in an orientation parallel to the sur-
face. The slower rate of evaporation of water means that a water-borne basecoat can-
not rely upon water evaporation to achieve his rapid viscosity rise. ICI, through its
patented microgel technology has managed to stimulate the rapid viscosity rise. The
microgel pseudoplastic rheology means that the paint at the spray gun tip behaves
like a thin liquid while the paint on the car panel is highly viscous. The microgel par-
ticles are acrylic-based and swell rapidly in the presence of small amounts of organic
co-solvents such as butyl cellusolve in alkaline solution e.g. pH 7.6. These are sup-
plied to the European and world automotive industry for production line applica-
tions. These basecoats are cured at 130–140 °C [116]. The lower film thickness of the
basecoat and the flash-off time required before applying the clear top coat reduces
the popping problem. Control of sagging during application requires that the water-
borne basecoat is shear thinning, which also reduces surface distortion during sub-
sequent application of the clear coat [117].
7.7
Environmental Aspects and Future Trends
Water-borne coatings for automotive applications have a broad application spec-

trum. The prospects for the increasing use of automotive water-borne coatings lies in
their economic advantages and in the possibility of reducing solvent emissions dur-
ing application to comply with legal requirements. Savings in organic solvents as
diluents, savings in insurance premiums, lower energy consumption in spray cab-
ins, ventilation zones, and drying ovens, all contribute to the overall economy of wa-
ter-borne coating materials. Water-borne coatings can generally be classed as less
toxicologically harmful than corresponding solvent-based paints. Nevertheless, lung-
penetrating paint mists (aerosols) of water-based paints present a health hazard and
appropriate protective measures (e.g. use of respirators) must be taken depending on
the workplace concentration. The main problems arise due to the relatively high
7.7 Environmental Aspects and Future Trends 187
freezing point, high surface tension and low evaporation rates of water compared to
organic solvents. Moreover the presence of water causes rusting problems of ferrous
substrates and also make the water-borne systems very prone to attach by microor-
ganisms. Although water-borne systems are not considered toxic, they require care-
ful selection of resin/binders and additives such as biocides, cosolvents, coalescing
agents, etc., in order to avoid toxicity caused by these components. Future approach-
es will encompass improvements in scratch and environmental etch resistance, bet-
ter color options, better performance features all at a lower cost to the manufacturer.
Acknowledgment
The author wish to thank BASF Coatings Division for their support in writing this
chapter.
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communication. 72 (1989) 139.
8
Applications in the Adhesives and Construction Industries
Dieter Urban and Luke Egan
8.1
Introduction
Adhesives are high-molecular-weight substances which bond materials to one an-

other without significantly changing their structure. The action of adhesives is based
on two key properties: they must firstly “wet” solid surfaces and adhere to them, and
secondly, they must be cohesive, i.e. have internal strength.
Adhesives of natural origin were mainly used prior to the beginning of the 20th
century and by early civilizations as long ago as 2000 BC. These included animal
glue, casein, natural rubber and starches. Today, specially developed adhesives based
on semi- or fully synthetic products are used for a wide variety of bonding applica-
tions (Fig. 8-1).
The development of synthetic adhesives paralleled the development of plastics
which began in 1845 with the nitration of cellulose to give cellulose nitrate, the first
semi-synthetic plastic, whose ethereal solution was used by the shoe industry in 1910
for bonding leather. The products discovered in 1872 by Adolf Baeyer by polycon-
densation of phenol with formaldehyde were the basis for the first fully synthetic
plastic, Bakelite, which was obtained by Bakeland in 1909 by thermally curing reac-
tive phenolic pre-condensates. But it was not until 1930 that phenol-formaldehydes
and urea-formaldehyde condensates developed by C. Goldschmidt in 1896 (Kaurit)
were used widely as adhesives.
Polymerization processes discovered in the 1920s resulted in a large number of
new thermoplastics and elastomers, of which, in particular, polychloroprene, and
polyisobutylene were used as the basis for new adhesive technologies. Polyurethanes
and epoxies – developed in the mid-1930s – further broadened the range of adhesive
raw materials.
Thermally stable plastics were more recently developed which enable adhesive
bonds that withstand temperatures up to 350 °C. Concurrent development of new
bonding technologies (e.g. sandwich construction) now makes it possible to adhere a
multitude of various materials to one another. As such, classical connection meth-
192 8 Applications in the Adhesives and Construction Industries
Natural adhesives
Animal glue
Gluten (hide glue, bone glue)
Casein
Blood albumin
Vegetable glue
Albumin, wheat, pectin
Starches, artificial gum
Natural gum, gum arabic, tragacanth
Natural rubber, gum rosin, natural resins (colophony)
Synthetic adhesives
Physical binders
Bonding by evaporation (water- and solvent-borne adhesives)
Cellulose ester, cellulose ether
Synthetic rubber (polychloroprene, copolymers of butadiene with acrylonitrile or
styrene)
Copolymers of acrylics, vinyl esters, vinyl ethers
Derivatives of natural rubber (chlorinated or cyclized rubber)
Polyurethane elastomers
Bonding by cooling (hot melt)
Ethylene copolymers
Polyalkylene terephthalate
Polyamide
Butadiene or isoprene based block copolymers
Chemical reacting adhesives
Urethanes, epoxides, silicones
Urea, melamine, and phenolic resins
Cyanoacrylate, (meth)acrylates
Fig. 8-1 Synthetic and natural adhesive raw materials.
ods, such as welding, riveting, screwing, sewing, etc., continue to be replaced by ad-
hesive bonding techniques.
Adhesive bonding has now become a routine joining method in a host of various
industries – including automobile, furniture, shoe, construction and packaging. A
particularly impressive example of new adhesive technology is in aircraft and rocket
construction, where supporting structures are adhesively bonded on assembly
lines [1–9].
In Western Europe, about 1.5 million tons of adhesives (dry weight) were used in
1996 [10] compared to 2.3 million tons in North America [11]. The world market in
1996 for adhesives and sealants was about US$ 21 billion compared to approximate-
ly US$ 6.4 billion in North America [11].
8.2
Pressure-sensitive Adhesives
Pressure sensitive adhesives (PSA) are highly viscous, viscoelastic liquids which ad-
here to virtually all surfaces when pressed down gently. They are used in manufac-
turing “easy to apply” self-adhesive products, such as labels and tapes. Pressure sen-
sitive adhesives typically have permanent tack and adequate cohesion, so that further
curing operations after applying the tape or label are generally unnecessary.
The first self-adhesive products were adhesive plasters [12], which were developed
in the USA in 1845 by the medical doctor H.H. Day [13] and in Germany in 1882 by
P. Beiersdorf [14]. The use of self-adhesive tapes for industrial purposes marked the
beginning of “dry-adhesion” technology. A new branch of industry began to coat var-
ious support materials with pressure sensitive adhesives and to make self-adhesive
products from them. In 1935, R.S. Avery [15] invented a coating unit for self-adhe-
sive paper labels using a wooden cigar box filled with an adhesive solution. The ad-
hesive dripped through holes cut in the bottom, on to a roll of paper that ran below.
This was probably the first curtain coating process.
Until the beginning of the 1970s, pressure sensitive articles were produced
mainly by coating from organic solutions. Solvent-based rubber/resin mixtures and
comparatively smaller amounts of acrylate solutions were processed almost exclu-
sively.
The first water-based acrylate dispersions were developed as long ago as the 1930s.
They were produced on an industrial scale for the first time at the beginning of the
1940s. However, acrylate dispersions for pressure sensitive adhesives were not intro-
duced into the market until the beginning of the 1950s. The first areas of application
were self-adhesive book binding and map protection films. It was then possible for
the first time to make flexible PVC films self-adhesive without the need for a primer.
This excellent property also made it possible to use dispersions for electrical insula-
tion tapes. The use of self-adhesive films in advertising applications (e.g. promotion-
al graphics, signs) began at virtually the same time. Furthermore, acrylate disper-
sions satisfied the demand for removability without leaving a residue.
A continuous increase in pressure sensitive adhesive dispersion production oc-
curred throughout 1960s. The rapid development of a number of new applications
accelerated this process. The crucial factor was the ground-breaking, systematic
work in the 1970s on high speed coatings technologies [16]. The development of new
application equipment and corresponding high-solids dispersions has enabled coat-
ing rates to be increased from less than 60 m min–1 to as high as 600–1000 m min–1
today.
As so often it occurs in new technical developments, completely unexpected
advantages became evident with newly developed acrylic dispersions. The inherent
properties of polyacrylates made by emulsion polymerization enabled hitherto
unknown speeds during down-stream converting operations (i.e. slitting, die cutting
and stripping). It was also found that existing “solvent” coating units could be modi-
fied to permit economical processing of aqueous dispersions. This increased efforts
to use aqueous polyacrylate dispersions as pressure sensitive adhesives.
The total market demands for pressure sensitive adhesives (tapes and labels) is
about 300 000 tons of polymer in North America and about 200 000 tons in Europe.
Aqueous polymer dispersions have a share of about 30 % in North America and 40 %
in Europe. About 30 % in North America and 45 % in Europe are applied from
organic solution while hot melts have a share of 40 % in North America and 15 % in
Europe [17, 18].
8.2.1
Self-adhesive Labels
Self-adhesive labels (and decals) are pieces of paper, plastic film or metal foil coated
with pressure sensitive adhesives which adhere to any solid surfaces after removal
from a release liner. They are typically used to convey various kinds of information –
for example, product or package contents, barcodes, price stickers, instructions, and
technical data.
The most important adhesive raw material compositions for adhesive labels are
polyacrylate dispersions, styrene-butadiene rubber solutions, and styrene-butadiene-
styrene (SBS) and styrene-isoprene-styrene (SIS) hot-melt adhesives. Permanent and
removable UV-cross-linkable acrylic hot-melt adhesives have recently also been in-
troduced [19–22].
In the 1970s, Japanese paper label manufacturers started converting from rubber
solutions to water-borne systems because of very strict environmental protection reg-
ulations, resulting in acrylic dispersions becoming the most important group of PSA
raw materials in Japan. In North America, 85 % of the PSA label market was solvent
born in 1975 [23] but in 1991 approximately two-thirds of the market was water-
borne [24].
In Europe, the conversion was carried out in the 1980s and now the use of acrylic
dispersions in self-adhesive products is widespread and well advanced. The impor-
tance of acrylic dispersions continues to increase for reasons of environmental pro-
tection (nonflammable, no hazardous solvents), high solids contents, good aging re-
sistance, and excellent coating and processing properties.
About 2.9 billion m2 of self-adhesive labels were produced in Europe in 1996,
corresponding to 35 % of world production. At average application rates of 24 g m–2,
this corresponds to a demand for adhesives of 70 000 dry tons year–1 in Europe.
In North America 3.5 billion m2 of self adhesive labels were produced in 1999. As-
suming the same coating weight, the adhesive demand in North America was 84 000
dry tons year–1.
Polyacrylate dispersions
Adhesion and cohesion of polyacrylate dispersions can be varied over a broad range
and matched to many applications through the type and combination of low Tg (“soft”)
and high Tg (“hard”) monomers, the choice of auxiliaries, and the control of the
molecular weight and process parameters [26–29]. Some examples are given below.
The influence of glass transition temperature (Tg) of acrylic homopolymers on tack
(according to A. Zosel [30, 31]) at various temperatures is shown in Fig. 8-2.
Fig. 8-2Tack of polyacrylates as a function of composition and

temperature.
It can be seen that tack is greatest at temperatures 50–80 °C above the Tg of the
homopolymers. In addition, the tack increases with increasing hydrocarbon chain
length of the acrylic monomer. For use at room temperature, polyethylhexyl and
polybutyl acrylate have the greatest tack [27].
Besides polymer composition, the molecular weight of the polymer also affects ad-
hesion properties. A practical measure for assessing the average degree of polymer-
ization, in particular for process control, is Fikentscher’s K-value, which is obtained
by measuring the relative viscosity of a dilute polymer solution [32]. This characteris-
tic constant, which can be determined quickly and simply at a single concentration,
enables a rough estimate of the intrinsic viscosity and molecular weight [27].
The following measures may be used for varying degree of polymerization:
addition of a chain transfer agent, crosslinking additives, mixing high-molecular-
weight with low-molecular-weight components, and variation of the polymerization
process [27].
The following example is intended to clarify the effect of molecular weight. Acrylic
dispersions of identical composition, but of different K-value, varied through differ-
ent amounts of a chain-transfer agent, were investigated (Fig. 8-3) [27]. The peel
strength is low at very low K-values and high at a K-value of 50 (cohesive fracture). At
K-values above 50, the failure mechanism changes from cohesive into adhesive, and
the peel strength drops to a low value. If the K-value is increased further, the peel
strength drops slightly.
Substrate wetting and polymer cohesion strength are responsible for these results.
Although wetting is good at low K-values, the cohesion of the film is very low. The
higher the K-value, the higher the internal strength of the film and the worse the wet-
ting, i.e. the lower the tack or adhesion.
peel strength in N / 2 cm peel rate 300 mm / min
20
cohesion failure
adhesion failure
15
10
0
20 50 80 K-value
Fig. 8-3 Peel strength as a function of molecular weight (K-value),
according to W. Druschke [27].
However, adhesion is not affected by the average molecular weight alone, but also
by the molecular weight distribution. This can be seen in Fig. 8-4, which shows the
peel strength in N / 2 cm peel rate 300 mm / min
20
cohesion failure
adhesion failure
15
10
0
10:0 8:2 6:4 4:6 2:8 0:10
lower/higher molecular weight component
Fig. 8-4 Peel strength as a function of the content of high-molecular-
weight component, according to W. Druschke [27].
peel strength of various mixtures of relatively high molecular weight acrylic polymer
(K-value ca. 90) with low molecular weight material having the same composition
(K-value ca. 55). With increasing content of high-molecular-weight component,
i.e. an increase in the average degree of polymerization, the transition from cohesive
to adhesive fracture occurs again with a sudden drop in the measured peel values.
The maximum peel strength is obtained at a high molecular weight component con-
tent of 80 % [27].
When an acrylic dispersion with good low temperature peel strength (A) is mixed
with one having high cohesive strength (B), the actual performance of the mixtures
can deviate strongly from a linear mixing relationship. As Fig. 8-5 shows, the shear
values are significantly reduced by small amounts of dispersion A and low tempera-
ture peel strength drops to zero at only 20 % of component B.
Fig. 8-5 Shear values at 20 °C and low temperature peel strength at

–23 °C depending on the mixing ratio of a high peel dispersion A and
a high shear dispersion B [33]
Interestingly, copolymerized functional monomers like acrylic acid, for example,

results in an increase in cohesion (Fig. 8-6) and produces a significant increase in the
shear strength.
The two contradictory requirements for high tack and needed internal strength
can be best achieved in polyacrylate dispersions when adhesive and cohesive compo-
nents are produced stepwise during the emulsion polymerization. The transfer of
free radicals to pre-formed polymer chains results in the formation of branches,
which crosslink on recombination. Crosslinking affects the viscoelastic behavior in
two ways: by slightly raising the glass transition temperature and by increasing the
modulus level above the glass transition region. It also reduces the mobility of the
crosslinked polymer chains. This behavior is pronounced in polyacrylates and can be
shear in min 1/2 inch x 1/2 inch, 500g Fig. 8-6 Shear strength as a
function of copolymerized
acrylic acid.
1 500
1 000
500
0
0 1 2
acrylic acid in pphm
used to improve cohesion. Adhesion can be improved using a chain transfer agent,
which suppresses crosslinking and produces lower molecular weights.
Figure 8-7 shows that even small amounts of chain transfer agent cause a signifi-
cant reduction in cohesion. The maximum peel strength is achieved at 0.2 pphm and
the maximum quick-stick (or loop tack) at 0.3 pphm of chain transfer agent. An opti-
peel (Cr) quick-stick (Cr) cohesion

[N/inch] [N/inch] [min]
300 mm/min 300 mm/min 1/2 x 1/2 inch, 500 g
peel strength in N / inch time in min

20 100
80
15
60
10
40
5
20
0 0
0 0,1 0,2 0,3 0,4 0,5
chain transfer agent in pphm
Fig. 8-7 Effect of the chain transfer agent on the adhesive properties of an
acrylic dispersion.
mum balance between plasticity and bond strength is clearly achieved at a certain
degree of crosslinking.
The polyacrylate dispersions optimized in this way for pressure sensitive ad-
hesives are produced and supplied with solids contents between 50 % and 70 %.
Average particle sizes are typically between 100 nm and 1000 nm. However, disper-
sions with a high solids content (> 60 %) and low viscosity (<500 mPa s) need to have
a bimodal or multimodal particle size distributions. The viscosities of most commer-
cial products are generally between 10 and 1000 mPa s but high-viscosity dispersions
– greater than 10 000 mPa s – are also used in certain packaging applications. Poly-
mers used in pressure sensitive applications have glass transition temperatures of
between –60 and –20 °C.
Formulation modifications
Acrylate dispersions can be used directly in only a small number of applications.
Technical or economic considerations often make modification necessary [34]:
– optimization and refinement of the adhesion properties;
– production of a large number of self-adhesive products using a small number of
starting materials;
– optimization of the formulation from a commercial point of view; and
– matching of the viscosity, rheology and wetting behavior of the adhesive to the pro-
posed coating method and substrate.
This is generally done by mixing acrylic dispersions with one another, and adding
tackifying resins and plasticizers. Wetting agents, defoamers and thickeners are
added to adapt the adhesive to the prevailing coating conditions. Fillers or pigments
are used to color the adhesive material (e.g. brown adhesive tapes for packaging) or
to achieve special effects (e.g. zinc oxide in medical tapes).
Dispersion mixtures
In some self-adhesive products (for example, protective films), the goal is a weak tack
which does not increase after extended bonding times. These products are based on
special self-crosslinking acrylics. In order to improve the tack, cohesive products
with good tack are admixed. In certain applications requiring chemical resistance
(e.g. against plasticizers), a dispersion with superior resistance can be mixed in cer-
tain proportions to increase the overall formulation performance. In wet labeling ap-
plications (e.g. bottles), which previously used “natural adhesives” such as casein, a
blend of acrylic dispersions, natural latex, and wax dispersion have been employed.
Note that blends of acrylics and styrene-butadiene latex (SBR), for example, produce
dry films which are opaque – because of differences in refractive index. The formu-
lator can take advantage of this effect to impart opacity to a substrate. But it is im-
portant to note that when blending acrylics and SBR, water resistance of the dried
films can be affected in unexpected ways (Fig. 8-8).
70
60
Water Update (%, after 24hrs) 50
40
30
20
10
0
100/0 80/20 50/50 20/80 0/100
PSA Blend Ratio (Acrylate / SBR)
Fig. 8-8 Water resistance of dried PSA films depending on the blend ratio
acrylic/styrene-butadiene latex.
Addition of tackifying resins

Resins are used to improve the tack of pressure sensitive adhesives. They must be
compatible with the polymer (i.e. mixture has a single Tg) and modify its viscoelastic
properties resulting in improved polymer flow characteristics, substrate wetting, and
adhesive bond formation.
The most suitable products for improving the tack of polyacrylates are modified
natural resins, such as dimerized or hydrogenated gum rosins and esterified abietic
acids. With resins whose softening points are about 70 °C, pressure sensitive adhe-
sives with high shear strength but relatively low tack are obtained. If these resins are
combined with softer resins, the tack is significantly increased. Besides the general
increase in tack, addition of resin also specifically increases the adhesion to poly-
olefin surfaces. However, the addition of resin may impair the aging resistance of
the adhesive. Preferred applications for acrylate–resin combinations are paper labels
and double-sided adhesive tapes (for example, carpet laying tapes). Hydrocarbon
resins based on petroleum oil derivatives are preferred for tackifying styrene–butadi-
ene dispersions [24, 35].
To retain the advantage of the “solvent-free” feature offered by polymer disper-
sions, resin dispersions should be used instead of resin solutions. Resin dispersions
are available, for example, from Akzo Nobel/EKA Chemicals (Netherlands, USA),
DRT/ND Dispersions (France, USA), and Hercules (Germany, USA). However, it
should be noted that a resin dispersion generally reduces cohesion to a greater extent
than does a resin solution – because of the surfactants present. In addition, the water
resistance, evident from blushing, is often reduced. Polymeric tackifier has been re-
ported to increase the elastic properties of a pressure sensitive adhesive resulting in
improved peel strengths, especially at high peel rates [36].
Addition of plasticizers
Plasticizers increase the flow properties of the adhesive film. This results in faster
wetting of the substrate surface to be bonded and consequently increases the initial
peel strength. This naturally occurs at the expense of cohesion and heat resistance.
In contrast to resins, which normally increase the Tg of the adhesive polymer, plasti-
cizers decrease the Tg and make the polymer softer. The tack-increasing effect of
resins can be augmented by addition of small amounts of plasticizers. Particularly in
the case of resins with high softening point that have a deadening action on the
adhesive, addition of a small amount of plasticizer results in a lowering of the soft-
ening point. A resin-plasticizer combination consequently increases the tack very
effectively. Small amounts of plasticizer (2–5 %) are frequently added to the acrylic
dispersions in order to obtain gentler removal.
The main plasticizers used are the classical plasticizers (i.e. phthalates such as
DOP, DBP and DIDP). Adipates are also suitable as polymeric plasticizers, but are
rarely used owing to price reasons and their somewhat lower compatibility. A special
polymeric plasticizer polypropylene glycol alkyl phenyl ether (Plastilit 3060) from
BASF, has extremely good compatibility with acrylate polymers and does not mi-
grate. This product has now proven highly successful in a number of applications
(including pressure sensitive adhesives, acrylic sealants and paints).
Thickening of pressure sensitive adhesive dispersions

Suitable protective colloids and thickeners include animal glues, gelatin, casein, veg-
etable gum, dextrins, enzymatically digested starches, alginates, cellulose derivatives
(methyl-, carboxymethyl- and hydroxyethylcellulose), polyvinyl alcohols, polyacrylic
acids, polyacrylamides and polyvinylpyrrolidones, amongst others. They increase the
viscosity and water retention, modify the rheology for optimum coatability and
speed, and in addition generally also improve the mechanical stability and compati-
bility of the dispersions with electrolytes and fillers. In order to achieve optimum re-
sults, precise metering and suitable selection and combination of the protective col-
loids and thickeners are necessary. Since the water resistance of polymer films from
dispersion decreases with increasing addition of thickener, the proportion of thick-
ener should always be minimized.
Addition of wetting agents

Thickened dispersions generally have little problem wetting various surfaces. Even
surfaces with extremely low surface tension, such as silicone paper and corona treat-
ed polyolefin film, can be wetted under the uniform pressure imparted by the liquid
adhesive on to the substrate during the coating operation. A high resistance to flow
(i.e. high viscosity) prevents subsequent dewetting and minimizes the occurrence of
coating flaws (e.g. fish eyes).
The situation is quite different, however, in high speed, low viscosity coating sys-
tems such as modern vario-gravure where the dispersion film, which is initially uni-
formly distributed on the surface, re-coalesces relatively quickly if its surface tension
is excessively high. In this case, the surface tension of the pressure sensitive adhe-
sive dispersion must be matched to that of the substrate to be coated (film or silicone
paper). This is achieved by adding corresponding surfactants, so-called wetting

agents. These surfactants naturally increase the risk of foaming and in some cases
increase the water sensitivity of the adhesive film. The amount added should again
be kept as low as possible. The sodium salt of a sulfosuccinic acid ester (Lumiten I-SC,
BASF, Aerosol OT70-PG, Cytec) is a relatively low-foaming surfactant whose partic-
ular effectiveness as wetting agent arises due to its tendency to migrate to newly
formed surfaces very quickly.
Addition of antifoams
Surfactants (emulsifiers and wetting agents) often cause foaming, which results in
coating defects particularly when operating at high speeds. This is prevented by ad-
dition of antifoams. The effectiveness of antifoams, for example higher alcohols,
non-ionogenic acetylenic compounds, or aliphatic hydrocarbons with non-ionogenic
constituents, varies depending on the other auxiliaries present in the formulation
and in addition can drop with increasing storage time. The antifoam may float, settle
or diffuse into the polymer and thus, is no longer available at the liquid–air interface
where it is needed. It is therefore recommended that the dilute antifoam only be
added immediately before processing or, even better, sprayed directly on to the foam
surface by means of an atomizer if needed.
It should be noted that excessive amounts can impair flow of the dispersion,
which rapidly results in flaws (pinholes, fisheyes) in the coating. A general rule of
thumb is that the amount of antifoam in initial experiments is 10 % of the amount of
wetting agent, i.e., for example, one part of wetting agent and 0.1 part of antifoam
per 100 parts of dispersion. Owing to interaction with the auxiliaries in the disper-
sion, the most effective antifoam for each adhesive must be determined experimen-
tally.
Companies which offer suitable antifoams include: Air Products and Chemicals
Inc., Allentown PA (USA); BASF AG/Corporation, Ludwigshafen/Mount Olive
(Germany/USA); Ashland Chemical Co., Drew Industrial Division, Boonton, NJ
(USA), or Drew Ameroid Europe, Ultra Additives Inc, Patterson, NJ (USA); Henkel
AG, Düsseldorf (Germany); ICI Surfactants, Middlesbrough (England), Muenzig
Chemie, Heibronn (Germany).
Addition of fillers or pigments

Fillers cause significant deadening of the adhesive, which can be compensated again
by a slightly increased amount of tackifier. In labels made from relatively thin paper,
small amounts of fillers or pigments can be added in order to increase the hiding
power.
Zinc oxide has proven successful as an antiseptic, moisture-absorbent filler in rub-
ber-based medical adhesive tapes. In contrast, modern medical adhesive tapes with
non-woven or woven fabric as support material use polyacrylates owing to their low-
er skin irritation action. These contain virtually no filler. If necessary, white col-
oration is produced using TiO2.
Fine sand (SiO2) also has a very strong deadening action. Even on addition of only
10 %, the tack can no longer be measured. Calcium carbonate filler exhibits much
better behavior. The smallest reduction in tack is caused by titanium dioxide, but this
is relatively expensive.
For homogeneous incorporation of fillers or pigments, it is advantageous to pre-
pare a paste with a little water. Additives to the water, such as ammonia, polyacrylic
acid salts and polyphosphates, aid in dispersing and also prevent the filler particles
from subsequently re-agglomerating. A “wetting fluid” comprising one part of am-
monia, one part of Pigment Dispersant A (BASF), one part of Calgon N (sodium
polyphosphate, Benkiser, Ladenburg) and 97 parts of water, to which the pigments
are mixed to yield a paste, has proven successful.
Protection against microorganisms

The risk of bacterial, yeast or fungal contamination is naturally the greatest in the
neutral or weakly basic pH range. This pH range is in most cases established during
modification as it also provides the best compatibility of the dispersion with formu-
lation additives. Preservatives used include formols, benzisothiazolinones (Proxel,
Avecia, Wilmington, DE, USA and Manchester, UK), isothiazolones (Kathon , Rohm
and Haas, Philadelphia, PA, USA, Rohm and Haas France SA, Valboonne-Cedex,
France). Other preservative suppliers include Riedel-de Haën AG (Germany), Troy
Corporation, Florham Park, NJ (USA) and Arch Chemicals (Paris, France and
Cheshire, Connecticut, USA).
General notes on modification

The following is a suitable compounding procedure: the pH of the starting disper-
sion is firstly increased in order to improve compatibility. Secondary acrylate disper-
sions are then added, followed by resin solution or resin dispersion, other tackifiers,
plasticizers and, if used, a pigment and/or filler paste. The final step is adjustment to
the processing solids content and viscosity by thickening, dilution and addition of
wetting agent.
Guiding formulations
1. Acrylic permanent paper label (resin tackified)
Wet wt.
Polymer dispersion Acrylic dispersion, 60–70 % 116
Tackifier dispersion Tacolyn 1070, 55 %*
or Snowtack 880G, 57 %† 36.4
Defoamer Drewplus L-108‡ 0.1–0.5
Wetting agent Lumiten I-SC§ 0.5–1.5
Neutralizing agent Ammonia (10 %) to pH 7.5–8.5 0–2
Water As required to max. 65 % solids
Rheology modifier As needed for coating head 0–2
Application rate: 20 g solid m–2
Suppliers: *Hercules, Wilmington, DE, USA; †Akzo Nobel, Toronto, Ontario, Canada;
‡
Ashland/Drew Chemical; §BASF, Charlotte, NC, USA
2. All-temperature paper label (non-tackified)

Polymer dispersion Acrylic dispersion 100
Neutralizing agent Ammonia (10 %) to pH 7.5–8.5 3–5
Wetting agent Aerosol OT70-PG# 0.5–1
Rheology modifier As needed for coating head 0–2
Water To maximum 65 % solids
Suppliers: #Cytec
Styrene-butadiene dispersions
In North America approximately 5–10 % of the dispersions used for labels are based
on styrene-butadiene rubber (SBR) [24]. SBR used in pressure sensitive adhesives
are produced by emulsion polymerization with butadiene contents typically between
25 and 45 %. With careful control of process conditions (temperature, styrene
and butadiene feed rates) and ingredient feed levels (chain transfer agent, initiator,
monomers), intermediate molecular weight, lightly cross-linked elastomers having
an excellent balance of cohesive and adhesive properties can be obtained.
SBR based systems are primarily used in cost-sensitive paper label applications;
they are not used, when clear films with long-term UV or heat aging resistance are
required. While the hydrophobic nature of SBR promotes superior initial tack and
adhesion to low energy substrates, this feature also makes them susceptible to plas-
ticizer attack.
Compared to tackified acrylic PSA, styrene-butadiene based systems normally re-
quire significantly increased tackifier contents (up to 2 times) to achieve desired tack
and peels levels. SBR are compatible with both commercial rosin and hydrocarbon
based tackifying resins. Differences in chemical composition, softening point, and
surfactant stabilizers in tackifier dispersions can have a significant impact on the
peel-shear balance of the formulated product [26]. Since commercial SBR are avail-
able at relatively low solids contents (ca. 50–55 %), the formulated adhesives have
higher water contents compared to those based on acrylics. This subsequently trans-
lates into slower line speeds and/or higher energy demand during the drying opera-
tion. An antioxidant would be recommended for SBR applications requiring extend-
ed stability against heat exposure or oxygen attack.
Guiding formulation
SBR permanent paper label (resin tackified)
Wet wt.
Polymer dispersion Butonal NS 166, 51 %* 63.8
Tackifier dispersion Aquatack 6085, 60 % 36.2
Defoamer, wetting agent, and rheology modifiers added as needed.
Suppliers: *BASF Corporation, Charlotte, NC, USA; Arizona Chemical, Panama City, FL, USA
Coating
Self-adhesive labels and films are produced by coating support materials such as sil-
icone release liner, paper stock, and film webs with pressure sensitive adhesives
(Fig. 8-9). Various coating methods are used to ensure the correct amount of adhe-
sive is applied per unit area of substrate [37–40]. High viscosity adhesives can be ap-
plied using a knife-over-roll coater. In reverse-roll coating, the adhesive is transferred
to the substrate web after being taken up by an application roll rotating in a direction
opposite to that of the web. Knife coaters and reverse roll coaters are traditional sys-
tems originally developed for coating solvent-based adhesives. But with aqueous dis-
persions, coating speeds of only 100–120 m min–1 are possible with these coating
methods – at application rates of about 20 g m–2. For higher production speeds,
Meyer rod (150–250 m min–1), reverse gravure (300 m min–1), vario gravure
(600+ m min–1), and slot die technologies are available. These systems require low-
viscosity dispersions and their development in the 1960s paved the way for a major
breakthrough by acrylate dispersions for mass-produced pressure sensitive articles
in Europe. Improvements in coating speeds, reliability, coating consistency, and
product quality led to lower production costs and continuation of the trend to water-
based emulsion coating technologies.
Steam
Coating head Dryer
Laminating
station
Release
liner Backing
Fig. 8-9 Schematic representation
of PSA label coater. Unwind Rewind
Reverse gravure was introduced by BASF at the beginning of the 1980s for pres-
sure sensitive adhesive processing and basically consists of a blade pressed on to a
gravure cylinder rotating in a pan of wet adhesive in a direction opposite to that of
the web. Adhesive is transferred from the pan into the recesses of the gravure roll
and then on to the web. The blade and roll assembly are primarily responsible for
metering on the correct quantity of wet adhesive and establishing a consistent, defect
free adhesive coating. Gravure rolls (Fig. 8-10) with 14 to 18 lines cm–1 give a dry
coating weight of about 20 g m–2. A gravure roll with 36 lines cm–1 gives, for exam-
ple, about 10 g m–2 (in each case with an approximately 50 % solids adhesive). If de-
sired, the coating weight can be varied slightly by adjusting the blade position and by
modifying the viscosity of the adhesive. For significant changes, a roll with a differ-
ent grid must be used.
When high reverse-gravure coating speeds (600+ m min–1) are attempted, coating
weight is found to drop off drastically above about 300 m min–1. This behavior occurs
at high speeds because of the shorter residence time of the gravure roll in the dis-
persion reservoir – i.e., so short that the gravure line cells are no longer completely
Fig. 8-10 Portion of a gravure roll (left), cross-sectional schematic (right).

(a) 10–20 µm chrome layer, (b) 10–15 µm nickel layer, (c) 70–250 µm
copper layer, (d) steel base roll.
filled and too little dispersion is applied to the web. However, if the dispersion is
forced into the engraving under pressure, it is possible to vary coating weight over a
broader range, even with a constant number of lines. For example, application rates
from 15 to 30 g m–2 can be achieved at 600 m min–1 with an 18 lines cm–1 gravure roll
and from 20 to 40 g m–2 with a 14 lines cm–1 gravure roll.
Vario gravure is a substantial refinement of the standard reverse gravure method
(Fig. 8-11). The side seal consists of two polyethylene “margin wipes” pressed
against the polished ends of the gravure roll. Two grooves, providing pressure re-
lease and lubrication, are incorporated into each margin wipe. Rubber parts are also
built into the margin wipes to seal the side edges of the coating blade – the entire
“casting box” assembly is sealed by a lateral force applied on to the sides of two mar-
gin wipes. The upper blade is additionally pressed against the gravure roll surface,
which simultaneously prevents air being drawn in and results in very low air en-
trainment (i.e. low foaming).
substrate
adhesive
blade adjustment
margin wipe
out
PSA dispersion
in
blade adjustment
Fig. 8-11 Vario gravure coating head.
Coating weight is controlled mainly via the pump pressure, designed to operate
without pulsation (Mohno pump). Due to the excess pressure prevailing in the cast-
ing box (0.2–0.6 bar), not only are the recesses of the gravure roll surface filled, but a
film, i.e. an excess, is also applied on to the roll. This is the only way that a coating
weight of 20 g m–2 can be maintained at higher speeds (400–600+ m min–1). The flow
rate of wet adhesive through the pump can also be coupled to the web speed in order
to keep coating weight constant during speed changes.
Water based pessure sensitive adhesives can also be directly applied on to the sub-
strate web using a slot die coater (Fig. 8-12). Die coating is widespread in the USA
(est. 60–70 % of total label production), but is only used occasionally in Europe.
adhesive
substrate
width adjustment of slot die opening
die
die lip offset adjustment
PSA dispersion
Fig. 8-12 Slot-die coating head. feed line
Coating weight can be easily varied over a broad range at different web speeds.
Uniform distribution of medium-viscosity adhesive over the web width is achieved
with a special die geometry where the outlet aperture is larger at the web edges than
in the center. This method provides an impressive final coating – characterized by
unusual levelness.
8.2.2
Self-adhesive Tapes
Self-adhesive tapes are flexible substrates coated with pressure sensitive adhesives
which are wound up in roll form and cut to different widths.
About 4.3 billion m2 of adhesive tapes were produced in Europe in 1996 [41]. Sev-
enty percent of these are packaging tapes, while the remainder are double-sided ad-
hesive tapes, masking tapes and other adhesive tapes (medical tapes, electrical insu-
lation tapes, household tapes, office tapes and protective films). Solvent-based, resin-
modified rubber solutions, used mainly for packaging adhesive tapes, are still domi-
nant in this segment. The stringent requirements on tack and cohesion for tapes
have still not been achieved by any other adhesive system in such a balanced way.
The proportion of water-borne adhesives used in the European tape market is about
14 % [19]. Water-borne adhesives are mainly used for double-sided adhesive tapes
and electrical insulation tapes.
In North America, about 4.5 billion m2 of adhesive tapes were produced in 1999.
Assuming an average coating weight of 40 g m–2, this corresponds to a polymer de-
mand of 180 000 tons year–1. About 70 % are used for industrial and packaging tapes,
the rest is used for consumer, surgical, electrical and masking tapes [18]. Water-
borne systems are used mainly to produce carton-sealing tapes.
Packaging tapes
Packaging tapes are required to form the contact points necessary for box or carton
closure (typically corrugated), even on gentle pressure. This means that the adhesive
must have high tack and good adhesion. In Europe, natural rubber is predominately
used to meet these requirements. Although acrylate dispersions have better aging
resistance, they have lower tack at the high cohesion levels needed.
Experiments have shown that the lower tack values can be fully compensated
through increased positioning or “application” pressure. In North America, carton
sealing tapes made from oriented polypropylene and water-borne acrylic PSA are
also produced. Anchoring of the dispersion adhesive to the polypropylene film is
achieved by corona pretreatment. A release coating is not necessary. The main re-
quirements for this application are withstanding the continuous shear and low-angle
peel forces transmitted to the tape at the carton closure. Coating weights of about
15–35 g dry adhesive m–2 are typically used. Paper backed tapes, such as masking
tapes, require coating weights in the 30–60 g m–2 range.
Foil duct tapes

Foil duct tapes, used in North America for heating, ventilation and air conditioning
systems, are constructed of 50 µm aluminum foil coated with 50–100 µm of an
acrylic dispersion PSA to provide high adhesion and functionality at extreme “use”
temperatures. Once coated, the adhesive is covered with a release liner to prevent ad-
hesion to the top side of the foil and subsequent blocking of the tape roll. Some foil
tapes use strands of fiber reinforcement laminated between foil and kraft paper lay-
ers to improve tensile strength [24].
Electrical tapes
Flexible PVC tapes of various types are predominately used for electrical insulation
purposes and to a lesser extent, for pipe insulation. In Europe, acrylate dispersions
have been used in the manufacture of electrical tapes for more than four decades.
Coating weights of ca. 25 g dry adhesive m–2 are typically used. Their advantage is
that they can be coated on to flexible PVC films without a primer. However, the use
of dispersions requires a high level of knowledge of the compositions and interac-
tions between particular flexible PVC substrates and acrylic adhesives. As a result,
suitable dispersions must be carefully selected and in many cases, it is necessary to
use more than one dispersion type to achieve required performance levels. Of prime
importance are plasticizer resistance screening tests on the adhesive, carried out in
order to examine for undesired changes in adhesive properties due to plasticizer mi-
gration from the PVC film.
Masking tapes
This term covers tapes for protecting surfaces during painting, sand blasting, etc.
The support material used is crepe paper of various quality and extensibility with nat-
ural rubber predominately used in the adhesive. Nonetheless, adhesives made from
mixtures of certain acrylate dispersions are highly suitable for “painters-grade”
masking tapes. Key requirements of masking tapes include adequate adhesion and
then easy removability without leaving a residue – even after extended storage times
or after exposure at high ambient temperatures. Coating weights of ca. 45 g m–2 dry
adhesive are used.
Double-sided adhesive tapes

Double-sided adhesive tapes or “mounting” tapes have been used to replace conven-
tional attachment methods in a range of different end-use applications. They are
used on a wide variety of surfaces, for example, as an assembly aid in the automotive
industry, in graphic arts for plate mounting and in home and office uses that previ-
ously required mechanical fasteners (e.g. nails and screws). The central support sub-
strate used includes non-wovens, textile fabrics, foams and other materials and in
some cases, support-free mounting tapes are also available. Foam mounting tapes
are especially useful because the foam provides stress distribution for increased
shear strengths.
While acrylate dispersions are often used, the most demanding applications em-
ploy solvent based acrylates that are subsequently crosslinked chemically or thermal-
ly to achieve performance requirements. In applications requiring exceptionally high
adhesive coating weights (up to 100 g dry adhesive m–2), dispersions having high
solids contents have been advantageous to increase drying rates during the coating
operation.
Protective films
Protective films are used to protect high-value items like painted or polished metal
surfaces (e.g. automobile paint finish), anodized aluminum, acrylic sheets, lac-
quered furniture surfaces and automotive carpets from scratching, soiling and mar-
ring during manufacture, shipping and installation. A range of support substrates
are used, including paper, flexible PVC, PE-, PP- and polyester films [24]. Here too,
acrylate dispersions are being used instead of the cross-linkable acrylate solutions
used in the past. In particular, self-crosslinking emulsion adhesives providing cru-
cial cohesion and anchoring to PE films have been developed especially for protective
films [24, 42]. Coating weights of about 5 g dry adhesive m–2 are employed.
8.2.3
Test Methods
Tack, adhesion and cohesion are the three main properties required of a pressure
sensitive adhesive.
The tack is the ability of a pressure sensitive adhesive to adhere immediately to a
surface. A pressure sensitive adhesive with good tack forms the contact points nec-
essary for adhesion of the tape or label after only brief contact with a substrate. Sol-
vent based rubber adhesives can have very good tack, depending on the formulation.
Acrylate solutions and dispersions, as well as hot-melt contact adhesives, meet the
usual demands.
The peel strength (adhesion) is a measure of the separating force necessary to peel a
label or tape off from the surface to which it was applied. The term describes the
strength of adhesion or “grab” to a surface. Acrylate compositions require a few
hours before achieving full adhesion. Rubber adhesives and hot-melt contact adhe-
sives exhibit high peel values after only a relatively short contact time.
The shear strength (cohesion) is the ability of a pressure sensitive adhesive to with-
stand applied forces or loads. Good shear strength is required when labels are stuck
to curved surfaces and for processing purposes, i.e. die-cuttability, slitting and to
minimize edge-ooze of roll products. When assessing shear strength, a distinction
must be made between the performance at room temperature and at elevated tem-
peratures. Pressure sensitive adhesives designed having adequate room temperature
shear strengths should also be formulated to resist failure at higher service tempera-
tures. While acrylic dispersions exhibit only a slight change in shear strength at ele-
vated temperatures (due to internal gel structure), hot-melt adhesives tend to soften
and the shear strength drops significantly.
Depending on the use, different requirements are made of pressure sensitive ad-
hesives with respect to adhesion and cohesion (Fig. 8-13).
adhesion
permanent packaging
labels tapes
removable protective
labels films
cohesion
Fig. 8-13 Adhesion level of self-adhesive articles.

A protective film must be removable without leaving a residue, i.e. must have very
low adhesion, even after long bonding times, in conjunction with high cohesive
strength. By contrast, a packaging tape must stick immediately and durably, i.e.
must have both very high adhesion, even after brief contact, and high cohesion. In
paper labels for permanent bonding, high adhesion is needed in order to ensure rap-
id bonding to the various surfaces, while the cohesion need only be sufficiently high
to avoid formation of adhesive filaments during label stamping and stripping opera-
tions. Removable labels have low adhesion and sufficient cohesion for removal.
Numerous methods are available for quantifying these different property profiles.
For better comparison of the properties of pressure sensitive adhesives, standardized
test methods have been developed by various organizations, including:
– FINAT – Fédération Internationale des Fabricants et Transformateurs d’Adhésifs
et Thermocollants sur Papiers et autres Supports
– PSTC – Pressure Sensitive Tape Council.
These and other PSA test methods were compared in a review article by R.P.
Muny [43]. One common feature of these established test methods is that they are all
destructive measurements. In the first phase of the test, a bond is formed on contact
of pressure sensitive adhesive with the substrate. Initially, depending on the applied
pressure, only individual, small points of adhesion form, whose number and size in-
crease during the contact phase due to elastic deformation, viscous flow and wetting
of the substrate with the adhesive. Contact formation is, therefore, determined by
mechanical behavior and surface properties, such as surface tension, roughness, and
adsorbate layers. Other important influencing factors are contact time, contact pres-
sure and temperature. During the second phase, the bond is separated under the ac-
tion of a tensile force, with the bond being deformed. Both processes, i.e. contact for-
mation and separation, are influenced by the test conditions, which are different in
each measurement method [27, 30, 44].
It is conceivable to carry out nondestructive measurement of an adhesive joint us-
ing nuclear magnetic resonance methods (NMR imaging). However, such methods
are still under development [45].
Peel strength
The most common adhesion test is peel strength testing [27], in which the force
which occurs on peeling the adhesive layer off from a substrate is measured.
Conditioned test strips with a certain width are rolled on to test panels using a
roller with a defined weight. Stainless steel with a surface of defined roughness is
used in method PSTC-1 while glass is employed in the FINAT method. But in both
cases, after a certain dwell or bonding time, the peel measurement is carried out in a
mechanical testing machine at constant peel rate and at a peel angle of either 180° as
in Fig. 8-14, or alternatively at 90°. There are various standards for the peel strength
test which differ essentially through the type of cleaning of the test panels and the
bonding times. For example, the bonding time is a maximum of 1 min in the PSTC
test, and 20 min and 24 h in the FINAT method. Since the dwell time has a signifi-
cant effect on the level of adhesion, different values are obtained by the two methods
mentioned [27].
clamp
support substrate (paper, film)
test substrate method dwell time

adhesive (steel, glass,
polyolefin) A.F.E.R.A. 4001 max. 10 min
PSTC-1 max. 1 min
FINAT 20 min
24 h
clamp
Fig. 8-14 Peel strength at 180° [27].
Even after a bonding time of 1 h, the wetting process is not complete in all cases
(Fig. 8-15). Besides the immediate value, a measurement is therefore often taken af-
ter, for example, a bonding time of 24 h, corresponding to FINAT test method 1 [27].
Besides numerous other authors [46–49], the main contributor to understanding
of the very complex peel mechanism in self-adhesive tapes is Kaelble [50, 51]. He has
shown that the peel strength is dependent on the moduli of elasticity and the thick-
nesses of both the adhesive and the support, on the peel angle, and the interaction
forces at the adhesive-substrate interface [27]. Peel strength also depends on temper-
ature and peel rate. At a given temperature, the peel strength increases with increas-
ing peel rate. At low peel rates the viscous properties are dominant, polymer mole-
dwell time peel strength in N / 2 cm
10 min 4,0
30 min 4,6
1h 5,3
3h 5,5
24 h 8,0
Fig. 8-15 Peel strength of an acrylic pressure sensitive adhesive depend-

ing on the dwell time, according to W. Druschke [27].
cules have time to slide past one another, to disentangle and to dissipate energy. At
high peel rates the elastic properties of the polymer network predominate, the poly-
mer molecules are not able to disentangle, and so the polymer modulus or “stiff-
ness” increases. Since the mobility of polymer chains increase with increasing tem-
perature, the peel strength will decrease as well – at a constant peel rate [52].
Tack
Tack is defined as the limiting value of the adhesion as the contact time approaches
zero. Targets for tack measurements are shortest possible contact time and lowest
possible contact pressure. With this aim, a number of methods have been devel-
oped [53, 54]. The best known tack measurement methods are quick-stick, probe
tack, Zosel tack and rolling ball [27]. All these methods are ultimately a refinement of
the subjective finger test, which still plays significant role in forming a qualitative
practical opinion [27].
In the quick-stick method corresponding to FINAT test method No. 9, a test strip
is formed into a loop, brought into contact with a glass plate and then immediately
peeled off again, as shown in Fig. 8-16.
clamp
support substrate clamp
adhesive
support substrate
adhesive
test plate
(steel, glass, polyolefin)
Fig. 8-16 Quick-stick tack measurement [27].
This FINAT method differs from the PSTC (PSTC-5) quick-stick method, in which
peeling is carried out at an angle of 90° without formation of a loop [55]. The Tag and
Label Manufacturers Institute (TLMI, Iowa City, IA 319-337-8247) specifies a loop
tack test and within their manual, includes a host of useful TAPPI and ASTM meth-
ods for testing paper and plastic film substrates used in pressure sensitive labels, re-
spectively.
The advantage of the quick-stick methods compared with other tack measurement
methods is that the test can be carried out in any mechanical test machine with only
minimal contact pressures. Disadvantages of the method include a relatively long
contact time, different contact times within a test area and different contact areas.
Moreover, the peel angle is not constant in the FINAT method.
A widespread tack measurement method is the probe tack method proposed by
Wetzel [56] and refined by Hammond [57]. In this method, known as the Polyken
probe tack method (Fig. 8-17), a cylindrical ram with a diameter of 0.5 cm is pressed
from below against the adhesive layer at a defined pressure and speed and removed
again at a defined speed after a certain contact time (see ASTM D2979-71).
substrate
adhesive
weight weight
support support
piston
Fig. 8-17 Polyken Probe Tack method [27].
Contact times in the region of 0.1 s are possible using this method. The fact that
the measurements can be carried out simply and quickly and the conditions varied
easily and widely is advantageous. However, a very complex instrument is necessary.
In addition, the very small ram contact area of only 0.2 cm2 means that only small ar-
eas of the adhesive layer are measured. Air inclusions in the adhesive layer can result
in incomplete wetting of the piston surface [27].
An instrument developed at BASF by A. Zosel [30–31] for fundamental stud-
ies [58–63] on the theory of adhesion operates on a similar principle to the probe tack
method (Fig. 8-18).
The polymer to be tested is applied to a flat steel plate in a defined layer thickness
and dried. With the aid of an electric motor, the sample platform within the test
chamber is moved against the piston and then away again in the opposite direction
after contact. The shortest contact time that can be set is 0.01 s. The piston is con-
nected to a piezoelectric force transducer. Variable parameters are the piston area,
contact force, contact time and approach speed of the tack experiment. The instru-
ment allows measurements from –50 °C to 200 °C. This method also allows basic
studies with variation of other key parameters, such as separation speed, surface ten-
sion of the test piston, and composition of the adhesive layer [64, 65].
force transducer
rod
test chamber
sample
steel support
electrical motor raises

and lowers test chamber
Fig. 8-18 Zosel tack measurement.
For adhesive layers whose tack is not too low, the rolling ball tack method may be
used [66]. In accordance with PSTC-6, a steel ball of defined diameter is rolled down
an inclined plane at a certain tilt angle on to the adhesive test strip, as shown in
Fig. 8-19. The distance traveled before the ball stops is a measure of the tack.
Fig. 8-19 Rolling ball

method [27].
In contrast to the other tack measurement methods mentioned above, the rolling
ball test requires simple equipment and is easy to carry out. The main difference to
the other tack measurement methods is the fact that the rolling ball method does not
measure force. The meaningfulness of the method is also impaired by the following
characteristics:
The surface of the ball can change its nature even during the first rotation, because
of transfer of traces of adhesive – ball contamination.
The adhesive values are relatively dependent on the viscosity and on the thickness
of the adhesive layer [27].
Reproducibility of adhesion measurements

Figure 8-20 shows a statistical evaluation of tests on a commercially available adhe-
sive tape.
Test Number Mean Standard Coefficient of

of samples deviation variation (%)
Peel strength after 10 min 25 3.8 N/2 cm 0.31 N/2 cm 8

Peel strength after 24 h 42 9.3 N/2 cm 0.54 N/2 cm 5
Quick-stick 50 10.2 N/2 cm 0.34 N/2 cm 3
Sample tack 43 11.3 N cm–12 1.24 N cm–12 11
Zosel tack 25 13.9 J m–2 4.67 J m–2 34
Rolling ball tack 50 3.9 cm 1.46 cm 38
Fig. 8-20 Statistical evaluation of the test results [27].
The scatter in the values after exclusion of outliers is 3–38 % of the mean, depend-
ing on the test. Apart from the very low scatter in the quick-stick method, the scatter
is lower for methods with longer contact times. Prerequisites for such results are
very uniformly defined test specimens and exact compliance with defined test condi-
tions [27].
Shear strength
The cohesive properties of a pressure sensitive adhesive are generally determined by
measuring the shear strength.
Corresponding to FINAT test method No. 8, the shear strength is the time re-
quired for a certain area (25 mm × 25 mm) of a self-adhesive material to slide off a
standard surface in the parallel direction to the surface with a load of 1 kg (Fig. 8-21).
The standard surface used is glass. In PSTC-7, a 12.5 × 12.5 mm adhesive contact
area on corrugated or stainless steel is subjected to a 1 kg load and the time to adhe-
sive failure is recorded.
Fig. 8-21 Shear strength

measurement.
8.3
Laminating Adhesives
Laminating adhesives are used to permanently bond various types of substrate webs
together in industrial manufacturing processes. The term lamination has gained
general acceptance for this industrial process. These multi-layer laminated products
are generally known as laminates and can consist of three, and in many cases more,
distinct layers in the total construction. Depending on the sector of industry and
product class, a distinction is made below between film-to-film lamination for flexi-
ble packaging, glossy film lamination and technical lamination applications such as
furniture assembly.
8.3.1
Flexible Packaging
The process of laminating single-layer web materials to give flexible multilayer film
structures has been an established method for many years. Alternate production
techniques include extrusion coating and co-extrusion, where plastics are melted
and extruded in thin layers through an extrusion die.
A wide variety of flexible laminates can be produced on fast, high-performance
laminating machines using suitable adhesives. Materials with specific properties are
utilized in each layer which altogether impart the performance attributes needed for
the particular application. The multilayer film for vacuum-packed coffee, for exam-
ple, consists of polyethylene so that the pack is heat-sealable, an aluminum foil layer
for aroma retention and light barrier, and a polyester film for mechanical strength
and good printability. Multilayer structures are widely used in packaging of foods,
such as cheeses, snack foods (potato chips), bacon, juice pouches and boil-in-bag
meals where oxygen barrier, water and heat resistance, and oil or fat barrier charac-
teristics are required.
Common laminating adhesives include solvent containing and solvent free,
crosslinking polyurethanes, and two-component, water-based polyurethanes – the
latter have been increasing in importance in recent years because of environmental
pressures. The choice of adhesive depends on the type of film to be bonded and on
the end use application. In food packaging, for example, food regulations and the re-
sistance of the adhesive (e.g. to boiling water) are also important.
Polymer dispersions
The prime advantage of aqueous polyurethane and polyacrylate dispersions over sol-
vent-containing systems is that recovery or disposal of significant amounts of solvent
is unnecessary. In the packaging industry, potential for residual solvent traces in the
adhesive and subsequent migration into food are also major concerns. Therefore,
solvent-containing adhesives have already been replaced by environmentally friendly
water-borne adhesives in a number of applications.
Film laminates are produced by coating adhesive on to one side of the primary
film, drying, and then laminating a second film on to the dried adhesive layer under
heat and pressure. Multiple layer structures are typically built up by applying further
adhesive and film layers at subsequent coating and laminating stations. Application
rates between 1 and 3.5 g dry adhesive m–2 are typical, depending on the film or web
type the adhesive used. Adhesive purchases into flexible packaging applications (in-
cluding paper and plastic laminates) totaled in USA approximately 150 million dol-
lars in 1997 [67].
In low-performance laminates, dispersions are employed as the only adhesive
component. If additional boiling resistance or sterilization capability is required,
from 3 to 5 % of a suitable curing agent should be added – e.g., water-dispersible
polyisocyanates. The water-dispersible polyisocyanate does not just act as crosslink-
ing agent yielding increased heat resistance, but also significantly increases adhe-
sion to most films [68]. Figure 8-22 shows the reaction of a trifunctional polyiso-
cyanate with an acrylate polymer and the OH groups of a corona-pretreated film.
Fig. 8-22 Reaction of a two-component aqueous lamination adhesive

(acrylate dispersion + water-dispersible triisocyanate) with corona-pretreat-
ed films.
Addition of curative of this type results in a significant increase in adhesive

strength; however, covalent reaction occurs to a small extent owing to steric factors.
The majority of the adhesion increase is attributable to the formation of hydrogen
bonds predominantly formed between OH and NH groups and polar groups of the
individual substrate.
A mixture of polymer dispersion and polyisocyanate has a maximum processing
time of about 5–7 h. If this time is exceeded, the laminate adhesion and hence peel
strength drops. Additionally, pH must be maintained between 3 and 4, higher pH re-
sult in shorter pot-lives.
Polyurethane dispersions adhere strongly to a broad range of corona-pretreated
plastic films. Achievable adhesion levels with PU dispersions are in many cases
higher than with acrylates. As mentioned above, PU can be crosslinked for use in
higher-end applications, or used alone to produce medium-performance laminates.

In either case, low initial “green-strengths” after forming the laminate bond are com-
mon. Moreover, it can take as many as seven days to achieve final laminate peel
strengths (by chemical reaction of isocyanates with hydroxyl groups), making it nec-
essary to store laminate rolls temporarily prior to downstream converting.
A specially designed high performance acrylic dispersion that does not require ad-
dition of crosslinking agent and which yields excellent green strengths has been de-
veloped [69]. Due to the rapid development of peel strengths, laminates can be used
immediately after production – thus, eliminating the need for inventory storage.
Moreover, adhesive pot-life issues are eliminated because of the absence of a reactive
second component.
Guiding formulation
Two-component polyurethane laminating adhesive
Wet parts
Dispersion Polyurethane dispersion (40 %) anionically
stabilized 100
Crosslinking agent Water-dispersible, aliphatic
polyisocyanate, NCO content approximately 18 % 3–5
Test methods
With film laminates made by adhesive bonding, the aim is to form the strongest pos-
sible laminate, thus, peel strength (i.e. laminate adhesion) is typically measured. The
test is usually carried out with 15 mm wide test strips where the film layers are
peeled apart using a tensile tester. The peel strength is specified in N/15 mm. The
test report should furthermore indicate the failure mode; possibilities include film
tear, cohesive failure, and adhesive failure to either of the film surfaces involved (in-
cluding printed layers). The peel strength in the region of a heat-sealed seam is
known as the seal seam strength.
8.3.2
Glossy Film Lamination
Glossy film lamination involves the covering of printed paper or board products with
an optically clear, high-gloss plastic film. The process improves the brightness of the
printing inks and protects the printed material from external influences (e.g. scratch-
ing, bleaching and moisture). Examples include book covers, advertising and pack-
aging materials. Other methods besides film lamination are used to “finish” print
products, including both physically and chemically cured coating systems. Glossy
film lamination is used to a large extent in Europe but in North America, a special
form of film lamination, predominates, called “thermo-lamination” [70]. In thermo-
lamination, oriented polypropylene (OPP) films with a pre-applied heat-sealable ad-
hesive layer are thermally bonded to the substrate, therefore, eliminating the need
for additional adhesive.
High-gloss film laminates have been available in Europe since the 1960s. Lamina-
tion is frequently still carried out using solvent-containing adhesives. Embossable
paper board laminates were only made possible by high adhesion, two-part solvent-
containing polyurethanes with crosslinking agents. However, the limited pot lives of
two-component systems require increased care from the processor.
Efforts to eliminate solvents to comply with more stringent emission regulations
likewise here resulted in the use of aqueous polymer dispersions. One-component,
self-crosslinking dispersions with shelf lives equal to those of standard polymer dis-
persions were developed, solving the pot life problem.
Wetting and flow of the adhesive on the film are the main prerequisites for high
clarity lamination. This requires the polymer dispersion adhesive layer to be as plas-
tic and film-forming as possible during the lamination process. However, such ad-
hesive films would then be too soft and would result in partial separation between
film and board during subsequent bending and embossing operations. A consider-
able advance was made, however, with the development of aqueous acrylate-based
polymer dispersions which crosslink after evaporation of the water, after the film has
formed. Crosslinking takes place at room temperature using a reactive ketone-dihy-
drazide chemistry designed into the polymer dispersion (Fig. 8-23).
Fig. 8-23 Chemical crosslinking reaction of a one-component acrylic adhesive.
The polymer particles contain co-polymerized carbonyl groups which, on film for-
mation, react with hydrazide groups of the water-soluble acid dihydrazide to form
hydrazone. Increased cohesion strength results due to both inter-particle and intra-
particle crosslinking reactions. A similar process also occurs between corona-pre-
treated polypropylene film and the emulsion adhesive thereby significantly increas-
Fig. 8-24 Infrared absorption

spectrum of polyethyl-
ene films, according
to W.-D. Domke and 0,8
H. Steinke [71].
C=O
COOH
0,6
0,4 corona treated PE film
unteated PE film
(according to W.-D. Domke u. H. Steinke)
0,2
1900 1800 1700 1600 1500
wave number in cm-1
ing the adhesion strength of the laminate. As shown in the IR spectra for the PE films
in Fig. 8-24, additional carbonyl and carboxyl groups are observed on the film surface
after pretreatment [71], which can then react with the dihydrazide crosslinking agent.
The measurement of peel strengths after drying shows that significant crosslink-
ing occurs after only approximately 2 h and is complete after about 48 h. In practice,
this means that bending and embossing of freshly produced board laminates should
only be carried out after this time period, in order to maintain film-to-film bond-
ing [72].
Test methods
Drying
The progress of crosslinking over time can be recorded by measuring the surface
tack. This can be carried out using the Zosel tack measurement tester described in
Sect. 8.2.3 (Fig. 8-18). This enables measurement of the separation work of adhesive
layers throughout the course of drying.
Resistance to Delamination
After allowing sufficient crosslinking time, the lamination is formed, embossed and
evaluated after certain time intervals. Formed and embossed laminates are classified
as “failures” if the film is observed to have delaminated in the high-stress zones, as
evidenced by pale strips or spots in the otherwise high-gloss, if possible dark, lami-
nation.
Yellowing
High-quality, durable laminates are expected to maintain print color and gloss levels
even after prolonged light exposure. In addition to adhesive, the behavior of the top
film layer and underlying paper and printing should also be evaluated by including
appropriate control samples light exposure tests. Accelerated tests can be carried out,
for example, using a Q-UV type exposure instrument with a radiation spectrum and
intensity matched to that of natural sunlight. One-component acrylic adhesives per-
form very well in this respect, while conventional solvent-containing two-component
polyurethane adhesives yellow after a relatively short exposure time.
Gloss
No reliable test methods for measuring the surface gloss of film laminates have, so
far, been established. As such, the assessment of surface film gloss is best carried
out visually. Evident “graying” is an indication of tiny air bubbles between board and
film. These may be caused by inadequate application of adhesives, insufficient dry-
ing, or coalescence of the adhesive during lamination. Optical microscopy has also
proven useful in confirming defect types in laminates.
8.3.3
Furniture and Automotive
Solvent based, hot-melt, and water-based dispersion adhesives are typically used in
producing technical laminates for the furniture and automotive industries. The mar-
ket share for aqueous dispersions is about 40 %. The main products are “heat-acti-
vatable” polyurethane dispersions, which provide excellent adhesion and extremely
high bond strengths to a range of substrates. Important applications are furniture
lamination (lamination of medium density fiberboard to decorative sheeting) and
the lamination of moldings for interior automotive parts (e.g. dashboards, door inte-
rior panels) [73]. In North America, the total automotive adhesive market is estimat-
ed to be roughly $ 200 million (in 1997) [74].
Polyurethane dispersions are secondary dispersions typically produced by poly-
merization of isocyanates and diols in organic solvent. After polymerization water is
added followed by solvent removal. The polyester–polyol component can be designed
to form crystalline structures (Fig. 8-25), which make a significant contribution to
the internal strength.
The cohesive polyester-polyol crystals of commercially available PU adhesives melt
at about 50 °C – the lamination adhesive is thermally activated and becomes soft and
capable of heat-sealing (Fig. 8-26). During cooling, the polyester–polyol segments re-
crystallize, resulting in a rapid increase in the internal strength of the adhesive film.
This effect is utilized in furniture lamination, in which the polyurethane disper-
sion is usually mixed with a reactive crosslinking agent. The polyurethane adhesive
is applied using a spray gun. After the adhesive has dried, a blocking-resistant film
forms, and the fiberboard elements can be stacked. They are then pressed with the
decorative sheet at 60–80 °C, for example in a membrane press. On cooling, recrys-
tallization produces a rapid increase in strength. This is necessary to counter the re-
Fig. 8-25 Crystalline structures of a polyurethane adhesive.
Fig. 8-26 Differential heat flow measurement of a water-borne PU adhesive.
covery forces in the thermoformed decorative sheet which are effective in the first
minutes after pressing. The increase in cohesion due to the crosslinking reaction of
water-dispersible isocyanate is, by contrast, a slower process, with the final strength
only being achieved after days.
The reversible melting of the polyester-polyol segments is the physical basis for
the thermal activation ability. The possibility of heat activation is a very important ad-
vantage of polyurethane adhesives. It is also an example of switchable properties of

polymers, where heat is the switch.
Formulation modifications
The addition of suitable resin dispersions and small amounts of plasticizer enables
the thermal activation temperature to be reduced, although this also results in a re-
duction in heat resistance. In contrast, the addition of crosslinking agents improves
adhesion and water resistance and increases the heat resistance. The crosslinking
agents used are water-dispersible triisocyanates, carbodiimides and polyaziridines.
The reactivity of the crosslinking agents is reduced by various methods so that an ad-
equate processing time is available. Mixing with other acrylic dispersions allows the
properties to be modified and the costs of the adhesive to be reduced.
Guiding formulation
Two-component polyurethane dispersion for furniture lamination
Wet parts
Dispersion Luphen D 200 A, 40 %,* or Dispercoll U 53§ 100
Crosslinking agent Water-dispersible polyisocyanate 5
Suppliers: *BASF AG, Ludwigshafen, Germany; §Bayer AG, Leverkusen, Germany
Test methods
The static peel strength of the laminate made from PVC furniture sheet and MDF is
assessed visually for delamination after storage at elevated temperature.
8.4
Construction adhesives
8.4.1
Floor-covering Adhesives
The term floor-covering adhesives denotes all materials for laying flexible floor-cov-
erings. These include secondary and unitary backed carpets, felt backed vinyl, vinyl
composition tile (VCT), homogeneous vinyl sheet, rubber, and various vinyl and
polyurethane backed carpet tile products. Rigid coverings, such as natural stone, ce-
ramic and parquet, are not included here.
The main driving force for the development of modern floor-covering adhesives is
the need for reduced volatile organic content (VOC). Though there are regional dif-
ferences, reducing emissions of organic solvents is a worldwide consumer driven
trend based on environmental and health concerns (sick building syndrome).
In Europe at the beginning of the 1960s, flexible floor-coverings (such as linoleum)
were bonded using alcohol-soluble resin adhesives. However, these were unsuitable
for the new PVC floor-coverings on the market, for which solvent-containing poly-
chloroprene adhesives consisting of 75 % of organic solvents and 25 % of poly-
chloroprene and resins were used. These contact adhesives had to be applied to both
8.4 Construction adhesives 225
sides, i.e. to the back of the floor-covering and to the floor. A precise laying technique
was vital as the floor-coverings, which were laid after the solvent had evaporated,
could not be corrected once laid. This technique was soon also used for bonding
high-quality carpeting.
A severe disadvantage of contact adhesives with a solvent content of 50 to 70 % was
the emission of large amounts of solvents. Poor ventilation and the presence of an
ignition source resulted in explosions, burns and even fatalities.
The first polyacrylate dispersion for the production of aqueous floor-covering ad-
hesives became available in Europe in the mid 1960s. The adhesive consisted of
40 parts of Acronal 80 D (50 %), 40 parts of chalk and – to improve the wet tack –
20 parts of balsam resin solution (70 % in toluene). The solvent content was only
6 %, and the bond strengths which could be achieved for PVC floor-coverings corre-
sponded to the level of polychloroprene contact adhesives. In addition to significant-
ly reducing the risk of accident, further advantages of the new type of adhesive were:
– application of adhesive to one side only
– the floor-coverings could be corrected
– good aging resistance
– fresh adhesive residues could be removed from the floor-covering and tools using
water
Solvent based polychloroprene adhesives have a different setting mechanism
compared to water based flooring adhesives. Polychloroprene adhesives develop
their bond strength through recrystallization of the elastomer from solution. In the
case of emulsion adhesives, the polymer particles are initially swollen by the resin
solution. During evaporation of the water, a film-formation phase occurs in which
the polymer film, due to the residual solvent, has particularly high tack and low
cohesion. The final strength is then achieved by two processes occurring in parallel:
Firstly, post-flow of the polymers on to the substrate surfaces results in an in-
creased contact area and consequently in an increase in adhesive strength; secondly,
evaporation of the residual solvent and recrystallization of the small and rigid abietic
acid molecules increase the cohesion of the polymer film to its final strength.
At the beginning of the 1970s, rapid growth commenced for back-coated textile
floor-coverings, which were also bonded using one-side adhesives. At the end of the
1980s, solvent-free floor-covering adhesives were produced for the first time with
Acronal A 323 in combination with a plasticizer. In these, the tackifying resin solu-
tion was replaced by a resin melt. Adhesives formulated in this way have proven ad-
hesive properties and are solvent-free substitutes as defined in the Technical Rules
for Hazardous Materials, TRGS 610 [75].
The next generation of floor-covering adhesives was developed in 1994. In these,
solvents, plasticizers and resins were deliberately omitted. Although plasticizers are
not solvents in the sense of TRGS 610, they are nevertheless low-molecular-weight
substances with a certain vapor pressure and are consequently a source of emissions.
Resins were omitted because the usual abietic acid derivatives are odor carriers. The
absence of the action of these two proven starting materials was compensated by a
larger proportion of the softer and tackier acrylate dispersion Acronal A 200 or Pri-
mal CA-187 (see guide formulation 2) [76].
The adhesive formulated in this way has very low emissions as defined in the re-
quirements published by the Association of Emission-Controlled Laying Materials
(Gemeinschaft Emissionskontrollierter Verlegewerkstoffe, founded in Germany) at
the beginning of 1997. These requirements have no legal foundation, but are based
on a voluntary self-commitment by the member companies for processor and con-
sumer protection. The emissions are measured using a chamber test method (see
Test Methods), which enables firstly, volatile carcinogenic (suspected or proven) con-
stituents to be identified and measured after 24 h (processor protection) and second-
ly, the long-term total emissions of volatile organic compounds (TVOC) to be deter-
mined after 240 h (consumer protection). Corresponding to the TVOC after 240 h,
three emission classes are defined: EC 1 very low emissions (TVOC <500 µg m–3),
EC 2 low emissions (500 to 1500 µg m–3) and EC 3 not low emissions (TVOC
>1500 µg m–3). For all classes the maximum emission of carcinogenic compounds
after 24 hours has to be less than 10 µg m–3.
In North America reductions in solvent levels in floor-covering adhesives have
been essentially driven by environmental and VOC concerns. In March 2001, the
California South Coast Air Quality Management District (SCAQMD) approved a pro-
posal, Rule 1168, to reduce solvent levels, specifically non-exempt VOC, in floor-cov-
ering adhesives from approximately 150–200 g L–1 to approximately 50–70 g L–1. Oth-
er state agencies are expected to implement similar solvent and VOC criteria in years
to come. These regulatory changes necessitate a further shift from solvent-rich adhe-
sive systems towards water-based adhesive technology.
Total North American carpet consumption in 1999 was approximately 1.6 billion
square meters, split between two main sectors, residential (75 %) and commercial
(25 %). Residential carpets are typically installed using glue-less installation tech-
niques (e.g. tack-strip). However, carpets in commercial installations including
schools, retail establishments, hospitals, workplaces and hospitality facilities are in-
stalled employing specially designed or multipurpose adhesive systems. These adhe-
sives are typically formulated employing non-carboxylated, high-solids, styrene-buta-
diene lattices (SBR HSL), hydrocarbon resin-oil blends, and fillers as the primary
components. In the past, such adhesives were formulated with resin solutions based
on hydrocarbon solvents (e.g. mineral spirits) and/or plasticizers. Environmental
pressures led to near elimination of solvents and plasticizers in the 1990s and intro-
duction of increasingly lower VOC adhesives made with increasingly higher viscosi-
ty “naphthenic” oils.
Flooring mastics based on non-carboxylated SBR HSL are employed primarily in
carpet and mineral fiber or felt-backed vinyl glue-down applications over most com-
mon sub-floor surfaces. Such SBR based adhesives are not recommended for “un-
backed” vinyl (PVC) applications due to plasticizer migration from PVC to the adhe-
sive and bond loss issues. Conventional “felt” backings provide an effective barrier to
plasticizer migration. In contrast, acrylic copolymer based floor-covering adhesives are
employed in direct vinyl contact applications where plasticizer resistance is required.
The main constituents of the SBR HSL based flooring adhesive are the resin–oil
blend, surfactant, latex and filler (see guiding formulation 1). Carefully selected
resin–oil systems are employed for both cost and property reasons (early wet tack
development, legging or webbing, initial or “green” strength, final bond strength,

aging resistance and low VOC). Webbing and bond strength are also sensitive to for-
mulation latex content, typically in the order of 10–15 %. The rosin acid and non-ion-
ic surfactants in this formulation serve to stabilize the oil in water emulsion during
compounding and to provide end-product in-can stability. Urea can be employed to
achieve freeze-thaw resistance (low molecular weight alcohols and/or glycols can
also be considered). Caustic solution (e.g. 20 % KOH) is added to neutralize the rosin
acid and to achieve sufficiently high pH so that when the non-carboxylated HSL is
added, pH shocking effects with coagulation are avoided. Clay is added for reinforce-
ment purposes and for cost–performance optimization. Alkali sensitive emulsions
(e.g. Latekoll D) are added for thickening purposes.
The key parameters to control are formulation water content, clay/latex ratio and
resin/latex ratio, depending on the desired adhesive cost structure. Not surprisingly,
too much filler or too little resin and/or oil will result in inferior properties. Excess
water will result in slower drying, and probably the need for more “water sensitive”
thickeners. Like many other SBR based adhesives, HSL based flooring mastics in-
clude in-can and dry-film preservatives as well as an antioxidant package to ensure
long-term performance.
The total volatile organic content (TVOC) is a key property of floor-covering adhe-
sives. In the mid 1990s, the Carpet and Rug Institute (CRI) introduced a voluntary
TVOC specification for floor-covering adhesives, defined as the Green Label Pro-
gram in North America. The method employs a small chamber test apparatus
described in ASTM D-5116. For CRI Green Label certification, 24-h emission rates
from adhesives must be <10 mg m–2 h–1 for TVOC, <3 mg m–2 h–1 of 2-ethylhexyl
alcohol, and <0.05 mg m–2 h–1 for formaldehyde. TVOC and formaldehyde are
quantitated employing thermal desorption GC–MS and HPLC techniques, respec-
tively.
In North America, formulation technology based on high solids content styrene
butadiene lattices and naphthenic oils are widely used in the market place. Low
TVOC products have evolved to meet the CRI Green Label requirements and to pro-
vide cost-effective, high performance adhesives for carpet and felt-back vinyl floor-
coverings.
Floor-covering adhesives made from water-based polymer emulsions contain ap-
proximately 10–20 % dry polymer in both European and North American systems.
Floor-coverings are bonded using an application rate of about 250–500 g m–2.
1. High solids content styrene butadiene (HSL) and naphthenic oil based flooring
adhesive for carpet and felt backed vinyl floor-coverings with emissions satisfying
CRI Green Label TVOC requirements. Such adhesives are not recommended for
homogeneous or solid vinyl sheet goods where plasticizer migration is a concern.
Wet parts
Hydrocarbon resin Neville LX 1200* 9.7
Rosin acid Melhi 2.2
Naphthenic oil Tufflo 1200‡ 12.0
Surfactant Igepal CO-897 (70 %)§ 0.2
Surfactant Igepal CO-530 0.1
Anti freeze Urea (50 %) 1.4
Neutralizing agent Potassium hydroxide (2.5 %) 8.7
Filler Huber 95 (70 % clay slurry)# 41.4
HSL dispersion Butonal NS 104 (71 % s.c.)** 20.4
Thickener Latekoll D (pH adjusted 8 % solution)** 3.9
Total 100
Procedure: Add resins to oil at 140–150 °C, stir until homogeneous, then cool to
95–98 °C. Surfactant, urea and KOH solution are slowly added under mild agitation
to form an emulsion. The clay, SBR, and thickener are then added to the resin emul-
sion in the order indicated above.
2. Very low emissions corresponding to the requirements of the German association
of Emission-Controlled Laying Materials (GEV)
Wet parts
Dispersion Acrylic dispersion 24.4
Plastiziser Plastilit 3431** 2.0
Antifoam Agitan 282†† 0.2
Dispersant Pigment dispersant NL** 0.5
Chalk Ulmer white XM‡‡ 42.0
Thickener Latekoll D 2 %** 10.9
Resin melt Gum resin WW: Plastilit 3431 = 8:2 16.0
Resin Poli melt 15§§ 4.0
Total 100
Suppliers: *Neville Chemical Company, Pittsburgh, PA, USA; †Hercules Incorporated, Wilmington,
DE, USA; ‡Lyondell Lubricants, Houston, TX, USA; §Rhone-Poulenc, Cranbury, NJ, USA;
#
J.M. Huber Corp., Wrens, GA, USA; **BASF, Charlotte, NC, USA; Ludwigshafen,
Germany; ††Münzing Chemie, Heilbronn, Germany; ‡‡Omya, Cologne, Germany;
§§
Erbsloeh, Krefeld, Germany
Test methods
North American industry standard test methods for floor-covering adhesives are cur-
rently not available. However, methods are under development by ASTM committee
D14.70.12, Carpet Adhesives. As a guiding method for evaluating carpet to plywood
peel strength the adhesive is troweled on to plywood (application weight ca.
300 g m–2), after 20 min the carpet or vinyl is laid and pressed down at room temper-
ature, and, after a certain curing time at room temperature or 60 °C, the floor-cover-
ing is peeled off at 90° angle using a tensile tester.
Drafts of European test standards for measuring peel and shear strengths of floor
and wall coverings were submitted for approvals in early 1999 by Technical Commit-
tee CEN/TC193. These methods, referred to as prEN 1372 and prEN 1373 respec-
tively, are fundamentally quite similar to methods developed in Germany through a
collaboration between floor-covering manufacturers, official test institutes, and ad-

hesive and raw material producers. German test standards and specifications for
peel and shear strength discussed below are summarized in DIN 16860 for PVC
floor-coverings and in DIN 53269 for textile floor-coverings.
Peel resistance
The peel resistance is the force, per unit width of floor-covering, which results when
peeling-off a bonded sample perpendicular to the original adhesive bond line. Ac-
cording to regional requirements, the adhesive is applied to plywood, cement board
or other substrate using a trowel spreader and, after a certain “open” or evaporation
time, a 5 cm × 30 cm floor-covering strip is laid on to the adhesive bed and pressed
down, preferably using a fixed weight roller (e.g. 5 kg). After a storage time under de-
fined standard laboratory conditions, the floor-covering strip is peeled perpendicular
to the adhesive join at a certain speed using a tensile testing machine (Fig. 8.27). The
peel forces which occur during this operation are measured and specified in
N mm–1. According to DIN 16860, the average peel strength must have a certain
minimum value (e.g. 1 N mm–1). Other factors such as early bond strength develop-
ment, water resistance, and accelerated oven aging (e.g. 50 °C) can also be evaluated
using variations of this general method.
Fig. 8-27 Measurement of peel resistance.
Shear strength
The shear strength is the force per unit area which results in fracture of bonded sam-
ples parallel to the bond joint. Adhesive areas of 1000 mm2 (ca. 2.5 cm × 5 cm) are
produced on plywood or other cementitious substrates using a template and trowel,
then the floor-covering is laid on to the adhesive area and pressed down. After a stor-
age time under standard laboratory conditions, the floor-covering is removed parallel
to the adhesive join at a defined speed using a tensile testing machine. The shear
forces which occur during this operation are measured and specified in N mm–2 .
According to DIN 16860, the mean of the shear strength must have a certain mini-
mum value (e.g. 0.3 N mm–2) to be considered “passing”.
The curing of water-based adhesives is typically dependent on temperature and
humidity conditions. For this reason, it has proven useful in the development of wa-
ter-based adhesives for carpets and other floor-coverings to also test peel strength as
a function of time. There are two additional test methods for this:
Green strength development

The 5 cm wide floor-covering strip is laid in the wet emulsion adhesive after a
10–20 min drying time, and then pressed down. Floor-covering specimens are
peeled off at a certain speed perpendicular to the adhesive join after a further 10, 20,
30, and 60 min. The peel forces, which occur during this operation are measured and
specified in N/5 cm strip. Depending on drying conditions and adhesive composi-
tion, peel strengths on the order of 10–15N/5 cm strip should be expected within
15–30 min after applying the floor-covering strip. When peel testing SBR HSL based
mastics in particular, it is equally important to also report the degree of web or leg
development as a function of time. While not necessarily correlated with final adhe-
sive bond strength, installers nevertheless commonly look for early web develop-
ment as an indication of adhesive quality.
Open time
Open time represents the maximum recommended time after troweling that the
floor-covering should be laid into the adhesive. To quantify this parameter, a 5 cm
wide floor-covering specimen is placed in the partially dried emulsion adhesive after
30, 45, 60 and 90 min airing times and pressed down. The floor-covering is immedi-
ately peeled off at a certain speed perpendicular to the adhesive join. The peel forces,
which occur during this operation are measured and specified in N/5 cm. After ex-
ceeding the open time, unacceptably low peel strengths and poor adhesive grab on to
the floor-covering substrate are observed. As with green strength development, tem-
perature and humidity conditions also have a significant impact on the open time ac-
tually found under installation conditions. Typically, longer open times and delayed
green strength development are expected at higher humidity and lower installation
temperatures (i.e. because of slower water evaporation from the adhesive itself).
These two methods have a reproducibility of ±20 %.
Chamber method for emission measurement

North American “CRI Green Label” and European chamber TVOC methods for
flooring adhesives are fundamentally similar. In both cases, the adhesive sample is
applied to a stainless steel or glass plate and immediately sealed in a stainless-steel
test chamber carefully maintained under well defined temperature and humidity
conditions (e.g. 23 °C, 50 % rel. humidity). VOC are collected onto adsorption tubes
containing suitable adsorbents after flowing purified air through the chamber at a
controlled rate. The CRI Green Label method requires volatile and formaldehyde
samples be collected at the 24 h point. However, the German Association of Emis-
sion-Controlled Laying Materials specifies that substances known or suspected of

being carcinogenic must be determined at the 24 h point (in accordance with
Hazardous Materials Regulation/TRGS 905), but also that long-term emissions be
determined after 10 days. After desorption, the emitted substances are determined
by gas chromatography (GC-MS coupling) or liquid chromatography. The long term
emissions are quantified using toluene as standard substance for volatile substances
in low concentration. Loading of the chamber should be at 0.4 m2 m–3 and the air
exchange rate at 0.5 chamber volumes per hour (1.0 air exchanges per hour in the
ASTM protocol).
8.4.2
Sub-floor and Wall Mastics
Sub-floor and wall mastics are employed in a host of building and home construc-
tion applications. Sub-floor type mastics are typically used for fixing plywood sub-
flooring to lumber floor joists and more recently applied to secure plywood roof
sheathing to roof rafters and trusses of existing roofs. In both of these applications,
nails are also used to hold the plywood in place, but the adhesive greatly augments
the structural strength. For example, in wind exposure tests [77], adhesives were
found to increase resistance to wind uplift forces by factors of 2–3 compared to tradi-
tional nail down methods, important for homes and buildings in areas prone to tor-
nadoes and hurricanes. Plywood-lumber sub-floor mastics are employed in quality
construction systems to eliminate nail pops and floor squeaking. Improved mastic
systems are required which are compatible with commercial oriented strand boards
(OSB) used increasingly in place of standard plywood in both sub-floor and roofing
constructions.
Sub-floor mastics are generally supplied in cartridge form (310 cm3 and 860 cm3
tubes) and applied as a 6 mm bead using standard caulk gun applicators. Overall
market in North America for this class of adhesive is approximately $35 million
year–1 with 3 % growth per annum. The market consists predominately of formulat-
ed solvent based styrene–butadiene polymers, moisture-cure polyurethanes, and
high performance water based acrylic systems. Increasing VOC concerns coupled
with lower solvent threshold limits in California [78] are driving the eventual move-
ment to environmentally friendly, low VOC water-based mastics.
An estimated 75 % of the mastic products sold in North America indicate compli-
ance to stringent AFG-01 (i.e. “Adhesives for Field Gluing”) requirements. ASTM D
3498 is quite similar to the AFG-01 standard originally written by the American Ply-
wood Association. These methods define a series of six test specifications (Fig. 8-28),
five of which involve shearing plywood to lumber wood block specimens in com-
pression mode after various carefully controlled material conditioning and specimen
curing protocols (Fig. 8-29).
The sixth test, called oxidation resistance, is a mandrel flexibility check on films of
dried mastic after exposure to oxygen at high temperature in an oxygen bomb appa-
ratus. Water based mastics formulated with acrylics or styrene-acrylic polymer dis-
persions typically pass oxidation resistance requirements. The most challenging pa-
Fig. 8-28 Plywood on lumber shear test

Force (AFG-01).
Adhesive
Bond Line
Plywood
Lumber
Conditioning Assembly curing Test specifications

of materials
Dry lumber 48 h, 37 °C/30 % rh 28 days, 37 °C/30 % rh Shear >1000 N

Wet lumber 48 h soak lumber; 28 days, 37 °C/90 % rh Shear >1000 N
48 h, 37 °C/90 rh
for Plywood
Frozen lumber 48 h soak lumber 5 days, –14 °C Shear >667 N
48 h; –14 °C for lumber 21 days, 4 °C/50 % rh
and plywood 7 days recovery
Moisture 48 h, standard 28 days, 22 °C/50 % rh Shear >1000 N;
resistance conditions 3 cycles of 4 h H2O/o.n. <10 % bond failure
dry 37 °C
7 day recovery
Gap filling 48 h, standard 28 days, 22 °C/50 % rh Shear >667 N
conditions (16 gauge wire)
Oxidation 3 days, 22 °C/50 % rh; bend over 6 mm
resistance 2 days, 48 °C/50 % rh; Mandrel: no cracking
500 h, 70 °C/20bar O2
Fig. 8-29 Performance specifications for Adhesives for Field Gluing Plywood to
wood framing (AFG-01) rh relative humidity, o.v. over night, 1 N = 0.2248 lbf.
rameters to balance, however, involve moisture resistance and frozen lumber.

Frozen lumber adhesion is promoted through the use a combination of coalescents
and freeze-thaw aids (e.g. glycols, alcohols). Levels of such additives are kept to a
minimum in order maintain maximum resistance to moisture.
The wall mastic market in North America is roughly twice the size of the sub-floor
market mentioned above. Typical wall mastic applications include:
– wood bonding to concrete walls and floors
– bonding drywall or gypsum board and paneling to studs and framing structures
In concrete bonding applications, use of adhesives eliminate the need for time
consuming drilling operations and prevents damage to the concrete substrate. Drywall
adhesives are used increasingly as builders look for ways to replace time consuming
hammer and nail approaches [79]. Test specifications for drywall adhesives are de-
scribed in ASTM C-557, Adhesives for Fastening Gypsum Wallboard to Wood Framing.
Like sub-floor mastics, wall mastics are also manufactured in solvent based,
polyurethane and water based formulations. Due to reduced strength requirements
(i.e. relatively low inherent strength of drywall), drywall mastics are typically filled to
a higher degree and thus, are less costly compared to AFG-01 sub-floor mastics.
Guiding formulation
Solvent-free plywood-lumber sub-floor adhesive
Wet parts
Dispersion Acronal DS 2159* 56.7
Dispersant Pigment disperser N* 0.1
Dispersant Sodium tripolyphosphate 0.1
Defoamer Nopco NXZ† 0.05
Tackifier Snowtack 301 A‡ 3.6
Anti freeze Ethylene glycol 3.0
Coalescent Eastman DBA§ 2.3
Filler Duramite†† 11.4
Filler Clay†† 22.7
Thickener Latekoll D* 0.3
Total 100
Ingredients are combined in the order indicated above at room temperature with
high-speed agitation.
Adhesive properties: 70 % solids content, pH 9, 40 % polymer on dry
AFG-01 testing: Moisture resistance: 3100 N (>1000 N required)
Frozen lumber: 880 N (>667 N required)
Bond failure: None (<10 % required)
Suppliers: *BASF Corporation, Charlotte, NC, USA; †Henkel, Ambler, PA, USA; ‡Akzo Nobel,
Woodstock, CT, USA; §Eastman Chemical Company, Kingsport, TN, USA; ††ECC Interna-
tional, Atlanta, GA, USA
8.4.3
Sealants
Sealants or caulks in accordance with ISO 6927 are materials which remain plastic or
elastic and are used for sealing a joint between two separate construction parts, thus,
eliminating passage of the “elements” through the joint (i.e. hot or cold air, mois-
ture, insects). While a caulk needs only fulfill the above general purpose, sealants are
considered higher end products that must additionally perform after repeated exten-
sion-compression cycles originating from material temperature and humidity fluctu-
ations. Historically, the starting point for sealants was the natural raw material lin-
seed oil, mixed with chalk to give window putty.
Synthetic polymers suitable as binders for the production of caulks and sealants
include silicones, polyurethanes, polysulfides, and aqueous polymer emulsions. The
importance of these sealants in the construction industry has also increased consid-
erably through the increased use of prefabricated elements. The movement of com-
ponents must be absorbed and compensated by the joint sealant. These movements
can be expansion, contraction, or shear.
While silicones, polyurethanes and polysulfides set through a chemical reaction,
water based emulsion sealants achieve their functional end state by simple physical
drying, i.e. evaporation of the water. The majority of emulsion sealants are com-
posed of acrylic emulsions and to a lesser extent vinylacrylic and other copolymers.
Polymer emulsion sealants can be used on all sorptive substrates, such as con-
crete, aerated concrete, cement panels, plaster and wood. They are used for sealing
all types of internal joints, connecting joints (internal and external) and expansion
joints (internal and external) with a movement capability of 10–15 %. In Europe, the
joint design is stipulated in the relevant standards, for example DIN 18540.
The total caulk and sealant market in North America is estimated 500 000 tons of
formulated sealants [80], with acrylic emulsion sealants comprising approximately
15 % of the total market, and 23 000 tons dry acrylic resin. Water based sealants, sold
primarily in cartridge tubes, are used predominately in construction applications
whereas reactive urethanes and silicones are used in more demanding construction
and automotive applications.
Formulation ingredients
The properties of an emulsion caulk or sealant are affected by the type of emulsion,
and by the type and amount of the fillers and/or pigments, plasticizers and thicken-
ers [81].
Fillers reinforce and increase the volume of the sealant. Fillers also reduce formu-
lation costs and affect the technical properties of the sealant itself. Common fillers
for sealants are calcium carbonate (chalk), aluminum silicate (clay), barium sulfate
and silicic acids. Finely divided fillers, such as talc and Microdol 1, reduce the sur-
face tack while simultaneously stiffening the film. Thixotropic fillers, for example
fumed silica or SiO2, improve the gunnability and reduce the sag of the composi-
tions. Pigments are used to color sealants; the white pigment used is usually titani-
um dioxide.
Depending on the degree of compatibility, plasticizers and coalescents reduce
the glass transition temperature of the polymeric component and thereby enhance
low-temperature flexibility and film elongation. While improving formulation cost,
excessive plasticizer detrimentally affects film strength, tack and therefore, dirt pick-
up resistance. For the production of polymer emulsion sealants, phthalates, diben-
zoates, polyisobutenes and Plastilit 3060 have proven successful. With Plastilit 3060
(propylene glycol alkylphenyl ether) as plasticizer, sealants with faster skin forma-
tion after application and lower Shore hardness which are particularly elastic at low
temperatures are obtained. Experimental testing to ensure long-term polymer-plasti-
cizer compatibility and minimum tendency to volatilize or migrate to the exposed
surface is always recommended.
Dispersing aids and surfactants improve the incorporation of fillers and pigments
and improve the sealants’ storage stability. In general, low molecular weight polycar-
boxylic acid salts are used.
Silane-based coupling agents can be employed to improve adhesion to difficult
substrates (e.g. glass, aluminum). A new class of hydrolysis resistant silanes are now
available [82] which minimize self-crosslinking reactions, improve storage stability
and provide desired enhanced adhesion performance even after extended package
aging. Sealants containing small amounts of silane adhesion promoter are referred
to as “siliconized”.
Anionic thickeners based on polycarboxylic acids, associative thickeners and
fumed silica are used to adjust the rheological behavior of sealants. Highly disperse
fumed silica with a average particle diameter of from 10 to 30 µm is used as
thixotropic agent to ensure that the sealant flows out of the cartridge well even under
gentle pressure, but has low sag after removal of the shear stress.
Addition of suitable antifreeze agents, for example ethylene glycol, protects the
sealants against freezing during storage and transport.
Both “wet phase” biocides and “dry film” preservatives should also be added to the
sealants produced using polymer dispersions in order to achieve adequate protection
against microbiological attack. The suitability of these preservatives must be estab-
lished and monitored experimentally.
The mechanical properties of water-based sealants are essentially determined by
the ambient temperature and atmospheric humidity. Figure 8-30 shows the tensile
stress of a sealant at 50 % elongation as a function of time under various climatic
drying conditions.
Sealant types
Three types of water-based sealant are commercially available; clear, translucent, and
filled sealants. The majority of the market (>75 %) consists of the filled variety. Clear
and translucent sealants are used when a clear or translucent “look” is desired and in
applications requiring higher adhesion performance, elongation, and dried film
strength. While fillers serve to reduce formulation cost and surface tack, thus, dirt
pickup, they reduce adhesion performance and film elongation.
Clear and translucent sealants consist primarily of polymer dispersion (ca.
75–95 % by weight) and various formulation auxiliaries such as plasticizers, de-
foamers, preservatives, thickeners, and freeze-thaw agents. Since fillers are not used,
formulation solids content is essentially defined by the solids content of the polymer
dispersion used, which for currently available materials, is typically <65 %. Higher
water contents promote slower sealant drying rates. Relatively hard acrylic copoly-
mers (Tg = –10 to +10 °C) are needed in clear sealants to minimize surface tack and
subsequent dirt pick-up. Translucent sealants are formulated similarly but with
small amounts of fumed silica thickener to adjust flow properties.
Filled sealants are typically formulated with approximately 25–35 wet parts poly-
mer dispersion per 100 parts total formula, with filler to binder ratios in the range
from 2 to 4. With high filler loads, formulation solids contents in the vicinity of 90 %
are possible. Because of the “stiffening” effect of most fillers, filled sealants are pro-
Fig. 8-30 Tensile stress values of a dispersion sealant at 50 % elongation

and various climatic influences, r.h. relative humidity.
duced either with lower Tg emulsion polymers (–40 to –30 °C) and low plasticizer lev-
els or with higher Tg copolymers (<0 °C) and higher levels plasticizers which “soften”
the dried sealant film.
1. Filled sealant with good elasticity (even at low temperatures) and a broad adhesion
spectrum
Wet parts
Dispersion Acrylic dispersion, pH 8 with NaOH 20 % 31.5
Plasticizer Plastilit 3060* 2
Pigment paste Plastilit 3060/Kronos 2056 TiO2† (1:1) 10
Emulsifier Lumiten N-OG* 0.2
Dispersant Pigment dispersant N* 0.1
Filler, CaCO3 Omya BLP 3† 55.5
Thixotropic agent Silicic acid HDK H 20‡ 0.7
Total 100
Sealant properties: filler/binder ratio = 2.71, solids content = 89 %
Polymer dispersion properties: 65 % solids, Tg = –30 °C
2. High solids, rapid drying, low cost formulation for common gap filling applica-
tions; paintable
Wet parts
Dispersion Acrylic dispersion 23.8
Plasticizer Palatinol N, C-9 phthalate* 10
Surfactant Emulphor OPS 25, non-ionic* 0.3
Dispersant Pigment disperser N* 0.6
Filler Mikrodol 1, CaCO3 61
Sealant properties: filler/binder ratio = 4.3, solids content = 90 %
Polymer dispersion properties: 60 % solids, Tg = –10 °C
Suppliers: *BASF Corporation, Charlotte, NC, USA; †Omya GmbH, 50968 Cologne, Germany;
Tipure R901-01 TiO2 also available from Dupont Chemical, Wilmington, DE, USA;
‡
Wacker-Chemie, 81737 Munich, Germany; Aerosil 200 fumed silica also available from
Degussa Corporation, Ridgefield Park, NJ, USA.
Production of sealants
Vacuum planetary mixers have proven particularly successful for the production of
water-based polymer emulsion sealants.
The dispersion is adjusted to pH 8 using 20 % sodium hydroxide solution. Thick-
ener and dispersant are then added, and the mixture is stirred briefly at low speed.
The plasticizer is then added directly.
It has proven favorable in experiments to grind finely divided pigments (for exam-
ple titanium white and iron oxide black) with the same amount of plasticizer in a roll
mill and to incorporate the resultant pigment paste into the dispersion before the
fillers. This suppresses the formation of pigment particle agglomerates, which can
otherwise easily occur. After a stirring time of about 8 min at 30–40 rpm, the fillers
are added in 3 or 4 portions; after each addition, the mixture is stirred for about
5 min until smooth. The speed is then gradually increased to about 80 rpm. After the
final addition of filler, the stirring arms are scraped and stirring is continued for a
further 5 min. The homogeneous mixture is then deaerated for about 5 min under a
vacuum of 900 mbar with stirring at 20 rpm and then packed into polyethylene or
foil carton cartridge tubes. A minimum shelf life of 6 months can be assumed in
properly sealed cartridges.
Test methods
Resistance to flow
The resistance to flow is the property of a sealant to remain in the specified shape
after processing. For testing, a U-profile is filled with sealant (EN 27390, DIN 52454,
ISO 7390, ASTM D-2202).
Elastic recovery
Elastic recovery is the magnitude of the recovery of a sealant after prior elongation
followed by release. For the measurement, two concrete test specimens are joined to-
gether, the joint is stretched by 50 %, and after 24 h the separation is measured after
release (EN 27389, DIN 52458, ISO 7389, ASTM C-736).
Adhesion-elongation test
Two concrete test specimens are joined together and pulled apart in a tensile testing
machine at 6 mm min–1 until the breaking point is reached (DIN 52455, EN 28340,
ISO 8339, ASTM C-735).
The mechanical properties of a good emulsion-based sealant should be an elastic
recovery of 60–70 %, a tensile stress of 0.1–0.15 N mm–2 and an elongation at break
of 200–300 %.
In North America ASTM C-834 and C-920 are used. These are actually umbrella
specifications constructed from a host of individual ASTM test methods [83]. In gen-
eral, latex sealants are typically unsuitable for sealing joints which are constantly ex-
posed to water or subjected to strong expansion movements. However, sealants can
be developed which satisfy the specifications defined in ASTM C-834 for “latex seal-
ing compounds”. Higher performance “elastomeric joint sealants” based on sili-
cone, polyurethane and advanced acrylic emulsion technologies are typically de-
signed to satisfy the ASTM C-920 standard. ASTM C-920 class A sealants are those
that can withstand deformations as high as 50 % while class B sealants tolerate de-
formations as high as 25 %.
Notes for use

Water-based sealants generally adhere sufficiently well to sorptive substrates without
pre-coating. However, in order to achieve greater reliability, in particular to bind dust
particles, pre-coating of the joint edges with dilute sealant (for example 1 part of
sealant with 3 parts of water) has proven successful in practice.
The sealant is introduced into the joint using a manual or compressed-air caulking
gun. The surface is then smoothed using a wet flat brush.
Jointing should not be carried outside in the rain or at temperatures below +5 °C
since the dispersion is still water-sensitive after application. Depending on the tem-
perature and relative atmospheric humidity, it requires 30–60 min to form a suffi-
ciently thick skin on the surface. Tools should be cleaned with water immediately
after use as the residues can only be removed mechanically once they have dried.
8.4.4
Ceramic Tile Adhesives
In contrast to the traditional thick-bed method in which tiles are laid in thick layers
of mortar, the thin-bed method involves adhesive bonding. This means that the tiles
are laid into a wet adhesive bed trowel applied on to a substrate. The thickness of the
adhesive bed is variable and depends both on the size of the tiles and on the nature
of the tile undersurface. The greatest advantages of the thin-bed method are the high
application speeds and lower mortar coat or application weights (i.e. cost). However,
the thin-bed method can only be used if the substrate surface is relatively flat. This
prerequisite is achieved in most cases by using appropriate substrate preparation
techniques (e.g. cementitious self-leveling repair underlayments and floor patching
compounds) and industry proven construction materials, such as cementitious
backerboard, gypsum wallboard, underlayment grade plywood or prefabricated con-
crete panels. In thin-bed ceramic tile applications, both cementitious adhesives

(mortar) and non cementitious systems (mastics) are applied.
Ceramic tile mortar adhesives (thinsets)

Thinset mortars are employed in demanding interior and exterior floor and wall ap-
plications where there may be standing water or high moisture exposure. Both one
component polymer modified thinsets and two component cementitious adhesives
are used. Ethylene vinyl acetate copolymers (EVA) are the predominant powder poly-
mer base used in one component polymer modified thinsets, they are described in
Chapter 13. Recently styrene acrylics or straight acrylics and styrene butadiene co-
polymer powders gain an increasing market share. Two component thinsets systems
combine a cementitious powder mix and a separate polymer dispersion admixture.
Polymer modification imparts a wide range of performance improvements to
ceramic tile mortar adhesives, including improved bond strength, water resistance,
flexibility, impact strength, freeze-thaw resistance, improved mix workability. Poly-
mers also aid in promoting adhesion to difficult substrates such as plywood and vit-
reous tiles (porcelain).
Two component thinset adhesives employ acrylic, styrene-acrylic and SBR poly-
mer emulsions in the admix component. The benefit of a styrene-acrylic polymer
compared to a straight acrylic backbone involves increased hydrophobicity, thus, im-
proved moisture and alkali resistance.
Ceramic tile adhesive mastics

One component, ready to use ceramic tile mastics are used in interior residential and
light commercial applications where only intermittent water exposure is expected.
They are used both for professional tile setting and – owing to their simple process-
ing properties – in the “do it yourself” (DIY) market. They have a broad adhesion
spectrum, a long working time and form a flexible adhesive film. Mastics are gener-
ally water based and are supplied as a smooth trowelable paste for setting smaller
sized tiles (<15 cm × 15 cm).
Guiding formulation
Low emission, ammonia-free, water resistant ceramic tile mastic without film form-
ing aids
Wet parts
Diluent Water 6.4
Defoamer Nopco NXZ* 0.1
Thickener Natrosol CG 450 † 0.6
Dispersion Acrylic dispersion 20
Filler Silica sand (0.16 mm) 39
Filler Calcium carbonate (23 µm) 17.1
Filler Calcium carbonate (7 µm) 17
Total 100
Suppliers: *Henkel Corporation, Ambler, PA, USA; †US Silica, Ottawa, IL, USA
Action of the additives

Cellulosic thickeners (Natrosol) are used to adjust the viscosity and regulate mix con-
sistency, working time and spreadability. Special thickeners (Attagel 50, an atta-
pulgite clay) are used to generate a flow barrier, so that the tiles do not slip under
their own weight. In cementitious systems, cellulosics are used to provide water for
cement hydration over an extended time period due to their natural tendency to
retain water. Surfactants improve the homogeneity and shelf life of adhesives with
high filler content and also have a tendency to extend open time.
Preparation of polymer-emulsion-based CTA mastics

Additives are incorporated into the polymer emulsion in the stated sequence. The
additives are added in portions, and the mixture is stirred after each addition until it
is smooth again. These high-viscosity mastic adhesives (ca. 500 000 mPa s) can in
principle be prepared using any mixing equipment with an appropriate stirrer geom-
etry. Planetary mixers and turbulent mixers are particularly recommended. Preserv-
atives are added to the adhesives to protect them against microbiological attack.
Test methods for assessing tile adhesives

Well defined test methods are available in North America and Europe for evaluating
ceramic tile adhesives. Test methods used in Germany for emulsion-based mastics
are described in DIN EN 1324 (adhesive shear strength) and DIN EN 1346 (correc-
tion or adjustment time). Cementbased CTA are tested by DIN EN 1348 (pull of
strength) and again DIN EN 1346 (open time). Classification is determined for both
types of adhesives by prDIN EN 12004. North American test methods and specifica-
tions for tile adhesives are described in the following American National Standards
Institute (ANSI) standards:
One-component CTA mastics with glazed wall tiles ANSI 136.1
Latex-Portland cement mortar with glazed wall tile, quarry tile
and porcelain and/or mosaic tile ANSI 118.4
Latex-Portland cement mortar with quarry tile on plywood ANSI 118.11
DIN Methods
In the pull-off strength test performed with cementions CTA, the tile adhesive is first
applied to concrete. After 20 min, earthenware tiles (50 mm × 50 mm) are pressed
into the adhesive bed. After a storage time under standard atmospheric conditions,
tension anchors (50 mm × 50 mm) are attached to the smooth tile surface using a
two-component adhesive (epoxy). A tensile tester is used to measure the force need-
ed to detach the tile from the concrete; it must be greater than 0.5 N mm–2.
To estimate adjustment time, earthenware tiles are laid in the adhesive bed as de-
scribed above, rotated by 90° after 10 min and then rotated back into the original po-
sition. The adhesion pull strength after storage must still be at least 0.5 N mm–2.
Also described in DIN 18156 Part 3 is a method for evaluating vertical slip of tiles
under their own weight.
ANSI Methods
The key mechanical tests defined in ANSI 136.1 involves tile-to-tile shear strength
after dry conditioning and after water immersion. In this method, adhesive mastic is
applied to the unglazed back of a 108 mm × 108 mm test tile using a specified tem-
plate to produce a pattern of equally spaced circles of adhesive on the back of the tile.
After 2 min airing time, the unglazed back of a second tile is carefully oriented on to
the adhesive bed – tile to tile separation is controlled with the use of spacer rods. Test
assemblies are then subjected to compression under a 6.8 kg load for a period of
3 min. Bonded tile assemblies are then dried for 72 h at 50 % rel. humidity and 22 °C
and then further conditioned for 21 days in an air circulating oven set at 49 °C. Wet,
type 1 shear strengths are determined by shearing wet test specimens at a defined
rate using a tensile tester, immediately after immersing the bonded test assemblies
in a water bath for 7 days. The minimum ANSI wet, Type 1 shear strength specifica-
tion for CTA mastics is 3.5 kg cm–2 (50 psig). ANSI 118.4 includes a complete series
of methods to evaluate application properties (initial and final set, open time, ad-
justability, vertical sag) of latex–Portland cement mortars and shear strength of
bonded tile assemblies.
8.4.5
Polymer-modified Mortars
Polymer modified Portland cement mortars are used in a range of primary construc-
tion and concrete and mortar repair applications (Fig. 8-31) [86, 90].
Waterproof Membrane
Fine screed
Damaged
Concrete Repair Mortar
Fig. 8-31 Application of repair mortar.
They are applied in bridge decking and airport runway applications, in repair ap-
plications, where the mortar layer can be as much as 5–8 cm thick, in industrial floor
screeds, where up to a 5 cm layer is applied over standard concrete, in fine screeds or
patching compounds, where up to 1.5 cm of repair mortar is applied on floors, in
self-leveling underlayments, where thickness from 2–3 cm to “feather edging” are
common.
Fundamentals of concrete and Portland cements, hydration chemistry and classi-
fication of admix agents were reviewed by Kosamatka, Panarese and Soroka [84, 85].
Polymers are added to Portland cement based mortar systems for a number of
reasons. Firstly, polymers improve the key properties of the fresh, non hardened
mortar, i.e. adhesion, workability and open time. Polymer additives also tend to have
a plasticizing effect on cementitions mortars, there by reducing the amount of added
water to achieve needed workability and mortar flow properties. Minimizing added
water results in fewer capillary pores, lower porosity and stronger cements. Sec-
ondary, the properties of a hardened cement mortar are improved. Properly selected
polymers, i.e., those with Tg lower than 15 °C, form a film within the mortar ma-
trix [86] thereby filling voids, pores and reducing the potential for ingress of water
and dissolved salts. This reduced permeability to salts (e.g. chloride) provides protec-
tion against corrosion of underlying steel reinforcing elements. With reduced water
ingress, polymer modification also promotes improved freeze-thaw resistance of the
mortar – a feature which is especially important in exterior or cold climate applica-
tions.
Improved tensile, compressive and flexural strength are generally realized in poly-
mer modified cement mortars, provided sufficient levels of defoamer are added to
counteract the tendency of emulsion polymer additives to induce excessive foam
generation.
Similarly, concrete used, e.g. in critical bridge decking applications is typically
polymer modified in North America to extend service life and reduce repair costs by
minimizing deterioration caused by exposure to the many forces of nature (Fig. 8-32).
Deterioration of concrete
concrete surface
H 2O Filler particle
Crack
Steel corrosion - Rust
CaCl
Reinforcing steel
SO2
Concrete damage Pores
pH = 12 - 13
CO2
Carbonation zone
Fig. 8-32 Deterioration of concrete.
As with ceramic tile thinset mortars, styrene-acrylics, acrylics and SBR polymer
emulsions and their dry polymer analogs, including EVA powders, are employed
across the range of polymer modified cementitious applications. While polymer-
modified mortars are used widely, for cost reasons, polymer modified concretes are
seldom used – with the exception of bridge decks where SBR are almost exclusively
employed. However, in Europe the use of additives in construction concrete is regu-
lated by technical guide lines.
When developing new polymer modified mortars these days, formulators should
also consider the impact of alkali exposure on long-term hydrolytic stability of the
polymer and the subsequent impact of any degradation on application performance
and service life. By their very nature, SBR are inherently resistant to alkali induced
hydrolysis compared to some vinyl acetate containing polymers which, by virture of
the vinyl ester linkage, are more prone to hydrolysis.
Guiding Formulations
Repair mortar
Part A: Liquid Component
Wet parts
Dispersion Carboxylated SB 54
Diluent Hydration water 83
Part B: Dry Component
Filler Silica sand 721
Cement Portland cement 273
Filler Microsilica 6
Polymer/cement ratio 0.1

Water/cement ratio 0.4
Performance after 1 day 28 days

Flexural strength (bar) 60 110
Compressive strength (bar) 270 560
Test methods
The test methods are summarized in Chapter 13.
8.4.6
Waterproofing Membranes
Concrete is the most prevalent building material used in the world today [84, 86].
While concrete typically exhibits tremendously high strengths, the fact remains that
it is nevertheless porous in nature and thus, is susceptible to direct moisture pene-
tration and water vapor ingress. Additionally, acids (i.e. CO2, SO2) may penetrate into
the concrete and lower the pH of cementitious materials. Along with migration of
chloride and other salts dissolved in water deep within the concrete, this may cause
severe irreversible damage to steel reinforcements present (i.e. corrosion). Certain
additives can be introduced into the concrete mix to minimize water and salt pene-
tration (e.g. latex admixture, calcium stearate), but due to the costs involved, these
approaches are employed in only the most demanding applications, such as, bridge
decks and parking garages. Moreover, concrete admixtures do not protect the con-
crete surface layer nor are they able to eliminate moisture penetration in cases where
direct hydrostatic pressure forces exist – protective waterproofing membranes are
needed.
A host of different commercial waterproofing systems have been developed to pro-
tect against the harmful effects associated with water intrusion into concrete. These
can be broken down into pre-formed membrane sheets and applied coating systems.
Pre-formed membrane sheets typically consist of rubber modified bitumen support-

ed on a polyethylene web with a release liner to protect the highly adhesive bitumen
layer. These products are available in rolls with total membrane thickness of approx-
imately 1–2 mm and can be fiberglass-reinforced to provide improved membrane
dimensional stability. The adhesive nature of the rubber-modified bitumen assures
excellent sealing at the roll overlaps. A host of applied coating systems exist based
on rubberized bitumen emulsions, solvent borne synthetic rubber and asphalt
solutions, two-part epoxies, two-part self-curing bitumen-free liquid applied mem-
branes [91], one-component water-based elastic coatings, and flexible one or two-
component cementitious waterproofing slurries. Water based systems employing
polymer emulsion binders will be discussed further below.
Waterproofing products are used in a wide range of construction and repair appli-
cations, applied directly on to pre-formed concrete, concrete blocks, bricks, and stone
products. The most important applications include foundation building walls,
bridges, balconies and terraces, tunnels, basements, planters, silos, and parking
decks. Coating systems are typically applied to uniform thickness (1–3 mm) using a
brush, roller, trowel or spray system. In all cases, strong adhesion and intimate con-
tact of the waterproofing layer to the underlying substrate, as well as proper water-
proof system design, are required to eliminate water seepage through or around the
membrane. Depending on the application, waterproofing membranes should also
exhibit chemical resistance (e.g. to oils and acids), should remain flexible over all po-
tential use temperatures and be capable of resisting hydrostatic pressures, even over
cracks.
Both, one-component, water-based elastic coatings and one or two-component
flexible cementitious waterproofing slurries have the advantage that, by virtue of the
water carrier, they are environmentally friendly and easy to clean after application.
They both yield monolithic, seamless, puncture resistant and watertight layers after
curing but which nevertheless allow water vapor to escape from the inside to the out-
side. Cementitious systems are particularly ideal on damp substrates – because of
hydration reactions which occur in the freshly applied membrane. As they consist of
polymeric binder, sand and Portland cement, through hydration reaction chemistry
they become integrally bonded to and thereby become a part of the underlying con-
crete. Minor cracks can be bridged at low temperatures, if a sufficiently low Tg, flexi-
ble polymer dispersion binder component is selected [87, 93]. Elastic waterproofing
membranes used on the exterior of concrete structures should also exhibit resistance
to the damaging effects of UV radiation, sulfur dioxide and acid rain, carbon dioxide
(carbonation), and repeated freeze-thaw cycles.
Rubber based waterproofing systems are typically based on styrene-butadiene
copolymers and SBS resins while acrylic and styrene-acrylic dispersions are em-
ployed in most flexible one-component and two-component cementitious mem-
brane systems.
In Europe, new regulations defined in ZTV-SIB (Additional Technical Contract
Conditions and Regulations for the Protection and Restoration of Concrete Building
Components) specify crack-bridging at –20 °C [88]. As a result, lower Tg polymer sys-
tems have been developed, which yield membrane flexibility and hairline crack
bridging at lower use temperatures. The industry has moreover shifted to systems
containing, as a rule, higher proportions of polymer binder (0.8 < polymer/cement
ratio < 1) compared with earlier membrane systems.
1. One-component flexible waterproofing membrane (500 µm dry film)
Wet parts
Diluent Water 123.0
Defoamer BYK 035* 5.5
Freeze–thaw additive Propylene glycol 27.1
Pigment disperser Pigment disperser NL† 5.5
Surfactant Triton X-405‡ 1.6
Thickener Natrosol 250 MXR§ 0.8
White pigment Kronos 2101 TiO2# 134.5
Filler Duramite** 318.2
Filler Atomite** 16.4
Filler Microtalc MP 10-52†† 99.5
Biocide Proxel GXL‡‡ 3.3
Grind until smooth, then add

Polymer binder Acrylic dispersion 475.7
Thickener Natrosol 250 MXR 2.8
Neutralizing agent Ammonium hydroxide 1.8
Total 1223
Pigment volume concentration: 42.3 %; solids content: 72.8 %
2. Two-component flexible cementitious waterproofing membrane

Dry component Wet component
F-110 Silica sand§§ 28.0 –
F-95 Silica sand§§ 27.3 –
Portland cement type I/II## 19.6 –
Pigment disperser N† 0.2 –
Lumiten E-P3108 defoamer 1.6 –
Styrene acrylic dispersion – 20.6
Antifoam – 0.2
Water (to desired flow) – 0.5
Mix dry and wet components separately, then blend dry mix into the wet phase.
Apply two or three layers of 400–600 µm each.
Water/cement ratio: 0.45; sand/cement ratio: 2.82; dry polymer/cement ratio: 0.60
3. Waterproofing membrane
Wet parts
Polymer binder Styrofan D 422† 98.4
Thickener Rheolate 300*** 1.5
Total 100
Formulation 3 is intended for sealing interior walls and floors in bathrooms and
other damp areas – preventing underlying moisture damage. Compounds based on
Styrofan D 422 can also serve as “wet” concrete curing compound (by spray applica-
tion), preventing premature concrete drying during the critical hydration stage.
Suppliers: *BYK Chemie, Wallingford, CT, USA: †BASF Corporation, Charlotte, NC, USA;
‡
Union Carbide, Danbury, CT, USA; §Aqualon, Wilmington, DE, USA; #Kronos, Houston,
TX, USA; **ECC International, Atlanta, GA, USA; ††Pfizer, Easton, USA; ‡‡Zeneca Bio-
cides, Wilmington , DE, USA; §§US Silica, Ottawa, IL, USA; ##Leghigh Portland Cement Co.,
Allentown, PA, USA; ***Rheox, Hightstown, NJ, USA
Test methods
The ANSI 118.10 test specification describes key test requirements for load bearing,
bonded, waterproof membranes for thinset ceramic tile and dimension stone instal-
lation. The standard applies to trowel applied, liquid, and sheet membranes. Re-
quirements include a seam strength evaluation, membrane tensile or breaking
strength, shrinkage or dimensional stability, “waterproofness” in accordance with
ASTM D 4068, and shear strength of ceramic tile and cement mortar applied on the
waterproofing membrane. Membrane water vapor transmission is typically deter-
mined according to ASTM E 96, employing a permeation cup apparatus (Fig. 8-33).
Waterproof membranes in Europe are tested according to [92].
Waterproofness is an indication of a particular membrane material’s ability to
withstand a 60 cm hydrostatic pressure head. The apparatus employed in this test is
shown in Fig. 8-34. The membrane film is affixed at the bottom end of the J-tube and
water is then carefully introduced to an overall height of 60 cm above the level of the
membrane.
Fig. 8-33 Moisture vapor transmission cup test

assembly.
Fig. 8-34 J-Tube apparatus for measuring the

hydrostatic pressure resistance of water-proof-
ing membranes.
Fracture of the membrane or evidence of wetness on top of the material (even the
formation of a single droplet) within the first 48 h exposure, are considered as visible
signs of water penetration and require rejection of the material.
The performance of a concrete curing compound is assessed by measuring the wa-
ter loss of green concrete according to ASTM C 156-94, the water loss after three days
may not be higher than 0.7 kg m–2, acievable with SB coatings (Fig. 8-35)
Water loss (kg/m2)

4
3
without coating
1
ASTM Spec.
with SB coating
0
Fig. 8-35 Water loss of green concrete 4 24 48 72
according to ASTM C 156-94. Time (hours)
8.4.7
Elastomeric Roof Coatings
Water based elastomeric roof coatings can be described as formulated liquid prod-
ucts, that are applied by spray or roller coating to a sloped roof surface, which have
the ability to form a continuous protective polymer film over the substrate upon
evaporation of the water. Elastomeric roof coatings are used in repair applications to
seal existing roof structures and also in new building construction applications, par-
ticularly for protecting polyurethane insulating foam roofs. Elastomeric polymer
films require a proper balance of properties for the film to expand and contract and
return to its original state every time external stress-strain forces have been applied
and removed. Acrylic polymer dispersions are ideal for the manufacture of water
based liquid elastomeric roof coatings.
In particular, white pigmented roof coating membranes are becoming increasing-
ly prevalent as a result of a new EPA program called “Energy Star”. This program is
aimed at promoting energy efficient buildings and in doing so, reduce building heat-
ing and/or cooling costs [89]. The program requires the roof membrane to demon-
strate both a minimum initial solar reflectivity and maintenance of that solar re-
flectance after three years field exposure (by ASTM E 903). Buildings covered with
white coatings, compared to black asphalt type roofs, reflect rather than absorb light
radiation resulting in cooler surface temperatures and reduced cooling demands for
buildings located in hot climates.
While field exposure conditions can vary, the Tg for an elastomeric copolymer
should be lower than the minimum low temperature for a given geographic region
where the roof coating is to be applied (i.e. <20 °C). This helps assure that during
cold weather, the membrane will remain flexible and thus, prevent the roof mem-
brane from cracking under contraction stresses.
A typical “white” roof coating formulation consists of polymer dispersion mixed
with various fillers and pigments and small amounts of additives to provide stability
and to build viscosity to the roof coating mixture. The mixture is applied to a clean
roofing substrate, in two or more coats, and upon drying forms a continuous film or
coating membrane. The polymeric component binds the materials in a monolithic
state and forms the film. This coating membrane must also be sufficiently flexible to
withstand the movement of the substrate due to the diurnal cycle. It also has to pro-
vide resistance to water intrusion, cracking, and weathering while maintaining adhe-
sion to the substrate under all exposure conditions.
Low-Tg (–20 °C) pure acrylic dispersions provide excellent adhesion to poly-
urethane roofing foam and many other construction substrates. They may contain
internal crosslinking agents that crosslink the polymer film after the water has evap-
orated. Crosslinking occurs both on the membrane surface and throughout the coat-
ing providing required elastomeric film properties with only very slight residual sur-
face tack – thereby maximizing dirt pick up resistance and long-term reflectivity.
The demand for dispersions in this market is estimated to be on the order of
20 000 tons wet per annum.
Guiding formulation
Water based elastomeric roof coating
Wet parts (g)
Diluent Water 6.88
Freeze Thaw Propylene glycol 2.23
Dispersing aid 30 % Pigment Disperser NL* 0.45
Binder Acrylic dispersion 28.45
Defoamer BYK 035† 0.45
TiO2 pigment Kronos 2101‡ 11.17
Filler Duramite§ 26.36
Filler Atomite§ 1.34
Filler Microtalc MP 10-52# 18.27
Biocide Proxel GXL** 0.22
Grind, then add Binder Acrylic dispersion 12.78
Thickener Natrosol 250 MXR†† 0.34
Neutralizing agent Ammonia Solution 0.23
Defoamer BYK 035† 0.91
Weight % solids = 72; volume % solids = ca. 59
% Pigment volume concentration = ca. 42; viscosity (Krebs) = ca. 105
Suppliers: *BASF, Charlotte, NC, USA; †BYK-Chemie USA, Wallingford, CT, USA; ‡Kronos, Houston,
TX, USA; §ECC International, Roswell, GA, USA; #Pfizer, Easton, PA, USA; **Zeneca
Biocides, Wilmington, DE, USA; ††Aqualon, A Div. of Hercules, Wilmington, DE, USA
Test methods
In 1997 an American National Standard, ASTM D 6083-97a (Fig. 8-36), was issued
for determining the acceptable performance of liquid acrylic flexible roof coating
mixtures based on laboratory testing. These specifications are based on a somewhat
Film physical property ASTM test Requirement
After 14 days drying at room temperature

Tensile strength D2370 ≥200 psig
% Elongation at break D2370 ≥100 %
After 1000 h aging in a xenon arc weatherometer
% Elongation at break D2370 ≥100 %
Accelerated weathering D4798 No cracking and
checking
Low-temperature mandrel flexibility D522 Pass (1/2 in at –15 °F)
Adhesion (wet) C 794 >2 lb in–1

Water swelling (%) D471 <20 %
Permeance – inverted (perms) D1653 <50
Tear resistance (lbf in–1) D624 >60 (die C)
Fungi resistance (after 28 days) G21 Zero observed
Fig. 8-36 Standard specification for liquid applied acrylic coating used in
roofing.
broader set of test requirements described in Dade County Florida, Protocol PA 129-
95 and Protocol PA 143-95.
The standard has minimum specifications, when testing the free film for tensile
strength, elongation at break, water swelling, permeability and tear resistance. These
tests are carried out after a minimum of 14 days drying at standard lab conditions
(22 °C and 50 % relative humidity). The coated film must also meet standards for, ad-
hesion to various substrates, tensile strength, elongation at break and mandrel flexi-
bility. These tests are carried out at various specified temperatures, relative humidity
and aging conditions.
Acknowledgments
The authors would like to express their sincere thanks to the following colleagues for
friendly assistance in writing the “Applications for Adhesive and Construction In-
dustries” chapter and for critical checking of the manuscript: H. Anders, G. Auchter,
O. Aydin, M. Drewery, W. Druschke, P. Fickeisen, P. Fitzgerald, H. J. Fricke, R.
Füßl, H. Jäger, J. Krobb, U. Licht, W. Mächtle, L. Maempel, H.W.J. Müller, J. Neu-
mann, J. Pakusch, H. Seibert, B. Schuler, K.-H. Schumacher, F. Schwarz, J. Torres-
Losa, J. Türk, A. Zettl, A. Zosel
251
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9
Applications in the Carpet Industry
Peter R. J. Blanpain, Richard L. Scott, Onno Graalmann, and J. Arthur Smith
9.1
Introduction
This chapter covers the use of synthetic polymer dispersions in the carpet industry.
In 1999, carpet accounted for approximately 60 % [1] of the volume of all floor cover-
ings (soft and hard) sold in the USA, with an estimated [2] sales volume and value of
1.6 billion m2 and $11.7 billion respectively. Of this volume, the tufted carpet and
rug segment, the largest user of polymer dispersions, is dominant with an estimated
1.4 billion m2, with broadloom’s share accounting for approximately 1.3 billion m2.
Europe and the Asia-Pacific countries produced during the same period an estimat-
ed 1.13 billion m2 [3] and 284 million m2 soft floor covering respectively.
Synthetic polymer dispersions have been used as binders for the backing of carpet
since the late nineteen-forties. The function of the polymeric binder in carpet back-
ings is primarily to anchor the pile fibers in place, give improved dimensional stabil-
ity, hand, and resistance to fraying or tuft loss at cut edges of the carpet.
Carpet backing is the fourth largest user of synthetic dispersions in North Ameri-
ca (NA) after paints and coatings, paper, and adhesive applications. During 1999, dis-
persion consumption in carpet backings was around 490 kt (wet) [4], which repre-
sents around 9 % of the estimated 5,300 kt total dispersions (wet) produced in the
USA. In Western Europe and the Asia-Pacific regions, dispersion usage during 1999
has been estimated at respectively 400 kt [3] and 100 kt wet.
9.2
History of Carpet
The history of the manufacturing of rugs and carpets began with weaving. Evidence
obtained from excavations near the Caspian Sea indicates that the spinning and
weaving of sheep and goat wool was practiced as early as 6000 BC. It is known that
the Egyptians of 3000 BC wove linen carpets ornamented by sewn on pieces of col-
ored woolen cloth. A Turkish knotted pile rug, dated back to 500 BC, was found in
254 9 Applications in the Carpet Industry
Siberia in the nineteen-fifties. The weaving of hand-knotted rugs spread throughout

the Orient, and Persia (Iran) became the predominant manufacturer.
Oriental rugs were carried to Europe by the Saracen conquerors of Spain, by re-
turning Crusaders, and later Italian merchants. The Spanish in the 13th century,
were the first Europeans to make hand-pile rugs. Moorish weavers were probably
taken from Spain in the 13th century to start the early French carpet weaving indus-
try at Aubusson. Deep-pile rugs, called Savonneries, were first produced in Paris
during the early 17th century. The revocation of the Edict of Nantes in the late 17th
century, that had guaranteed religious and civil freedom to French Protestants, drove
French and Walloon Protestants (the Huguenots) into England, The Netherlands
and Germany, where they made significant contributions to the early development
of the spinning and weaving industries in these countries. The chartering of carpet
weavers in Wilton and Axminster in 1701, and the introduction of carpet production
in Kidderminster around the 1740s, was the beginning of the establishment of Eng-
land as the world’s major woven carpet producer. This situation continued until the
1960s, when technology developed in America for tufted carpet production was in-
troduced into Europe. This resulted in woven carpet production declining in Eng-
land by about 70 % by the1970s, and the establishment of Belgium, The Nether-
lands, Germany, and Great Britain as Europe’s major tufted carpet manufacturers.
Before the 1790s, the carpet business in the USA was monopolized by expensive
woven imports from The United Kingdom. The US carpet industry had its modest
beginning in 1791 when William Sprague founded the first woven carpet mill in
Philadelphia. During the early 1800s, as carpet became more popular, other factories
were established in New England, New York, and Pennsylvania. Continued domina-
tion by British imports, stimulated efforts to improve methods of production, and in
1839 Erastus Bigelow’s invention of the power loom, which made the mass production
of woven carpet possible, reshaped the industry. This, together with the invention of
the Axminster loom in 1876 to produce woven carpets with a wide range of designs
and colors, increases in loom widths, and other advances in technology, further stim-
ulated the expansion of the US woven carpet industry. The woven carpet industry
continued to thrive until the end of the nineteen-forties and the advent of tufted carpets.
The tufted carpet industry had its beginning in the late 19th century, when a Dal-
ton (Georgia, USA) woman, Catherine Evans Whitener, produced bedspreads by
sewing thick cotton yarns with a running stitch, into an unbleached muslin base
cloth, and cutting the surface loops of the yarn so they would fluff out. After tufting,
the material was washed to cause the muslin to shrink around the tufts to mechani-
cally hold them in place. She sold the first bedspread in 1900, and generated so much
interest that a thriving cottage industry started. Bedspreads led to other small tufted
goods such as toilet covers, robes, and small “scatter rugs,” and by the 1930s there
were around 10 000 “Tufters” in the Dalton area.
During the late 1920s and early 1930s, increased costs, and falling prices due to in-
creased competition, resulted in the development of multi-needle tufting machines,
the mechanization of looms, and building of looms of greater width in order to meet
demands for more bedspreads. Tufting machines for producing carpet appeared in
the late nineteen-forties, and by the late nineteen-fifties, carpet affordable to virtually
9.3 Present Day Carpet Business 255
every home owner in the USA, was being produced in twelve foot widths, using ny-
lon fiber, and jute as the secondary backing cloth. The evolution of the US carpet in-
dustry since this time is depicted below in Tab. 9-1.
Tab. 9-1 Evolution of the US carpet industry (in million m2).
Year Tufted carpet Woven carpet Total
1950 [5] 16 65 81
1974 [5] 724 61 785
1992 [6] 1094 19 1113
1998 [6] 1404 30 1434
1999 [2] 1432 34 1466
9.3
Present Day Carpet Business
In 1999 [2], the US carpet industry produced an estimated 1.6 billion square meters
of carpet floor coverings, with a value of $11.7 billion. This represents 45 % of the to-
tal world carpet production. The state of Georgia accounts for 74 % of US production
nearly all of which is concentrated in the northwest corner of the state around the
city of Dalton [7]. As shown in Tab. 9-2, tufted carpet is by far the largest carpet type
produced with approximately 90 % of the total carpet volume, with broadloom carpet
representing around 90 % of the tufted volume. Second largest are the carpets
grouped under others (knitted, knotted, needlepunched, etc.) with around 8 % of the
total. Woven carpet has almost disappeared and today only represents around 2 % of
the total carpet manufactured.
Tab. 9-2 1999 US carpet production (in million).
m2 US $
Total Tufted 1432 10692

Woven 34 450
Other 129 548
Total 1595 11690
The situation in Europe, as indicated in Tab. 9-3, is somewhat different in that wo-
ven (13 %) and needlepunched (26 %) carpet floor coverings still have an appreciable
share of the total.
In the USA tufted broadloom carpet, the most important segment of the tufted
carpet business with an estimated 1.3 billion m2 in 1999, is constructed for use in
three markets:
– consumer residential: purchases for use in a home by members of a family.
– contract residential: purchases by persons other than the home owner for
new homes, apartments, condominiums, multifamily
units, recreational vehicles, manufactured housing, etc.
Tab. 9-3 1999 European carpet production (in million).
m2 I*
Tufted 682 6656

Woven 143 1746
Needlepunched 296 441
Total 1121 8843
*Courtesy: GUT e.V., Aachen, Germany
– contract commercial: purchases other than by a home owner for hotels, mo-
tels, college dormitories, school rooms, business offices,
banks, institutional buildings and industrial buildings.
In terms of square meters and market share percent, 1999’s production forecast
(USA) [1] for the three types of carpet is summarized in Tab. 9-4.
Tab. 9-4 Broadloom carpet by market type (in million).
Type m2 %
Consumer residential 707 54

Contract residential 262 20
Contract commercial 339 26
Total broadloom 1308 100
In all three, whilst the binder used for construction may be the same, the type and
formulation of the backing adhesives differ significantly, as each category of carpet
has different performance specifications. The formulations employed, and methods
of adhesive application, for producing the three carpet types will be detailed in sec-
tions following, together with insight into their end use property requirements.
9.4
Carpet Backing Binders
During the late nineteen-forties, the starches and natural gums initially used as
binders for improved tuft bind, were largely replaced by rubber dispersions. In the
nineteen-fifties, the major binders were natural latex, cold SB (styrene-butadiene)
and hot SB dispersions, the polymers usually being vulcanized to obtain good
strength. The mid nineteen-fifties saw the introduction of non-cure hot SB disper-
sions, which began to replace the sulfur cure SB. The late nineteen-fifties saw the
development of carboxylated styrene-butadiene dispersions (XSB) and their intro-
duction as binders for carpet backings. These XSB dispersions, as a result of the
easier and less costly compounding, faster drying rate, and improved performance
in terms of specific adhesion to the fabric substrates, have since become the work-
horse of the carpet backing industry. The 70s through to the early nineteen-eighties
was the era of the attached SBR foam cushion backings. Such carpets were con-
9.4 Carpet Backing Binders 257
structed using a compounded XSB dispersion pre-coat or tie-coat to bind the tufts in
place, followed by the application of a foamed compound of a high solids styrene-
butadiene latex (HSL), to provide under foot comfort, and prolong the useful life of
the carpet.
Foam backing is a process in which a high solids SB dispersion, a vulcanizing
agent (suspension of sulfur, zinc oxide, accelerators), chalk and emulsifier together
with air is frothed. The wet foam structure needs to be maintained until vulcaniza-
tion takes place. This can be achieved by gelling agents which destabilize the poly-
mer particles by smoothly decreasing pH and coagulating the latex within the mem-
branes of the wet foam. Non-gel foam is stabilized with emulsifiers which maintain
the foam structure during the evaporation of water until vulcanization takes place.
Vulcanization is carried out at about 100 °C resulting in an elastic polymer network.
The polymer/filler ratio varies from 1:0.5 to 1:2.
In 1975 it was estimated that one third of all the broadloom carpet produced in the
USA had an attached SBR cushion. Unfortunately, the highly competitive situation
prevailing at the time, compelled manufacturers to reduce the cost of the attached
foam by either increasing the level of the cheap calcium carbonate filler and/or re-
ducing foam application weights and density. This inevitably adversely affected the
durability of the foam to such an extent that failure occurred resulting in premature
wear of the carpet. As consequence of the bad name that attached SBR cushions ob-
tained in the eyes of consumers, today HSL foam backed carpet has virtually disap-
peared in the USA, with the exception of a few specialty floor coverings such as bath
mats.
The situation in Europe is somewhat different to that of the United States of
America. In general the styles of carpet produced in Europe have a much lower face
fiber content, the pile height being much lower and pile density higher. The foam
backing was also generally of higher density therefor thinner for an equivalent
weight. The transfer of heat into the foam product is much easier, and enabled high-
er production speeds to be achieved than were possible in the USA.
A similar situation to that observed in the USA has been experienced for similar
reasons, but at a much slower speed. The consumption of HSL for foam backing re-
mained fairly static for many years, the growth in the market being almost entirely
restricted to secondary backed products, and the market share of foam backed carpet
being gradually eroded.
In the late nineteen-nineties environmental pressure, particularly in Germany, re-
sulted in a very steep decline in the consumption of HSL for floor coverings. Several
of the ingredients used in the formulations for HSL foam in the floor coverings in-
dustry were brought into ecological question. Since 1998, when foam backed carpets
made up approximately 45 % of textile floor coverings in Europe, this has decreased
to approximately 20 % in 2000.
An alternative more ecologically friendly product was required. In Europe this was
achieved by replacing the HSL foam by a needlefelt product which is adhered to the
carpet by means of an XSB latex. In North America carpet underlays made of
polyurethane foam are commonly used to provide the soft comfort of residential
carpets.
Over the years, it is fair to say that virtually every type of polymer available in dis-
persion form has been tried for use in the backing compound for tufted carpet. How-
ever, because of its versatility and cost-effectiveness, it is the carboxylated styrene-bu-
tadiene (XSB) polymer dispersions that hold the major share of this business today
with an estimated 95 % of the volume sold in 1999, the remaining volume being
shared by ethylene-vinyl acetate, polyvinyl chloride and polyurethane dispersions.
During 1999, the US carpet industry consumed approximately 490 kt wet dispersion,
of which 463 kt were XSB [4]. The majority of the XSB is supplied direct to the carpet
mills by the three major dispersion producers BASF, Dow Chemical, Omnova, with
a minor proportion being supplied by so-called re-sellers or compounders such as
General Latex, Polymer Products, Southeastern Latex and Textile Rubber.
The XSB binders of today are considerably different from those at the time of their
introduction into carpet backings. Ongoing advances in polymerization technology
have enabled tailoring of the physical and polymeric properties of dispersions to bet-
ter meet the evolving demands of present day backing machines and performance
requirements. Whilst the dispersion formulations are the proprietary information of
the producers, some typical characteristics of the dispersions commercially available
today are given below.
Polymer type: Carboxylated styrene butadiene dispersion (XSB)

Bound styrene: Typically in the range 60–67 %
Carboxylation: Typically less than 3 % by weight of the polymer. The car-
boxylic acid may be itaconic acid alone or blends of itaconic
acid with either acrylic acid or methacrylic acid. The actual
type/level of carboxylation is proprietary information to each
producer.
Solids content: 51–53 % dry weight
pH: 7.5–9.0
Particle size: Up to 10 years ago, 170–200 nm used to be the norm. Today, as
consequence of the need to reduce 4-PCH content, particle
sizes are generally within the 140–155 nm range.
Volatile organic Over the last 10–12 years, and the advent of “Sick Building
components (VOC): Syndrome”, the dispersion producers have radically improved
their XSB manufacturing processes to minimize the level of
residual organic compounds. Today, the maximum target val-
ues, in ppm on wet dispersion, for the four major VOC are giv-
en in Tab. 9-5.
Surfactants: Type and level is the proprietary information of the individual
producers. They are usually selected not only for good stability
and low foaming during the dispersion manufacturing
process, but also to impart the required foaming properties to
the backing binder formulations during processing in the cus-
tomer’s plant.
Tab. 9-5 Maximum limits (ppm) of volatile organic components.
North America Europe* Denmark
Styrene 35 200 40
Ethylbenzene 10 50 20
4-Vinylcyclohexene 15 50 10
4-Phenylcyclohexene 60 200 50
Total <400
*Definedby EPDLA (European Polymer Dispersion and Latex Association)
and GuT (Association for environmental friendly carpet)
9.5
Carpet Laminating
9.5.1
Background
Several types of carpets including woven, needlepunch, knitted, and tufted are sub-
jected to the latex laminating procedure [8]. By far the most prevalent carpet con-
struction method is tufting. The first tufting machines were very similar to a giant
sewing machine that uses thousands of threaded needles in a row across the width of
the machine. Today’s machines are far more complex and sophisticated, although
they still work in the same basic way. The creel, or rack of yarn cones, are located in
front of the tufter. From the creel, the yarns are passed overhead through guide
tubes to puller rolls. The speed of the puller rolls controls the amount of yarn that is
supplied to the tufter and, with other factors, determines the carpet’s pile height.
The needles, which number up to 2000 for very fine gauge machines, insert the
yarn into a primary backing supplied from a roll of material located in front of the
machine. Spiked rolls on the front of the tufting machines feed the backing through
the machine.
Below the needle plate are loopers, devices shaped like inverted hockey sticks,
timed with the needles to catch the yarn and hold it to form loops. If a cut pile is
called for, a looper and knife combination is used to cut the loops. For cut-loop com-
binations, a special looper and conventional cutting knife are used.
Tufting has reached a high degree of specialization utilizing a variety of patterning
devices, many of which are computer-controlled. Stepping, or zigzag moving, needle
bars and individually controlled needles greatly expand patterning possibilities. Such
patterned carpet is frequently referred to as a graphic pattern. Other advanced tuft-
ing techniques are loop over loop and loop over cut (LOC) machines.
After completion of tufting, the unfinished tufted carpet will be dyed, if precolored
yarns are not used, followed by a finishing step to add a compound and usually a sec-
ondary backing material.
Carpet laminating or backcoating is an essential step in the carpet manufacturing
process. Since the backcoating is hidden from view, the attributes it imparts to the
finished carpet are rarely appreciated. Both the long term performance and the aes-
thetic value of the installed carpet are vitally dependent upon a correctly formulated
and a properly applied backcoating. Among the most important performance re-
quirements of a backcoating are:
– high tuftlock
– minimum pilling and fuzzing
– adhesion to secondary backing
– dimensional stability
– bundlewrap
– proper hand
– durability
– water resistance
– resistance to heat, light, and atmospheric contaminants
– flammability-pill, tunnel, radiant panel, smoke, vertical burn
– resistance to edge fraying
– odor
9.5.2
Carpet Terminology
Before proceeding further with carpet laminating, a review of carpet terminology

would be useful, since physical properties imparted by the SB latex backcoating re-
late directly to its construction. Figure 9-1 illustrates a typical cut pile carpet and the
physicals associated with it. A level loop carpet would appear the same but the tops of
the tufts would not be cut. Physicals and terminology for a level loop carpet would be
the same as for cut pile.
Fig. 9-1 Carpet terminology.

Tuft: One cut or uncut loop of a pile fabric

Bundle: A continuous tufted collection of fibers or filaments
Filament: A single continuous strand of fiber
Primary: Woven or non-woven fabric into which the pile yarn is inserted
by tufting
Secondary: A woven or non-woven fabric laminated to the tufted primary
to provide dimensional stability
Delamination: The force expressed in lb/inch required to remove the second-
ary backing from the primary carpet (ASTM D 3936, ISO
11857).
Tuftbind: The force expressed in pounds required to remove a single tuft
from its primary backing (ASTM D 1335)
Pill and fuzz: Hairy effect on the carpet surface caused by slippage of indi-
vidual filaments or fibers
Bundlewrap: A subjective rating, usually expressed as a percentage, to indi-
cate the degree of latex encapsulating the yarn
Bundle penetration: A subjective rating, usually expressed as a percentage, to indi-
cate the degree of penetration into the yarn
Hand: A subjective rating to indicate the stiffness of the finished carpet
9.5.3
Back-coating Applications
Over the last few years, direct coating with scrim lock has replaced pan application as
the preferred method for back-coating carpet. The major advantages associated with
direct coating are:
– less waste (mill and disposal savings)
– easier clean up
– overall ease of operation
– uncoated selvages (cost and clean up savings)
– uniform weight control side to side
– uniform coating side to side
– fresh compound always available
– less problems with filler fallout
– higher compound solids
– immediate response to cup weight changes
– short lag time for compound changes
– elimination of density variations (airing up or collapsing in pans)
– thixotropic effects eliminated (troughing, poor pickup)
– better visual weight control (puddle gain or loss seen immediately)
– faster drying due to lighter densities
Figure 9-2 depicts a typical direct coating unit with scrim coat. This schematic
shows a set up utilizing a bed-plate for the application of the pre-coat and a pan for the
application of the adhesive scrim coat. Variations of this include a roll over roll for
the pre-coat application and a roll over roll or Tillitson application for the adhesive.
Fig. 9-2 Direct coat-

ing with scrim coat.
9.5.4
Back-coating Formulations and Ingredients
Direct coating is used to back-coat both residential and commercial carpets. Back-
coating residential carpets involves two latex compounds. One is highly loaded with
filler and is deposited directly onto the tufted primary after having passed through a
mechanical froth machine. The froth machine lowers the density thus allowing for
proper placement and weight control. This compound is usually referred to as the
pre-coat or undercoat. Its primary purpose is to securely lock the tufts into the pri-
mary backing. Other properties affected by the pre-coat are pill and fuzzing, hand,
delamination, and flammability.
Along with latex, the pre-coat compound would typically contain water, filler, sur-
factant, and thickener.
Water is used to adjust the solid content of the compound, aid in the dispersion of
the filler, and extend shelf life.
The filler is almost always calcium carbonate due to its universal availability and
economical price. Its grind and purity are critical for compound stability and run-
ability. Typical pre-coat loadings are between 400 and 600 parts per 100 parts dry
latex. To enhance flame retardant properties, aluminum trihydrate can be substitut-
ed for all or part of the filler in the pre-coat.
Surfactants are used to increase stability and frothability of the compound. Sodi-
um lauryl sulfate (SLS) and ammonium lauryl sulfate (ALS), sodium sulfosuccina-
mate, and combinations of ALS and long chain alcohol are commonly used.
Thickeners are almost always sodium polyacrylates. They impart the proper vis-
cosity and rheology to allow proper placement of the compound. They also help to
suspend the filler in the compound.
Miscellaneous ingredients occasionally will be used, if a back-coating needs a spe-
cific appearance or specialized performance property. Miscellaneous ingredients in-
clude pigment, penetrant, defoamer, dispersant, chelating agent, anti-blistering
agent, antistatic agent, and stabilizer. A typical pre-coat formulation used in North
America is represented in Tab. 9-6.
Tab. 9-6 Pre-coat formulation (US).
Solids content (%) Dry parts Wet parts
Water – – 35
XSB latex 53 100 188
Calcium carbonate 100 550 550
Surfactant 35 2 5.7
Polyacrylate thickener 13 1 7.7
Total 83 653 786
Solids content of the formulation 83 %; viscosity 17–18 Pa s
In Europe a typical pre-coat formulation does not exist due to widely differing
styles and quality requirements. In general they contain more filler (600–1000 dry
parts of calcium carbonate), less surfactant (0.2–0.5 dry parts), and less thickener (0.4
dry parts), and viscosity of 3–5 Pa s.
The second compound used in residential carpet coating is referred to as the
adhesive scrim or skip coat. It is applied by means of a pan and lick roll directly to the
secondary backing. This coating provides the strength necessary to sufficiently ad-
here the secondary backing to the primary backing, which in turn imparts dimen-
sional stability to the carpet.
The adhesive scrim coat formulation is similar to the pre-coat with two exceptions.
First, since the compound is not frothed, surfactant is eliminated from the formula-
tion. Secondly, since a stronger compound is required for the adhesive coating, filler
loading is reduced. Loadings between 350 and 400 parts of filler per 100 parts of dry
latex are typical. Table 9-7 is representative of a typical adhesive formulation.
Tab. 9-7 Adhesive scrim coat formulation (US).
Water – – 12
XSB latex 53 100 188
Polyacrylate thickener 13 0.6 4.6
Total 82 475.6 579.6
In Europe the ingredients for secondary backing compounds are similar but the
filler loads can vary from 0–450 parts per hundred part of dry latex. The configura-
tion of the coating machines determines the compound to be used. On average the
viscosity is 5 Pa s.
Since most commercial contract carpets are glued directly to the substrate, the
need for a secondary backing is eliminated. Thus most commercial contract carpets
are coated with a single high strength compound referred to as a unitary coating. To
meet the enhanced performance requirements of commercial contract carpets a
high density, low filled compound is used. High density is achieved by using low
surfactant levels and lightly frothing the unitary compound. Filler levels are typically
in the range of 150–200 parts of filler per 100 dry parts of latex. The two most impor-
tant properties of a unitary coating are high tuft-bind requirements (11–20 lb,
50–90 N) and pill and fuzzing. Table 9-8 illustrates a typical North American unitary
formulation.
Tab. 9-8 Unitary backing formulation (US).
XSB latex 53 100 188.6

Surfactant 35 0.5 1.4
Polyacrylate thickener 13 0.4 3.1
Total 73 250.9 343.1
European unitary formulations would be very similar both in ingredients and filler
loads to the above North American formulation. Typical viscosity is 5 to 7 Pa s.
9.5.5
Industry Issues
Although direct coat has been universally accepted as the latex application technique
of choice, there still exist large variations in processing speeds due to a wide range of
dryer configurations and their efficiencies. Current processing speeds for a light
weight carpet can range between 10 to 60 m min–1.
As the industry becomes even more competitive, manufacturers will be forced to
continue to reduce fixed and variable costs. More and more high speed dryers will re-
place slow inefficient ones.
Computerized froth machines will become more common as mills focus on re-
ducing variable costs. Utilizing computerized frothing machines eliminates the need
to sample for density control and allows for a more consistent latex application due
to the consistent froth produced.
Feed forward application systems are beginning to be used by some manufactur-
ers. This system produces a more consistent compound application resulting in en-
hanced performance.
Electronic monitoring from the compounding area to final inspection is reducing
manpower requirements and increasing dryer efficiency dramatically.
Following is a list of process improvements currently being implemented or antic-
ipated for implementation in the future:
– movement toward high efficiency, high speed finishing ovens
– increased use of computerized froth machines
– feed forward application systems

– some carpet producers beginning to question delamination testing as best indica-
tor of “fit for use”
– increased use of polypropylene fibers for commercial carpet resulting in greater
need for latex that has an affinity for polypropylene
– greater need for blister resistant latex due to higher heat and more efficient ovens
– increased commitments through quality partnerships by both latex producers and
carpet manufacturers in the use of statistical process control
– movement towards low/zero ammonia systems to reduce emissions into the work-
place
– quality issues have replaced VOC issues as the primary concern of carpet manu-
facturers.
Since 1988 there has been a heightened awareness of volatile organic compounds
(VOC) emitted from carpet. In the early nineteen-nineties allegations stemming
from flawed scientific work arose connecting a chemical (4-PCH) emitted from car-
peting to adverse health effects. 4-phenyl cyclohexene or 4-PCH is a byproduct of the
SB latex manufacturing process and has a low odor threshold. It is formed by a Diels-
Alder reaction of styrene and 1,3-butadiene and is responsible for “new carpet odor”.
As a result of the allegations the Styrene Butadiene Latex Council (SBLC), the trade
association of US latex producers and the EPA (Environmental Protection Agency)
undertook extensive animal toxicological testing to investigate whether there was a
link between 4-PCH and adverse health effects. After exhaustive testing and numer-
ous reviews, the EPA declared 4-PCH to be an “unremarkable chemical” [9]. EPA has
repeatedly concluded that valid scientific data showed no link between 4-PCH or any
other carpet VOC emission, and adverse health effects.
Even though carpet emissions have been declared to produce no adverse health ef-
fects, the issue of new carpet odor had to be addressed. As a result, the SBLC mem-
ber companies have reduced VOC emissions by 95 % since 1988. With present low
VOC latex and proper drying technique, carpet manufacturers today can produce
odor free carpet. As well as creating an odor free environment for the carpet con-
sumer by reducing VOCs, the trend toward ammonia free latex is also creating a
more worker friendly environment in the manufacturing site.
Even though alternative backing systems are available, SB latex still accounts for
over 90 % of the carpet back-coating market. Due to its performance, versatility, and
economics, SB latex continues to afford the carpet manufacturer the best value in
back-coating systems today and for the foreseeable future.
266
References
1 Floor Covering Weekly, Statistical Report 6 Carpet and Rug Institute, 1999 Industry
’99, 49(19), July 17/24, 2000. Review, 1999.
2 US Department of Commerce, Bureau 7 CRI The Tufted Carpet Industry, The
of Census, Current Industrial Reports, Pride of Georgia, History and Current
Carpet and Rugs, 2000. Statistics, 2000.
3 Intercontuft, 2000. 8 Carpet and Rug Institute, Carpet
4 American Plastics Council Monthly Primer, 1997.
Statistical Report, December, 1999. 9 55 Federal Register 17404, April 24,
5 L. D. Martino, Carpet Backfinishing 1990.
Review, Brunswick Corporation, 1975.
10
Non-wovens Application
Koichi Takamura, Marilyn Wolf, and Jim Tanger
10.1
Introduction
Non-wovens are described as flat, porous sheet or web structures produced by bind-
ing and interlocking fibers, yarns, or filaments by mechanical, thermal, chemical, or
solvent means. They are porous sheets that are made directly from separate fibers,
molten plastic or plastic film. They are not made by weaving or knitting and do not
require converting the fibers to yarn.
Non-woven fabrics are engineered fabrics that may be of single-use, limited life, or
very durable. They provide specific functions such as absorbency, liquid repellency,
resilience, stretch, softness, strength, flame retardancy, washability, cushioning, fil-
tering, bacterial barrier and sterility. These properties are often combined to create
fabrics suited for specific jobs, while achieving a good balance between product use-
life and cost.
In combination with other materials, non-woven fabrics provide a spectrum of
products with diverse properties, and are used alone or as components of apparel,
home furnishing, health care, engineering, industrial, and consumer goods. They
are categorized according to application as either disposables or durables. Some
familiar products made with non-wovens are listed in Tab. 10-1 [1–3].
The worldwide production of non-wovens is estimated at 2.7 million tons (or
6.0 billion pounds) in 1999 [4–6]. Western Europe accounts for approximately 35 %
of the world production of non-woven products, followed by North America (30 %),
China (12 %), Japan (12 %) and others, as shown in Fig. 10-1. The value of non-
woven product shipment in North America reached an all-time high in 1997 with an
approximate value of $2.8 billion [7] and disposables account for nearly 70 % in
value. The non-woven industry in North America is expected to grow at 2–3 % annu-
ally and to be $3.2 billion in 2002.
China and Japan dominate non-wovens production in Asia followed by Taiwan
and Korea as shown in Fig. 10-2. Double-digit growth is expected in these countries,
and production in China and Japan reached to 350 000 tons each in 2000 with an an-
268 10 Non-wovens Application
Tab. 10-1 Some familiar products made with non-wovens.
Disposable products
Diapers, sanitary napkins and tampons
Sterile wraps, caps, gowns, masks
Drapings used in the medical field
Household and personal wipes
Filtration media
Laundry aids (fabric-dryer sheets)
Embroidery backing
Durable products
Apparel interlining
Carpet backing and upholstery fabrics, high loft padding and backing
Wall coverings
Agricultural coverings and seed strips
Electronic components (i.e. battery separations, disk liners, insulation liners, polishing cloth, etc.)
Envelopes, tags and labels
Insulation and house wraps
Roofing products
Civil engineering fabrics/geotextiles
Global Production of Nonwovens
W. Europe
Asia
Fig. 10-1 Global non-woven production

reached to 2.7 million tons in 1999. Western
Europe and Asia produced approximately
North America 35 % each.
nual growth rate of 11 % [5, 6]. China non-woven production increased 87 times dur-
ing the last two decades from 4000 tons in 1980.
The North American market for disposable applications was approximately
$1.9 billion in 1997, and represent roughly 15.5 billion yards (13 billion m2) and
900 million pounds (400 000 tons) of material. As seen in Fig. 10-3, filtration and
medical applications represent nearly 60 % of the dollar value, but fewer than 20 %
Nonwoven Production in Asia
Taiwan
100 kton
Japan
315 kton
China
315 kton Fig. 10-2China and Japan are two major
Korea non-woven producers in Asia. They reported
100 kton 11 % annual growth in 2000.
Total $1.9 billion 2

Total 15.5 billion yard (13 billion m )
2
Dryer Dryer
Sheets Wipes Sheets
Wipes Filtration
Filtration
Medical
Cover
Stock
Cover
Medical Stock
Fig. 10-3 1997 figures show disposable products account for nearly 70 %
in the dollar value and 85 % in volume in North America.
of disposable square yard volume. Cover stock applications dominate disposable vol-
ume, and approximately 80 % of this volume is used for diaper production [7].
The volume for durable non-wovens exceeds that used for disposables in Europe.
Europe has a longer history in the use of durable non-wovens, in particular geotex-
tiles and roofing substrates. This is in contrast to the North American market, where
disposable non-wovens play a stronger role as discussed above.
Electronic, Interlining, and Furniture/Bedding/Home applications account for ap-
proximately 55 % of $0.9 billion non-woven materials in durable applications in the
North American market, but furniture, bedding and home furnishing applications
are the largest volume (42 %) of non-wovens in this durable category as shown in
Fig. 10-4.
Total $ 0.9 billion Total 3.1 billion yard 2 (2.6 billion m2 )
Automotive
Electronic Construction
Automotive Electronic
Construction Materials
Interlining
Materials
Coating/ Laminates
Coating/
Laminates
Interlining Geotextiles
Geotextiles Furniture/
Furniture/ Bedding/Home
Bedding/Home
Fig. 10-4 Electronic, interlining and furniture related applications account

for 55 % of $ 0.9 billion in durable applications in North America, but
furniture related applications are the largest in volume.
North American, European and Japanese markets are shown in Fig. 10-5 compar-
ing total weight of products in 1999. Hygiene (cover stock in North America and con-
sumer goods in Japan) medical products and wipes account for greater than 50 % of
North American Production (800 kton) European Production (910 kton)

Coaging/ Coating
Laminates Civil Substrates
Geotextitle Engineering
Automotive Filtration
Carpet Backing Building

Furniture/ Medical
Hygiene
Bedding/ Home
Construction
Others
Materials
Interlining
Electronic CoverStock
Wipes Garments
Dryer Sheets
Floor Footwear/
Wipes Coverings Leather Goods
Upholstery/ Medical
Bed Linen Interlinings
Japanese Production (315 kton) Filtration
Others
Consumer
Goods
Industrial
Products
Medical
Construction
Fig. 10-5 Non-woven applications in North America, Europe and Japan

are compared by weight of products in 1999. Hygiene, medical and wipes
account for greater than 50 % in all these continents.
total production in these continents, though consumer goods in Japan appear to in-
clude some durable products.
10.2
Manufacturing Systems
Early thrust in non-woven usage emphasized replacing traditional knits and woven
fabrics in low-end applications. During this initial phase, proprietary technology was
used to produce fabric structures that performed not only better than items they
were designed to replace, but often when traditional fabrics could not. As a result,
new applications and markets were established and the industry expanded. Many
non-woven products listed in Fig 10-5 were virtually non-existent a generation ago.
The basic non-woven manufacturing systems have four principal elements or
phases: fiber selection and preparation, web formation, web consolidation, and fin-
ishing treatments.
10.2 Manufacturing Systems 271
10.2.1
Web Formation
Four basic methods are used to form a web, and non-wovens are usually referred to
by one of these methods: dry-laid, spun-laid, wet-laid and other techniques. Carding,
garnetting and air-laying are examples of the dry-laid processes. The dry-laid process-
es provide maximum product versatility, since most textile fibers and bonding sys-
tems can be utilized and conventional textile fiber processing equipment can be
readily adapted with minimum additional investment.
The wet-laid process is similar to paper making, where a dilute slurry of water and
fibers are deposited on a moving wire screen and drained to form a web. A wide
range of natural, mineral, and synthetic fibers of varying length can be used.
In the spun-laid process, polymer granules are melted and molten polymer is ex-
truded through spinnerets. The continuous filaments are cooled and deposited on to
a conveyor to form a uniform web. Even though filaments adhere to one another
during this cooling process, this cannot be regarded as the principal method of bond-
ing. The spun-laid process (also known as spun-bonded) has the advantage of giving
non-wovens greater strength, but raw material flexibility is more restricted.
Other techniques include a group of specialized technologies in which the fiber pro-
duction, web structure and bonding usually occur at the same time and in the same
place, as melt-blown and flash spun web formation methods.
Detailed description of these technologies can be found elsewhere [1, 4]. As seen in
Fig. 10-6, spun-laid and dry-laid are two preferred processes both in North America
and Europe. The spun-laid process showed the strongest growth during a last
decade [1, 7]. Products produced by the spun-laid technique account for 20–25 % of
the market in Japan and China [5, 6].
North American Market by Process European Market by Process
Wetlaid
Wetlaid
Spunlaid
Spunlaid
Drylaid
Drylaid
Other
Other
Fig. 10-6 Comparison of web formation technologies in North America

and Europe. Spun-laid and dry-laid are two preferred processes both in
North America and Europe.
10.2.2
Web Consolidation
Webs produced with the above described processed have limited strength in their
unbonded form and need to be consolidated. There are three basic types of bonding;
thermal, mechanical and chemical. The thermal bonding uses the thermoplastic
properties of certain synthetic fibers to form bonds under controlled heating. In
some cases the web fiber itself can be used, but often a low melt fiber or bi-compo-
nent fiber is introduced at the web formation stage to perform the binding function
later in the process.
In mechanical bonding the strength of the web is obtained through the physical
entanglement of the fibers. Needle punching and hydro-entanglement (also known
as spunlace) are two main mechanical bonding processes. Needle-punching can be
used on most fiber types, whereas hydro-entanglement is mainly applied to carded
or wet-laid webs.
Chemical bonding mainly refers to the application of a latex dispersion based
bonding agent to the web. The major binder application methods include saturation,
printing, spraying, and foaming. Factors to consider when consolidating a web with
binder are the end-use characteristics, the type of web substrate that is used, process
compatibility, line speed, drying capacity and cost [1].
Carded thermally bonded technology is losing significant share in the cover stock
market in North America and spun-bonded non-wovens accounted for 75 % of cover
stock in 1999 (Fig. 10-7). In contrast widely different technologies are utilized to pro-
duce non-wovens for wipes. Hydro-entangled products are expected to grow due to
superior strength and softness [7].
Cover Stock Wipes

Unbounded
Melt Blown Carded
Carded Web
Thermal Other
Bounded Carded
Thermal
Bounded
Unbounded Hydro-
Carded entangled
Web Carded
Chemical
Bounded
Wet Laid
Spun-
bounded Air Laid
Fig. 10-7 Spun-bonded products dominate the cover stock market in

North America due to better performance and lower cost. Hydro-entangled
products are expected to grow in wipes.
10.3 Polymer Dispersions for Chemical Bonding 273
10.3
Polymer Dispersions for Chemical Bonding
Most non-wovens use 5 % to 50 % of polymer binder to provide one or more of fol-

lowing characteristics: softness, non-linting, smoothness, stiffness, dry and wet ten-
sile strength, tear resistance, resiliency, flame retardancy, heat sealability, water re-
pellency, absorbency, durability, dry cleanability, abrasion resistance, pilling resist-
ance, color fastness, and bulkiness [1]. An article by Wiaczek [3] estimates that total
latex consumption in the US non-wovens market will reach 160 000 dry tons in 2001.
Latex binders fall into following two categories: those that provide rigidity to a
product and those that render a web soft and drapeable. Acrylics are the predomi-
nant binders used in non-wovens as shown in Fig. 10-8 [1, 8]. They are versatile and
offer the ultimate in durability, color stability and dry/wet performance. Ethylene
vinyl acetate binders provide high tensile strength and excellent absorbency. They
are less costly than acrylics. Styrene-butadiene latex offers an excellent combination
of flexibility and toughness. It also provides hydrophobicity and durability to prod-
ucts. Vinyl acetate binders offer good dry strength and toughness but tend to be hy-
drophilic. Vinyl acrylics are more hydrophobic than vinyl acetate binders, and main-
tain excellent toughness, flexibility and better color stability. Chlorinated polymers
such as poly(vinyl chloride) and ethylene vinyl polymers promote flame retardancy,
especially together with antimony oxide [11]. Characteristics of these latex binders
and typical applications of non-woven products are summarized in Tab. 10-2.
Vinyl
Chloride/
Others
Vinyl
Acrylic
Vinyl
Acetate
Acrylic
Ethylene
Vinyl
Acetate
Fig. 10-8 Acrylics are the predominant
binders used in non-wovens, but the
vinyl acetate ethylene latex showed Styrene-
strongest growth during the last decade Butadiene
For all these latices, monomer compositions are optimized to obtain desired
physicochemical properties, such as glass transition temperature, Tg, molecular
mass, cross-linking density, colloidal stability and specific surface functionality for
post chemical reactions.
Tab. 10-2 Basic characteristics and typical applications of latex binders used for non-wovens pro-
duction.
Latex binder type Characteristics Typical applications
Polyvinyl acetate Resilient, somewhat stiff, Highloft webs, filter media,

moderate durability, industrial, home furnishings
limited washability and
dry-cleanability
Acrylic Excellent adhesion, stiff to soft, Coverstock, interlinings medical/
excellent durability, health care, fabric softener, carder,
launderability, dry-cleanability, wet wipes
good cross-linking
Vinyl acetate- Flexibility, good adhesion, Medical and/or surgical, wipes,
acrylic copolymer good solvent resistance coverstock
Ethylene-vinyl acetate Good softness, durability Coverstock, wipes, air-laid pulp
and adhesion
Styrene-butadiene Good tear and tensile Filters, wipes, home furnishings
Poly(vinyl chloride) Stiff to soft, can be plasticized, Scouring pads, filter media,
heat sealable, low temperature wall covering
cure
Ethylene-vinyl chloride Excellent mechanical stability Underpads, highloft webs
Poly(vinyl alcohol) Resilient, water absorbent Filter media, medical
Acrylonitrile-butadiene Resilience, heat sealable, Synthetic leather
copolymer launderability, dry-cleanability
As shown in Fig. 10-7, widely different technologies are utilized to produce wipes.
This is also applicable to the binder application method. The acrylic latex can be
applied through saturation, foam impregnation or print bonding as shown in
Tab. 10-3.
Tab. 10-3 Typical latex-based formulations for wipes with saturation, foam and print bonding methods.
Saturation Foam Impregnation Print Bonding
Materials Weight, Solids, Materials Weight, Solids, Materials Weight, Solids,

g % g % g %
Acrylic latex 100 55 Acrylic latex 100 55 Acrylic latex 100 55

Water 120–450 Water* 80–150 Water1 150–450
Defoamer 0.1 100 Ammonia* Dye2
Surfactant 0–1 50 Surfactants 0–5 50 Thickener1
1
*Adjust to 10-25% solids *Adjust to 15-30% solids and pH=8 Adjust to 10–15% solids and 10Pas
Typical foam weight of 70–150 g/liter viscosity
2
Add to the desired color
10.4 Application Test Methods 275
10.4
Application Test Methods
A series of well-defined standardized test methods have been established through

various trade organizations, government and university research institutes. INDA
(Association of the Non-woven Fabrics Industry) Standard Test [2] and EDANA (Eu-
ropean Disposables and Non-wovens Association) Recommended Test Method [4]
are two major standards for non-wovens. International Standardization Organiza-
tion (ISO) and the American Society for Testing and Materials (ASTM) refine and
approve a wide range of test methods developed by these trade organizations. INDA
Standard Test Methods, and some corresponding EDANA, ASTM and ISO test
methods are listed in Tab. 10-4.
The crosslinking resins such as melamine can be used to enhance wet and dry ten-
sile strength, moisture resistance, heat resistance and solvent resistance (dry-clean-
ability) of non-woven fabrics. Figure 10-9 illustrates examples of the stiffness im-
provement of an acrylic latex bonded non-woven sheet as a function of the latex level
in the sheet at two different levels of the melamine resin [12].
Here, the stiffness was measured by the Handle-O-Meter (IST 90.3), where a fab-
ric specimen is pushed through a slot with a blade on an arm at a constant rate and
the resultant force on the center point of the fabric measured. Dent [13] recently re-
ported through theoretical analysis that the initial slope of the load-deflection curve
250
200 with 10%

Handle-O-Meter Reading, mN
Melamine
150
100 with 5% Melamine
50
without Melamine
0
0 20 40 60
% Acrylic in Sheet
Fig. 10-9 Improvement in the stiffness of an acrylic latex bonded

non-woven sheet as a function of the latex level.
276
Tab. 10-4 INDA Standard Test Methods for non-wovens and the corre-
sponding EDANA, ASTM and ISO tests.
Description INDA standard EDANA recommended ASTM method ISO

test method test method
Guideline test methods for non-woven fabrics

IST GL non-wovens ASTM D1117-99
Guideline test methods for evaluating non-woven felt IST GL felts
10 Non-wovens Application
Non-woven vocabulary IST 1 ERT 1.3-99

Absorption
Non-woven absorption IST 10.1 ERT 10.3-99 ISO 9073.6
Rate of sorption of wiping materials IST 10.2
Demond absorbency IST 10.3 ERT 230.0-99
Abrasion resistance
Inflated diaphragm IST 20.1 ASTM D3886-92
Flexing and abrasion IST 20.2 ASTM D3885-99
Oscillatory cylinder IST 20.3 ASTM D4157-92
Rotary platform IST 20.4 ASTM D3884-92
Martindale IST 20.5 ASTM D4966-98 ISO 12947-3
Uniform abrasion method IST 20.6 ASTM D4158-92
Bursting strength
Diaphragm IST 30.1 ERT 80.3-99 ASTM D3786-87 ISO 13938-1
Non-woven burst IST 30.2
Electrostatic properties
Surface resistivity IST 40.1 ISO 9073-6
Decay IST 40.2
Binder properties
Resin binder distribution and penetration IST 50.1 ASTM D5908-96
Appearance and integrity of highloft batting IST 50.2 ASTM D4770-00
Optical properties
Opacity IST 60.1 ERT 110.1-78 ISO 2471-198
Brightness IST 60.2 ERT 100.1-78 ISO 2470-1997
Permeability
Air permeability IST 70.1 ERT 140.1-99 ASTM D737-96
Water vapor transmission (multiple tests) IST 70.2 ISO 9073 8:1995
Liquid strike-through time IST 70.3 ERT 150.4-99
Water vapor transmission (Mocon) IST 70.4
Repellence
Surface wetting spray test IST 80.1 ISO 4920-1981 (E)
Penetration by water (rain test) IST 80.2
Penetration by water (spray impact test) IST 80.3
Penetration by water (hydrostatic pressure test) IST 80.4 ERT 120.1-80 ISO 811-1981
Penetration by saline solution (automated mason jar test) IST 80.5 ERT 170.0-89
Water resistance hydrostatic pressure test) IST 80.6 ERT 120.1-80 ISO 811-1981
Penetration by oil (hydrocarbon resistance) IST 80.7
Alcohol repellence of non-woven fabrics IST 80.8
Non-wovens run-off IST 80.9 ERT 152.0-99
Stiffness
Cantilever IST 90.1 ERT50.5-99 ASTM D5732-95 IS09073-7
Gurley IST 90.2
Handle-O-meter IST 90.3
Drape IST 90.4 ERT 90.4-99
10.4 Application Test Methods
277
Tab. 10-4 Continue.

278
Tear strength
Elmendorf IST 100.1 ASTM D5734-95 ISO 1974-1974(E)
Trapezoid IST 100.2 ERT 70.4-99 ASTM D5733-95 ISO 9073-1997(E)
Tongue IST 100.3
Tensile
Grab IST 110.1 ASTM D5034-95 ISO 13934-2:1999
Seam strength IST 110.2 ASTM D1683-90A
10 Non-wovens Application
Internal bond strength IST 110.3

Strip IST 110.4 ERT 20.2-89 ASTM D5035-95 ISO 9073-3
Thickness
Thickness of non-woven fabrics IST 120.1 ERT 30.5-99 ASTM D5729-97 ISO 9073-2:1995(E)
Highloft non-wovens IST 120.2 ASTM D5736-95
Highloft compression and recovery (measurematic) IST 120.3
Highloft compression and recovery
(plates and weights, room temperature) IST 120.4
Highloft Compression and Recovery
(plates and weights, high temperature, high humidity) IST 120.5
Weight
Non-wovens mass per unit area IST 130.5 ERT 40.3-90
Friction
Static arid kinetic IST 140.1
Dry-cleaning
Resistance IST 150.1 ASTM D2724-87
Appearance and integrity of highloft batting IST 150.2
Linting
Particulate shedding (dry) IST 160.1 ERT 220-0-96 & 300-84
Particulate shedding (wet) IST 160.2
Fibrous debris from non-woven fabrics IST 160.3
Tab. 10-5Excerpt from 2000 Global Comparison of Test Methods for
non-woven absorption [10]. (Absorption – Liquid Absorbency Time)
Properties INDA EDANA ASTM TAPPI AATCC ISO

IST 10.1-95 ERT 10.3-99 T432 OM-94 79-1995 ISO9073-6
Sample According to Condition test According to At moisture According to

conditioning ASTM D 1776 specimens according TAPPI T 402 equilibrium ISO 139
to ERT 60.2-99 65 ± 2 % RH, 21 ± 1 °C
Test specimen In MD direction cut 75 mm In MD direction cut Approximately Swatch or skein As directed in
size and a length sufficient 76 ± 1 mm wide and a 100 mm × 100 mm to fit tightly over EDANA 10.3-99
so the strip weight length so the strip weight embroidery hoop
is 5 ± 0.1 g is 5 ± 0.1 g
Equipment Wire basket, height 8 cm, Wire basket, height 8 cm, Drop measuring Embroidery hoop As directed
used diameter 5 cm, diameter 5 cm, device. A specimen 15 cm dia. or in EDANA 10.3-99
weight 3 to 8 g, weight 3 ± 1 g, support consisting more. Burette,
number 20 to 26 gage B&S 2 cm mesh; of a non-absorbent delivering
copper wire, 2 cm mesh; 0.5 mm diameter material 100 × 100 mm 15–25 drops
liquid container; stainless steel wire; with a central hole per mL; stopwatch;
stopwatch liquid container; of approx. 40 mm burette stand;
stopwatch diameter light source
Procedure Drop basket from height Drop basket from Drop liquid from Deliver one drop As directed
of 25 mm into liquid. height of 25 ± 1 mm height of at least of water (21 ± 3 °C) in EDANA 10.3-99
Time for specimen to into room temp. liquid. 10 mm on to the 1.0 ± 0.1 cm from
become completely wet Record time for the specimen. 1.0 mL hoop. It is important
is measured basket to sink completely 0.1 mL and 0.01 mL to condition the
below the surface of the are the amounts used. fabric.
liquid
Number of tests 5 5 10 5 5
Properties Absorbency time in s Liquid absorbency Average, max., and Absorbency in s As directed
10.4 Application Test Methods
reported time in s minimum absorption (of bleached textiles) in EDANA 10.3-99

time in s, the volume
279
used, and type of

paper used
gives the fabric stiffness or flexural rigidity, while the ratio of maximum load to ini-
tial slope gives the fabric friction or smoothness. Thus, a single measurement can
measure two basic parameters governing the fabric “hand” or “feel”.
In addition, TAPPI (Technical Association of the Pulp and Paper Industry) is ac-
tive in the wet-form non-woven segment of the industry [9]. Some of the standard
test methods established by AATCC (American Association of Textile Chemists and
Colorists) are also applicable to non-wovens. INDA recently published “2000 Global
Comparison of Test Methods” [10], which conveniently compares standard test
methods by the above listed organizations. Table 10-5 is an excerpt from the Absorp-
tion – Liquid Absorbency Time, which demonstrates two different principles used to
quantify similar properties.
Oathout [14] has discussed the water-absorption characteristics of eleven wiping
materials including one 100 % wood pulp with binder, paper making process, six hy-
dro-entangled, two knitted polyester and one woven cotton. In addition to the static
absorption measurements specified by IST 10.1 and 10.2, he describes results of the
dynamic wiping efficiency, or “wipe-dry” test. In this test, a wiper is affixed to the
bottom side of a 1 kg sled, which is placed on a stainless steel pan. A known amount
of the liquid challenge was placed in front of the sled pulled into and through the
pool at a wiping speed of 25 cm s–1. The test tries to simulate manual wiping opera-
tions. His results demonstrate that fabrics with bulky character, imparted through
creping or stitch-bonding exhibited superior “wipe-dry”.
281
References
1 E. A. Vaughn, Non-wovens World 9 1998-1999 TAPPI Test Methods, 1998,

Factbook 1991, ISBN 0-87930-227-5, TAPPI Press, Atlanta, GA;
Miller Freeman Publications, 1991. www.tappi.org
2 Association for the Non-woven Fabrics 10 2000 Global Comparison of Test
Industry, Cary, North Carolina, USA; Methods, Association of the Non-woven
www.INDA.org Fabrics Industry, 2000.
3 P. Wiaczek, Comparison of Trends in 11 E. D. Weil, Flame Retardant Non-
Latex Emulsions for Non-wovens and wovens, Non-wovens Binders and
Textiles: China and the United States, Additives Seminar, 53-61, TAPPI
International Non-wovens Journal, 1999. PRESS, 1988.
4 EDANA – European Disposables and 12 P. D. Wallace, Crosslinker resins in
Non-wovens Association, Brussels, non-woven binder systems, Non-wovens
Belgium, www.edana.org Binders and Additives Seminar,
5 All Nippon Non-wovens Association; TAPPI Press, 1988.
www.anna.gr.jp 13 R. W. Dent, An analysis of fabric ‘Hand’
6 China Non-woven Technical Association; and ‘Feel’, International Non-wovens
www.chinanonwovens.com Journal, Vol. 9, 2000.
7 Association of the Non-woven Fabrics 14 J. M. Oathout, Determining the Dynamic
Industry, Analysis – The Non-woven Efficiency with which Wiping Materials
Industry in North America, Cary, Remove Liquids from Surface, Interna-
North Carolina, USA. tional Non-wovens Journal, Vol. 9,
8 B. M. Koltisko, Vinyl Copolymer Materi- 2000.
als, Principles of Non-wovens, 221–248,
1992, Association of the Non-woven
Fabrics Industry.
11
Applications in the Leather Industry
Johannes P. Dix and Werner Kirchner
11.1
Introduction
Leather making is an ancient art. Methods for converting the fresh animal hide into
leather (Fig. 11-1) have been known for approximately 100 000 years [1].
Fig. 11-1 Structure

of leather.
Stone Age man, for example, used smoke or fat for preserving the hides. Tanning
with vegetable tannins (vegetable tanning) and with alum, a naturally occurring alu-
minum sulfate (mineral tanning), then became established in the Middle Ages. It
was only about 100 years ago that the development of chrome tanning (tanning with
chromium salts) produced the decisive breakthrough which has made it possible to
produce leather in an efficient, economical manner.
284 11 Applications in the Leather Industry
The excellent properties of chrome-tanned leather opened up new fields of use and
made possible the mass production of leather goods, for example in the shoe or ap-
parel leather sector. This created the need for fashionable styling of these leather
goods and for making them resistant to soiling and damage. It is this function that is
performed by leather finishing [1–7].
11.2
Market Situation
To describe the economic importance of polymer dispersions, a brief look at the

structure of the leather industry is helpful.
The leather industry is one of the oldest and most complex industries world-wide.
It is closely coupled to raw hide production and hence to meat consumption. Live-
stock is bred world-wide. Accordingly, tanneries are located all around the globe. The
articles made from leather differ greatly, ranging from shoe upper leather to apparel
leather and to automotive leather.
The leather industry has undergone global changes in the last decades. This struc-
tural change is still not complete. It is driven by the high proportion of leather pro-
cessing and leather production costs attributable to wages (Fig. 11-2). This has led
and is still leading to a relocation of leather manufacture from the traditional indus-
trialized countries of Europe and from the U.S. to low wage countries, especially in
the Far East (Fig. 11-3). At the same time, the industry, which is predominantly
based on small and medium size companies, is undergoing a process of consolida-
tion.
Costs of leather production in Europe: ca. 7.5 e/m2
Fig. 11-2 Breakdown of leather pro-

duction costs (without raw hide costs)
in Europe.
Fig. 11-3 Regional distribution of fin-

ished leather production.
11.2 Market Situation 285
Since finished leather production is determined by raw hide production (Fig.11-4),

the annual growth rate of leather produced is only small (ca. 0.8 % year–1). The pre-
dominant portion of leather produced is cattle hide (ca. 60 %), followed by small-an-
imal skins (sheep, goat) at about 30 % and pork leather at ca. 10 %.
Fig. 11-4 World-wide raw hide

production in 1990 to 1995.
The market volume of chemicals used in leather manufacture is about Euro

2.5 billion world-wide. The largest segment by far in terms of value is the product
range for tanning (ca. 50 %), followed by finishing (ca. 30 %). The finishing segment
subdivides into the categories of binders/top coats, finishing dyes and finishing aux-
iliaries (Fig. 11-5).
Finishing market volume: ca. e 0.75 billion
Fig. 11-5 Distribution of market

volume in leather finishing between
individual product ranges.
Base coats and pigmented coats are today already commonly applied in low-sol-
vent and solvent-free processes. Polyacrylate or polybutadiene dispersions are pre-
ferred here. Polyurethane dispersions and casein formulations are used as well,
depending on the end use. In the case of top coats, aqueous systems based on
polyurethane dispersions are used as well as, still, solvent-containing lacquers or
emulsions. However, here too increasingly tougher environmental regulations are
driving a changeover to solvent-reduced and waterborne systems.
About 180 000 tons annum–1 of binders are estimated to be used in leather finish-
ing world-wide. Of that, about 60 % are polyacrylate and polybutadiene dispersions
and about 12 % polyurethane dispersions (Fig. 11-6). At about 20 %, the solvent-con-
taining lacquers still account for a relatively large share today. However, this share
will in future decrease further in favor of polyurethane dispersions.
Fig. 11-6 World-wide use of binders

in leather finishing.
11.3
Leather Finishing
The tanned animal hide, i.e., the leather, usually becomes a sailable article with an
upgrading post-treatment. The further processing takes place in two stages:
In wet finishing, the character of the leather article (softness, strength, water re-
pellency) is substantially determined by the retanning and the fat-liquoring opera-
tions. The leather is also dyed. This is done using soluble dyes.
This is followed by the further processing of the dried leather (crust). It is this op-
eration which is commonly referred to as finishing. It makes a significant contribu-
tion to enhancing the performance characteristics. A surface coating provides better
protection against wetness, soiling and mechanical action. Surface properties such
as hue, luster or feel and also light- or rub-fastness are imparted or improved. At the
same time, leather damages or unlevelness (grain defects, scratches) are covered up.
The finishing of buffed leather or split leather permits the use and upgrading of oth-
erwise less suitable leather qualities. Similarly, many fashion effects are not possible
without finishing.
Interestingly, leather finishing was one of the first industrial applications for poly-
mer dispersions. In Corialgrund E, the then I.G. Farben commercialized a disper-
sion based on poly(methyl acrylate) in 1931. This was the first polymer dispersion on
the market and the starting point for the immense development of polymer disper-
sions for other applications too.
While Corialgrund E was primarily used as a barrier to avoid migration of the plas-
ticizer out of the nitrocellulose lacquers then used and thus to counteract finish em-
brittlement, the immense potential of polymer dispersions as binders for finishing
was soon recognized. They make it possible to apply thicker finish coats on the
leather. The thermoplasticity of polymer dispersions makes it possible to emboss the
leather surface and so create any desired surface texture. The use of polymer disper-
sions provides not only better adhesion of the finish to the leather, but also highly
flexible finishes that are stable to light and aging. It is accordingly no surprise that
polymer dispersions have become widely established in leather finishing.
11.3 Leather Finishing 287
11.3.1
Modern Finishing
The various leather articles with their specific requirements each require a specific
optimized process in the tannery. Classifying leather finishes according to, say, the
binders used or the method of application, the appearance or the ready-produced
leather article is thus possible only to a limited extent. Frequently there are many dif-
ferent ways of producing the desired article. Leather finishing is therefore regarded
as being more an art than a science.
11.3.2
General Construction of Finishing Coats
The finish is generally made up of a number of coats. Each coat has a certain pur-
pose. The coating technique can be the same for each coat, but need not be. It
depends primarily on the type of leather used and the effect desired.
11.3.3
Spray Dyeing
Metallized dyes, for example, are used to dye, or correct the hue of the surface of
leathers which have not been drum dyed and to match it to the hue of the finish. As
a result, damages to the finish in the course of the use of the leather article are less
pronounced.
11.3.4
Grain Impregnation
Grain impregnation is used to improve the firmness of the buffed grain layer. The
impregnating float or liquor has to absorb into the leather and must not become de-
posited at the surface. To this end, very dilute, finely divided acrylate dispersions
(solids content about 10 %) are applied in combination with capillary-active sub-
stances known as penetrators.
11.3.5
Base Coat
Depending on the crust leather used, the adhesion of the finish layer to the leather
has to be improved in some cases by means of a separate base coat. Adequate adhe-
sion is the precondition for many application properties and important to achieve the
required physical fastnesses for the ready-produced leather articles. Soft, finely di-
vided polyurethane dispersions have won out in this sector over polyacrylate disper-
sions.
11.3.6
Pigment Coat
Its components are pigments, binders and auxiliaries such as waxes and fillers. The
pigment coat imparts the desired appearance to the leather and levels out the leather
surface. The choice of binders is made according to the finishing effect and fastness
profile desired. Generally, polyacrylate dispersions are used in the pigment coat.
A distinction is made between finishes which preserve the natural character of the
leather (e.g., semi-aniline finish) and high hiding finishes which receive the desired
grain structure through embossment. Finely divided acrylate dispersions (<100 nm)
are useful for less hiding finishes. The butadiene-based dispersions used in leather
finishing have high filling effect and can enhance the hiding power of the finish.
As well as the degree of hiding, the hardness/softness balance of the pigment coat
has a significant influence on application and processing properties. Especially on
thin, soft leather types (e.g., nappa), hard pigment coats lead to an unwanted double-
skin appearance. Soft binders, however, tend to be tacky and cause processing prob-
lems in leather production. Auxiliaries (waxes and fillers) can be used to reduce the
tackiness within certain limits. The glass transition temperatures of the polyacrylate
dispersions used are typically between –10 and +10 °C.
Polyurethane dispersions are used in the pigment coat in particular when very
high fastness properties are required.
11.3.7
Top Coat
The top coat determines the ultimate appearance and the feel of the leather surface.
It further substantially influences the fastness properties of the finish. Instead of or-
ganic, solvent-containing lacquers and top coats (e.g., nitrocellulose emulsions), to-
day there is an increasing trend towards waterborne top coat systems. These are usu-
ally polyurethane dispersions which, owing to their specific properties (no emulsifi-
er, good film formation despite relatively high hardness), are superior to polyacrylate
dispersions in application terms.
The degree of luster of the finish is controlled using matting agents (e.g., silica de-
rivatives).
11.4
Application Methods
The application method used depends not only on the processing step but also on
the type of leather and the desired finishing effect. Currently applied methods of
coating will now be briefly described.
11.4 Application Methods 289
11.4.1
Spraying
Spraying is the most widely used method of application in leather finishing. Rotating
spray guns inside spray machines (Fig. 11-7) apply the low-viscosity finish liquor to
the horizontal leather. Even soft leathers can be processed by this technique.
Fig. 11-7 Spray machine.
Modern spray units are equipped with computer-controlled spray guns which rec-
ognize the outlines of the leather and so minimize overspray. They further operate
under high volume, low pressure conditions to reduce spray drift.
As well as the HVLP process there is the airless process whereby the spray jet is
not mixed with compressed air, but is generated by very high pressure in the spray
nozzle. This method is suitable for high amounts applied.
11.4.2
Roll Coating
Roll coating (Fig. 11-8) is the second most important method for application after
spraying. The leather passes between two rolls (color print roll and transportation
roll) by means of a transportation belt. The top roll transfers the relatively viscous
color to the leather. The texture and the direction of rotation (synchronous or re-
verse) of the color print roll determine the amounts applied. Soft leathers can be
processed on this machine only if the rolls turn in the same direction. Consequently,
these types of leather can be roll coated only with finishes that do not require high
amounts.
11.4.3
Curtain Coater
The casting process comes from the surface coating of wood. In this process
(Fig. 11-9) a casting head creates a curtain of liquid. The horizontal leather passes
through this vertically descending curtain. Casting finds application in particular in
Fig. 11-8 Roll coater.
grain impregnation and in pigment finish applications for patent leather and buffed
leather. This technique is not suitable for processing very soft leathers, since they
buckle as they pass through the curtain of liquid. This application technology places
particularly high demands with regard to shear stability and foam control on the dis-
persions used. The use of antifoams is limited by wetting and flow-out require-
ments.
Fig. 11-9 Curtain

coater.
11.5 Binders 291
11.5
Binders
Binders are among the most important components of a finish system, whether it is
a pigment finish or a top coat. They bind the color-conferring pigments, which have
no inherent affinity for leather, and protect the leather surface through their film-
forming property. Aqueous finishes generally utilize aqueous polymer dispersions.
As well as from binders and pigment preparations, finishes are prepared from rheo-
logical additives (thickeners, flow control agents, solvents in appropriate cases), mat-
ting agent, crosslinker and handle modifier. The following product classes are avail-
able as polymer dispersions:
– polyacrylate (copolymers)
– polybutadiene (copolymers)
– polyurethanes
The multiplicity of possible monomer combinations and their different blend ra-
tios, the various molecular weight distributions and degrees of crosslinking of the
polymers, the effect of process conditions and the colloid-chemical properties of the
dispersions make for an immense range of binder properties that can be obtained.
These include, for example, hardness and softness, elasticity, water resistance, cold-
flex stability and hiding power. In addition, film formation in the course of drying
has a decisive effect on many fastnesses of the finish. Owing to their different
chemistries, the three types of polymer dispersion differ in their application proper-
ties:
11.5.1
Polyacrylate Dispersions
Typical leather-finishing polyacrylate dispersions are based on ethyl acrylate or

copolymers of butyl acrylate with acrylonitrile or methyl methacrylate. Glass transi-
tion temperatures range from –10 °C to +10 °C. The polyacrylate dispersions used
are lightfast and compatible in the color batch. Owing to the monomers on which
they are based, polyacrylate dispersions are relatively inexpensive. They provide fin-
ishes having good application properties. However, they do not (as yet) meet the
highest requirements, as required for automotive leather for example.
11.5.2
Polybutadiene Dispersions
The polybutadiene dispersions used are customarily copolymers based on butadiene,

styrene and acrylonitrile. Their advantage is the substantial flexibility in thick layers,
as required in the finishing of split leathers for example. These systems are typically
crosslinked using zinc oxide. As the hiding component, polybutadiene dispersions
are also used in combination with polyacrylate dispersions. The double bonds in the
polymer make polybutadiene dispersions susceptible to oxidative aging (light, heat)
and sensitive to heavy metals.
11.5.3
Polyurethane Dispersions
Polyurethanes are polyaddition compounds of isocyanates with polyols and/or

NH-functional compounds. Owing to the incorporation of hydrophilic groups in the
polymer, polyurethanes form stable – usually anionically stabilized – dispersions in
water. Unlike the systems described above, polyurethane dispersions can be made
without an emulsifier. Finishes with polyurethane dispersions are notable for a very
high fastness level. Flexing endurance, even at low temperatures, and rub-fastness
(after crosslinking) meet the highest standards. Owing to the hydrophilic groups,
polyurethane dispersions possess very good adhesion to leather. Their chemistry
makes carboxylate-stabilized systems pH-sensitive. Since monomer costs are dis-
tinctly above those of the acrylates, the use of polyurethane dispersions is mainly re-
stricted to applications where the special properties of polyurethane dispersions are
essential.
Depending on the polyol component used, there are polyetherurethanes and poly-
esterurethanes. With regard to the isocyanate component, a distinction is made be-
tween aromatic and aliphatic monomers. The somewhat less costly aromatic sys-
tems, however, do not meet the extreme aging resistance requirements of automo-
tive leathers, for example.
11.6
Production of Selected Leather Articles
Guideline recipes for finishes for some selected leather articles will now be used by
way of example to discuss the particular requirements that have to be met by the
polymer dispersions used. The finisher has to adapt these guideline recipes to the
leather to be finished and to the final properties demanded (feel, appearance, fast-
ness).
11.6.1
Shoe Upper Leather
In terms of area, about 60 % of all leather produced is further processed as shoe up-
per leather. Shoe upper leather is the largest sector by far. Finish requirements are
dictated not only by the performance characteristics but also greatly by the particular
processing methods in the footwear industry.
In shoe making, the previously moistened leather is wiped (pulled) over the last by
heated irons. The folds appearing at the round edges of the shoe are smoothed away
by heat treatment with a hot air blower or a smoothing iron (the leather shrinks at
these high temperatures). So the finish has to be heat resistant. In addition, the fin-
ish must not scratch under the rubbing by the irons. The shoe sole is injection mold-
ed on in a further operation. The finish coat therefore has to be solvent-fast and the
dyes may not migrate into the shoe sole.
Shoe upper leather requires good flexing endurance and good adhesion of the fin-
ish. Rub-fastness is of minor importance.
An example of a finish recipe for shoe upper leather is:

Leather type: Cattle leather box-type
Base coat: (depending on crust)
Pigment finish: Pigments 100 parts
Polyacrylate dispersion (40 %) 200 parts
Waxes (40 %) 50 parts
Casein binder (20 %) 100 parts
Water 350 parts
Top coat: Polyurethane dispersion (35 %) 400 parts
Crosslinker (50 %) 30 parts
Water 550 parts
Thickener to a 4 mm Ford cup viscosity of approximately 24 s
Processing:
Pigment coat: 2 × spraying (each ca. 80 g m–2); dry
Plating: 2 s at 80 °C and 150 bar
1 × spraying (ca. 50 g m–2); dry
Top coat: 2 × spraying (each ca. 50 g m–2); dry
The non-thermoplastic casein binder ensures processability in the wiping process

by reducing sensitivity to heat and improving hot rub resistance. Useful top coats in-
clude a nitrocellulose lacquer or an aqueous system with a very hard and hence plat-
ing-fast polyurethane dispersion. If necessary, the latter can be crosslinked to im-
prove the rubfastness.
11.6.2
Apparel Leather
Apparel leather is the second largest sector after shoe upper leather. It accounts for
about 20 % of leather production in terms of area.
Apparel leathers preferably utilize sheep and goat leathers, but in some cases also
calf leather. Inevitably, fashion aspects are of primary importance with apparel
leathers. Other decisive aspects are wear properties such as softness and feel. With
regard to processing, the finish does not have to meet special requirements. One im-
portant performance characteristic is the light-fastness of the finish. Flexing en-
durance and rub-fastness are of lesser importance.
An example of a finish recipe for apparel leather is:

Leather type: Sheepskin
Pigment coat: Pigment 50 parts
Spray dye 50 parts
Wax (40 %) 100 parts
Water 600 parts
Top coat: Nitrocellulose emulsion (15 %) 500 parts
Wax (40 %) 20 parts
Water 480 parts
Processing:
Plating: 2 seconds at 80 °C and 30 bar
5 × spraying (each ca. 40 g m–2); dry
Hydraulic ironing: 0.5 s at 120 °C and 30 bar
Apparel leathers generally are not provided with a base coat. The pigment content
in the pigment coat has been reduced in favor of the spray dyes in order that a more
transparent, less coated appearance may be obtained for the finish. This is intensi-
fied by means of low concentration of the pigment finish and the large number of
spray applications. At present, solvent-containing top coats are still customary for ap-
parel leathers, but, as with shoe upper leather, there is an increasing trend toward
the use of aqueous top coats.
11.6.3
Automotive Leather
Although the amount of leather processed in the automotive sector, as leather seats
or steering wheel leather, amounts to only about 2 % in terms of area of total leather
production (and rising), finishing chemical demand greatly outweighs those for shoe
upper leather or apparel leather, for example, because of the high fastness require-
ments. These high fastness requirements in the automotive leather sector include –
depending on the specific requirements of the automotive manufacturer – adhesions
of greater than 4 N cm–1, flexing endurance’s (dry, 23 °C) of 100 000 cycles and
30 000 cycles at –10 °C. Similarly, rub-fastness has to meet extreme requirements:
>1000 rubs wet and a swelling resistance of >2000 rubs. In addition, these leathers
have to be aging resistant, i.e., they have to have adequate flexing endurance and rub-
fastness even after simultaneous exposure to heat, UV light and moisture. Nor may
any color shifts occur. To achieve these very high fastnesses it is predominantly nec-
essary to use polyurethane dispersions.
A guideline recipe for automotive leather is:

Leather type: Cattle hide
Base coat: Polyurethane dispersion (20 %) 200 parts
Water 600 parts
Polyurethane dispersion (35 %) 250 parts
Matting agent 80 parts
Water 290 parts
Thickener to a 4 mm Ford cup viscosity of 16–18 s
Water 420 parts
Thickener to a 4 mm Ford cup viscosity of approximately 24 s
Processing:
Base coat: 1 × spraying (ca. 100 g m–2); dry
Hydraulic ironing: 2 s at 80 °C and 80 bar
Pigment coat: 1 × spraying (70–100 g m–2); dry
Press embossing: 5 s at 80 °C and 250 bar
1 × spraying (50–70 g m–2); dry
The polyurethane dispersions used in the base coat are soft and very finely divided.
In contrast, the polyurethane dispersions used in the pigment coat are of medium
hardness. A portion of the polyurethane dispersions may also be replaced by poly-
acrylate dispersions. These must not have an adverse effect on the cold flexing en-
durance and so the polyacrylate dispersions used must have a low glass transition
temperature. The high rub-fastnesses are primarily achieved by the crosslinking of
the top coat. Useful crosslinkers include, for example, modified aliphatic polyiso-
cyanates. The leathers are strongly embossed to conform the surface structure of the
leathers to the interior styling of the car.
As an alternative to the application method described, the base and pigment coats
can also be applied by synchronous roll coating. However, for this the recipe needs to
be adjusted to a smaller water quantity and a higher color batch viscosity (about 50 s
in 6 mm Ford cup).
11.6.4
Furniture Leathers
Furniture leathers, unlike automotive leathers, need less high fastnesses. Light-fast-
ness is an exception. Primary furniture leather criteria are the feel properties and the
visual appearance of the leather. The use of soft polyacrylate dispersions has proved
advantageous here. The greater use of inferior leather grades increasingly forces the
use of binders that provide high covering.
An example of a recipe for furniture leather is:

Leather type: Cattle hide, buffed
Base coat: (depending on crust leather used)
Matting agent 80 parts
Wax (40 %) 80 parts
Polybutadiene dispersion (40 %) 100 parts
Water 290 parts
Thickener to a 4 mm Ford cup viscosity of 16–18 s
Water 520 parts
Thickener to a 4 mm Ford cup viscosity of 24 s
Processing:
Embossing: 3 s at 80 °C and 150 bar
1 × spraying (ca. 50 g m–2); dry
Top coat: 1 × spraying (ca. 50 g m–2); dry
Hydraulic ironing: 0.5 s at 120 °C and 30 bar
The requisite hiding performance is achieved through the partial use of the
polybutadiene dispersion. Furniture leathers are softer than automotive leathers.
Embossing is accordingly done under less pressure. Since the fastness requirements
are lower, the top coat is less crosslinked and the applied amount is lower. For aes-
thetic reasons, the leather is briefly plated after the application of the top coat.
11.7
Test Methods in Leather Finishing
The primary purpose of the test methods is to ensure that the finished leathers are as
a whole suitable for the stated purpose. Accordingly, many test methods simulate the
stresses to which the finished leathers are exposed in use. It must always be noted in
this context that the leather itself has a substantial influence on the tests as well as
the finish coat on the leather. The different leather types vary greatly in thickness,
softness, surface structure, hydrophilicity, etc. Even a single hide is not homoge-
neous in itself. For example, fiber density, leather thickness, pore structure and ab-
sorbency are different in the belly than in the butt. For this reason, the correspon-
ding test descriptions (e.g., DIN or ISO standards) provide precise definitions of the
areas of the leather from which the test specimens are to be taken. The test results
depend not only on the sampling position but also on the moisture content of the
leather specimens. The drier the leather is, the harder and less elastic are the leather
fibers. For this reason, the test methods prescribe that the test specimens must be
conditioned under standard atmospheric conditions (e.g., 50 % relative humidity
and 23 °C or 65 % and 20 °C).
Since finished leathers are predominantly used in the shoe industry, test methods
are largely adapted to these requirements. From experience, these test methods are
also suitable for evaluating other leather articles such as upholstery leather, apparel
leather and leather for bags and suitcases. The fastness level to be achieved varies
from article to article.
The International Union of Leather Technologists’ and Chemists’ Societies has de-
veloped, mostly binding, “Methods of chemical leather analysis” (I.U.C. methods)
and “Methods of physical leather testing” (I.U.P. methods). The German DIN sheets
for testing leather have in most cases been conformed to the above methods. I.U.F.
(International Union Fastness) describes guidelines and test methods drawn up by
the International Fastness Commission for leather dyes and dyed leathers.
The following methods are only the most important tests in common use. In addi-
tion, there are a multiplicity of specific test methods, either designed for certain
leather articles or required by certain customers.
11.7.1
Flexing Endurance
This test describes the behavior of the finish coat on repeated flexing of the leather.
It is among the most important tests of the finish.
The test is carried out both on dry and on wet leathers. It is described in
DIN 53351 or I.U.P. 20. The rectangular leather specimens are clamped into a flex-
ometer (Bally flexometer, Fig. 11-10) with a fold. The rotational movement of the up-
Fig. 11-10 Bally flexometer.

per axis makes the fold move back and forth on the surface of the leather. The finish
is assessed after 1000, 5000, 10 000, 20 000, 35 000, 50 000 flexes. For particularly de-
manding requirements, the test is continued to 100 000 flexes. Wet specimens are
flexed only 20 000 times at most. Any more will dry the leather too much.
After visual examination, the test specimen is evaluated according to the degree of
damage of the finish coat.
High flexibility is demanded, for example, by the shoe industry for work and
sports footwear. But leathers for the automotive sector (e.g., leather seats) also have
to meet such high requirements.
A variation of this test is flexing endurance at temperatures below freezing. Typi-
cal requirements are 30 000 flexes at –10 °C or 10 000 flexes at –20 °C.
11.7.2
Rub-fastness
The rub-fastness test examines resistance of the pigment coat to abrasion and the
transfer of color to other surfaces (crocking). The test is carried out on the VESLIC
rub-fastness tester (Fig. 11-11). This test is governed by the standards DIN 53339 and
I.U.F. 450.
Fig. 11-11 VESLIC rubfastness tester.
On a stretched leather a felt is rubbed back and forth. The felt is 10 mm × 10 mm

in size and weighted with 1 kg. The leather is stretched 10 %. The test is customarily
carried out in three variations:
Dry rub-fastness: dry leather, dry felt

Wet rub-fastness: dry leather, wet felt
Swelling resistance: wet leather, dry felt
The damage or change in the finish coat and the transfer of color to the rubbing
element are assessed after fixed rubbing intervals. This method provides data on the
sensitivity of the finished leather surface to rubbing through, abrasion or transfer of
color from the pigment coat under both dry and moist conditions.
Rub-fastnesses are also tested using the SATRA rub-fastness tester. In this test
a rotating pad of felt acts on the leather surface under a certain pressure and at a
defined speed of rotation. The leather is evaluated after fixed numbers of cycles. This
test is likewise carried out with both a dry and a wet felt pad.
As a further variation, the test can be carried out under exposure to various,
defined test liquids: perspiration rub-fastness, chemical rub-fastness, etc.
11.7.3
Dry and Wet Adhesion
This test determines the adhesion of the finish coat to the leather surface. It also pro-
vides evidence of possible inter-adhesion problems within the finish coat. These
arise in particular when excessive auxiliary quantities (especially waxes) are used or
the crosslinking of the preceding layer is excessive. Ideally, the adhesion of the finish
to the leather is such that, in this test, the finish can only be pulled off together with
the grain layer.
Strips of leather having a certain length and width are glued to a fixed basis
using a defined adhesive. The tensile tester is then used to pull this leather away
from the basis at an angle of 90°. The force measured during the pulling is recorded
and its average reported. This test is repeated at least four times with half the test
specimens being punched out along the backbone and the other half at right angles
to it.
To test the wet adhesion, the adhered specimens are immersed in water and tested
after a predetermined time.
11.7.4
Fastness to Ironing
This test is important for finished shoe upper leathers (see above) in particular. An
iron is moved once back and forth across the leather surface over a slightly rounded
edge as a preliminary test. The damage to the finish and any shift in hue are then
evaluated. The test temperatures are increased in intervals of 20 °C. A more sensitive
version of this test is carried out on the VESLIC rub-fastness tester using a heatable
test punch. Again the temperatures are increased in intervals of 20 °C. The result is
assessed in each case after five rubs.
11.7.5
Hot Air Fastness
In this test, which is likewise important for shoe leathers, the leather samples are
subjected for 1 min to the flow of hot air from a hair dryer (150 °C). The damage to
the finish and the change in hue are then assessed.
11.7.6
Aging resistance
The leather specimens are aged (a) at 50 °C for 7 days or (b) at 80 °C for 3 days. They
are then assessed to see whether heat aging has resulted in embrittlement, yellowing
or a change in the flexing endurance.
11.7.7
Fogging test
This test, which is important for automotive leathers in particular, determines the
condensation on cooled glass panes of volatiles from the leather or the finish coat. It
is described in DIN 75201. There are two different methods of measurement: (a) the
reflectometric method and (b) the gravimetric method. While the gravimetric
method indicates the condensed mass, for example after 16 h at 100 °C, the reflecto-
metric method describes the clouding of the cooled glass plate after 3 h at 100 °C.
11.7.8
Light-fastness
The test is carried out using not only daylight (I.U.F. 401) but also artificial light
(xenon lamp) (I.U.F. 402). The leather strip to be tested is exposed to the light to-
gether with a light-fastness scale. The light-fastness scale is made up of eight colored
cotton strips having different, defined light-fastness. The color change of the leather
is compared with the color change of the light-fastness scale.
11.7.9
Hot light aging
This test is important for automotive leather in particular. It assesses the effect of
light, heat and moisture on the flexing endurance, the rub-fastness and the color
fastness of the leather finish. Finished leather strips are exposed to a defined dose of
radiation in a test chamber at 20 % relative humidity. The color fastness is examined
after the first cycle, the flexing endurance after the second cycle, the rub-fastness af-
ter the third cycle and the color fastness once more after the last cycle. Requirements
differ from one car producer to the other.
References
1 Stather, F., Gerbereichemie und Gerberei- 5 Science and Technology for Leather
technologie, Akademie Verlag, Berlin, into the next Millennium, Proc. XXV
1967. IULTCS Congress, 1999, Tata
2 Schubert, R., in: Herfeld, H. (Ed.) Biblio- McGraw-Hill, New Delhi, 1999.
thek des Leders, Vol. 6; Lederzurichtung, 6 Wood, G., Osgood, M., Leather Finish-
Oberflächenbehandlung des Leders, Um- ing, in Leather Technologists Pocket Book,
schau Verlag, Frankfurt am Main, 1982. The Society of Leather Technologists
3 Heidemann, E., Ullmanns Enzyklopädie and Chemists, 1999, Chapter 9.
der technischen Chemie, Vol. A15 7 Heidemann, E., Fundamentals of
(Leather), Verlag Chemie, Weinheim. Leather Manufacturing, Eduard
4 Schubert, R., in: Kittel, H. (Ed.) Lehrbuch Roetherdruck, Darmstadt, 1993,
der Lacke und Beschichtungen, Vol. 5, and references cited therein.
W. A. Colomb. Heenemann Verlags-
gesellschaft, Berlin, 1977.
12
Applications for Asphalt Modification
Koichi Takamura
12.1
Introduction
The annual worldwide consumption of asphalt was over 90 000 000 metric tons in
1995 and the US used approximately one-third of that total [1]. The global asphalt
consumption in 1996 is represented in Fig. 12-1 [2]. Greater than 85 % of 30 000 000
metric tons consumed in USA was used to maintain and improve more than
3 000 000 km (2 000 000 miles) of asphalt roads (Fig. 12-2) with an annual road bud-
get of $85 billion [2]. Federal Highway Trust Fund Authorizations reached nearly
$21 billion in 1996. There are more than 6 000 000 km (4 000 000 miles) of roads, and
asphalt roads account for 94 % (3 270 000 km) of the paved roads in the US. The oth-
er 6 % (200 000 km) are paved with Portland cement concrete, which is primarily
used for the heavy traffic area of the interstate highway [1].
Global Asphalt Consumption
Asia/ Others North

Australia America
Fig. 12-1 The annual global asphalt

consumption. North America and
Europe consume two-thirds of total
90 000 000 tons. Europe
Asphalt production is not very uniform throughout the US. The Midwest has the
highest production (40 %), followed by the Gulf Coast (25 %), the East Coast (17 %),
the West Coast (11 %), and the Rocky Mountains.
Over 90 % (16 % of total asphalt consumption as in Fig. 12-2) asphalt used in the
US for non-paving purposes is sold to the roofing industry. Two thirds of that is con-
302 12 Applications for Asphalt Modification
Others Fig. 12-2 Use of asphalt in the US.

Emulsions for
Paving
Roofings
Asphalt
Cement for
Paving
sumed in the manufacture of shingles for houses, and the other third is used in com-
mercial built-up roof.
Almost 90 % of US paving asphalt consumption is for hot mix. The remaining
10 % of the paving asphalt usage (approximately 7 % of the total asphalt consump-
tion) is comprised of asphalt emulsions, primarily used for preventive maintenance and
rehabilitation techniques such as chip seal, slurry seal and microsurfacing. Emulsi-
fied asphalts are also used for construction in recycling of old paving materials.
The use of polymer modified asphalts for hot mix and asphalt emulsions has
grown significantly in the US during the last 10 years. The National Center for As-
phalt Technology (NCAT) has published a list of reasons for the use of asphalt mod-
ification [3, 4]. Asphalt has been modified to:
– stiffen binders and mixtures at high temperatures to minimize rutting and reduce
the detrimental effects of load induced moisture damage
– soften binders at low temperatures to improve relaxation properties and strain tol-
erance, thus minimizing non-load associated thermal cracking
– improve fatigue resistance, particularly in environments where higher strains are
imposed on the asphalt concrete mixture
– improve asphalt–aggregate bonding to reduce stripping,
– reduce raveling by improving abrasion resistance,
– minimize tender mixes, drain-down, or segregation during construction,
– rejuvenate aged asphalt binders,
– replace asphalt cement as an extender,
– permit thicker films of asphalt on open-graded aggregates for increased durability,
– reduce flushing or bleeding,
– improve resistance to aging or oxidation,
– stiffen hot mix asphalt (HMA) layers to reduce required structural thickness,
– improve pavement durability with an accompanying net reduction in life cycle
costs,
– replace Portland cement concrete with asphalt construction methods that reduce
lane closure times and user delay costs, and
– improve overall performance as viewed by the highway user.
According to the article by King et al. [3], patents for modifying asphalt with natu-
ral and synthetic polymers were granted as early as 1843 [5]. The polymers are added
to alleviate pavement problems and to realize economic, environmental, energy, ap-
plication and/or performance benefits. Test projects were placed in Europe begin-
ning in the 1930s [6]. In North America, neoprene latex was introduced in the 1950s
and found a small but steady market, primarily in Canada and the Western United
States [7]. Natural rubber latex, one of the materials mentioned in the earliest
patents, is still being used today, primarily in water-based emulsion applications
such as microsurfacing. Neoprene modified asphalts have been used for many years,
but have more recently been replaced by other types of elastomeric polymers such as
styrene-butadiene-styrene, SBS block co-polymers. Water based styrene-butadiene
rubber (SBR) latex has found wide usage as an additive to asphalt emulsions to im-
prove chip retention. The introduction of polymers into asphalt emulsions allows
them now to be successfully used for almost any paving application. Recent empha-
sis on sustainable development and the concern about global warming has encour-
aged further development of cold paving technology using asphalt emulsions. As-
phalt emulsions for paving already account for more than 40 % of total asphalt con-
sumption in France and nearly 30 % in Spain [2].
Polymer modified asphalt accounts for less than 10 % of total asphalt consump-
tion for paving in the US, thus corresponding to approximately 3 000 000 metric tons
a year in the US. The polymer content in these modified asphalt is, on average, 3 %
by weight, resulting in less than 100 000 metric tons of polymers being used for this
application. Although the exact figure is not available, the synthetic and natural lat-
tices account for approximately 30 % of the total polymer annually consumed in the
United States. Approximately 1 000 000 metric tons of polymer modified asphalt
were used in Europe in 1996 and 70 % of these are modified with elastomeric polymers.
12.2
Hot Mix Asphalt Paving
Hot mix paving and cold paving with asphalt emulsion are the two types of paving
technologies used for producing asphalt-based pavements [3]. In hot mix paving,
aggregates are heated to a temperature above 200 °C to remove residual water and
mixed with molten asphalt, which is at a temperature as high as 160–180 °C [3, 8].
The aggregate-asphalt mixture is then transported to the job site, spread and com-
pacted. The mix has to be sufficiently hot to be compacted adequately within the
specified density. In general, the job site has to be within a 1-h transportation dis-
tance from the mix plant. Because of the need for the aggregate and the asphalt to be
at high temperatures, there are considerable energy requirements and cost associat-
ed with the hot mix process. In fact heating aggregates accounts for nearly 90 % of
the total energy usage of hot mix paving.
The typical cold paving method includes mixing aggregates with asphalt emulsion
and thus it does not involve heating the components used to produce the asphalt-
based formulation. Asphalt emulsions will be discussed in Sect. 12.3.
12.2.1
Asphalt Specification
Asphalt used for paving has been graded with regards to its viscosity at 60 °C (140 °F)
conforming to American Association of State Highways and Transportation Offi-
cials, AASHTO M226 specifications, or 25 °C (77 °F) penetration graded asphalt con-
forming to AASHTO M20. These specifications are based on properties at one spec-
ified temperature and do not necessarily predict asphalt performance over the wide
range of climatic conditions that the pavement is subjected to in its lifetime.
Changes in crude sources and refinery processes caused deterioration of pave-
ments during the energy crisis in the late 1970s to early 1980s. The problem was rec-
ognized by the Federal government and led to the development of the Strategic
Highway Research Program (SHRP) to examine the entire paving technology for
both Portland cement and asphalt based pavements. For asphalt paving technology,
these studies included the entire road construction procedure, aggregate specifica-
tion and compaction method. The study also defined the laboratory testing proce-
dures and specifications for both the asphalt-aggregate mix, (such as a compaction
method for core sample preparation), rutting, fatigue and cold fracture testing of pre-
pared samples. The SHRP study also developed Superpave® Performance Graded
(PG) asphalt binder specifications based on the pavement’s temperature range [3, 4, 8].
The specification is based on the rutting, fatigue and cold fracture resistance of the
asphalt binder and defined by two numerical values representing the upper and low-
er temperature limits of particular asphalt in °C (e.g. PG64-22). The asphalt binder
becomes too fluid during hot summer days under strong sun resulting in permanent
deformation, which is called rutting. In contrast, the binder becomes brittle during
cold winter nights. A perpendicular crack across the pavement lane develops when
the stress generated by thermal contraction exceeds a critical value. The freshly
applied pavement is most susceptible to rutting, but it becomes more susceptible to
fatigue fracture when the asphalt binder is oxidized and loses its flexibility during
usage. Therefore, rutting and fatigue resistances are based on the fresh asphalt and
after the rotating thin film oven test, RTFOT. This test simulates asphalt heat aging
during the hot mix process. Cold characterization is based on the asphalt binder after
the pressurized aging vessel, PAV, test which is intended to reproduce 7–10 years of
oxidative aging of the asphalt binder on the road.
All Superpave specifications are based on the SI unit, emphasizing importance of
international recognition. The World Road Association (PIARC) in France has been
active in developing similar international specifications [9, 10].
PG Grading
The Superpave asphalt mix design system includes the performance grade (PG) as-
phalt binder specification. The Superpave asphalt binder tests try to determine phys-
ical properties that can be directly related to field performance in terms of rutting,
fatigue cracking and low temperature cracking. Superpave characterizes asphalt at
the actual pavement temperatures it will experience, and at the periods of time when
distresses are most likely to occur. A part of the Superpave binder specification is
shown in Tab. 12-1. Detailed specifications as well as test apparatus, procedures and
the PG specification can be found elsewhere [8, 11].
Tab. 12-1 Example of Superpave binder specification.
Performance grade PG64 PG70
–10 –16 –22 –28 –34 –40 –10 –16 –22 –28 –34 –40
Average 7-day
maximum
pavement design
temperature (°C) <64 <70
Minimum
pavement design
temperature (°C) >–10 >–16 >–22 >–28 >–34 >–40 >–10 >–16 >–22 >–28 >–34 >–40
Original binder
Flash-point temp.,
minimum (°C) 230
Viscosity maximum
3 Pa s, test temp. (°C) 135
Dynamic shear,
G*/sin(δ ), minimum
1.00 kPa, test temp.
at 10 rad s–1 (°C) 64 70
Rolling thin film oven residue
Mass loss,
maximum, % 1.00
Dynamic shear,
G*/sin(δ ), minimum
2.30 kPa, test temp.
at 10 rad s–1 (°C) 64 70
Pressure aging vessel residue
PAV aging
temperature (°C) 100 100 (110)*
Dynamic shear,
G*sin(δ ), minimum
5.00 MPa, test temp.
at 10 rad s–1 (°C) 31 28 25 22 19 16 34 31 28 25 22 19
Creep stiffness,
S, maximum,
300 MPa, m-value
minimum, 0.300,
Test temp.,
at 60 s (°C) 0 –61 –12 –18 –24 –30 0 –6 –12 –18 –24 –30
*110 °C PAV for the desert climate
Pumping and handling: The maximum viscosity of the unaged binder should be be-
low 3 Pa s at 135 °C to ensure that the binder can be pumped and handled at the hot
mix facility. A rotational viscometer (ASTMD4402) is used.
Permanent deformation: The rutting resistance of the binder is represented by the

stiffness of the binder at high temperatures that one would expect in use. This is rep-
resented by G*/sin(δ ), where G* is the complex shear modulus and δ is the phase
angle determined by the dynamic shear rheometry, DSR, measured at 10 rad s–1
(1.59 Hz). The complex modulus can be considered as the total resistance of the
binder to deformation under repeated shear, and consists of elastic modulus, G′ and
loss modulus, G″ (recoverable and non-recoverable components). The relative
amounts of recoverable and non-recoverable deformation are indicated by the phase
angle, δ. The asphalt binder will not recover or rebound from deformation if δ = 90°.
In practice, to minimize rutting, G*/sin(δ ) must be a minimum of 1.00 kPa for
the original binder and 2.20 kPa after aging the binder using the RTFO procedure.
To address rutting resistance, the Superpave specification promotes the use of stiff,
elastic binders.
Fatigue cracking: The Superpave specifies G*sin(δ ) < 5.00 MPa, thus promotes the
use of compliant, elastic binders to address fatigue cracking. Since fatigue generally
occurs at low to moderate pavement temperatures after the pavement has been in
service for a period of time, the specification addresses these properties using binder
aged in both RTFO and PAV.
Low-temperature cracking: When the pavement temperature decreases, asphalt

pavement shrinks. Since friction against the lower pavement layer inhibits move-
ment, tensile stresses buildup in the pavement. When these stresses exceed the ten-
sile strength of the asphalt mix, a low temperature crack occurs. The bending beam
rheometer is used to apply a small creep load to a binder beam specimen and meas-
ure the creep stiffness. If the creep stiffness is too high, the asphalt will behave in a
brittle manner, and cracking is more likely to occur. To prevent this cracking, creep
stiffness has a maximum limit of 300 MPa.
The rate that the binder stiffness changes with time at low temperatures is regu-
lated through the m-value. A high m-value is desirable since this leads to smaller ten-
sile stresses in the binder and less chance for low temperature cracking. A minimum
m-value of 0.300 after 60 s of loading is required by the Superpave binder specifica-
tion. Since low temperature cracking usually occurs after the pavement has been in
service for some time, this part of the specification addresses these properties using
binder aged in both the RTFO and PAV.
As a part of the Superpave activities, chemical and physical properties of more
than 70 asphalt samples commonly used in the United States were analyzed. These
asphalt samples were available through the Material Research Library (MRL) for re-
searchers in the field [12]. An example of the Superpave analysis of one of the MRL
asphalt, AAA-1 (Lloydminster) modified with 3 % Butonal® NS175 (SBR latex from
BASF Corporation) is shown in Tab. 12-2. The rotational viscosity measured by the
Brookfield viscometer is 1.11 Pa s at 135 °C, which is within the specification of
<3 Pa s. G*/sin(δ ) of the original (unaged) asphalt were 1.91 and 0.59 kPa at 64 and
70 °C, respectively, which allow us to estimate G*/sin(δ ) = 1.0 kPa at 67 °C. The
same measurement for the RTFO residue gave G*/sin(δ ) = 3.47 and 1.89 kPa at the
same temperatures, thus G*/sin(δ ) = 2.2 kPa at 69 °C. The upper limiting (rutting
resistance) temperature of this asphalt is 67 °C and thus this modified asphalt meets
specification of PG64.
Tab. 12-2 Example of Superpave characterization of SBR modified asphalt.
Viscosity at 135 °C (Pa s) 1.11

Rutting resistance by DSR
Original asphalt G*/sin(δ ) at 64 °C (Pa) 1.91
G*/sin(δ ) at 70 °C (Pa) 0.59
After RTFO G*/sin(δ ) at 64 °C (Pa) 3.47
G*/sin(δ ) at 70 °C (Pa) 1.89
Fatigue resistance by DSR
After RTFO and PAV G*sin(δ ) at 7 °C (MPa) 2.98
G*sin(δ ) at 10 °C (MPa) 2.38
Low-temp. crack resistance by BBR
After RTFO and PAV Creep stiffness, S, at –24 °C (MPa) 186
Creep stiffness, S, at –18 °C (MPa) 108
Rate of change of S, m value at –30 °C
Rate of change of S, m value at –24 °C 0.298
Rate of change of S, m value at –18 °C 0.364
Temp. at G*/sin(δ) = 1.0 kPa (°C) 67

Temp. at G*/sin(δ) = 2.2 kPa (°C) 69
Limiting high temperature (°C) 67
Temp. at S = 300 MPa (°C) –29
Temp. at m = 0.30 (°C) –24
Limiting low temperature (°C) –34
PG grading (°C) 64–34
The Superpave analysis specifies the PAV temperature of 100 °C for 20 h for this
sample (Tab. 12-1). The DSR analysis of the PAV residue gave G*sin(δ ) = 2.98 and
2.38 MPa at 7 and 10 °C, respectively. These values are significantly lower than the
requirement for the PG64 asphalt.
Polymer modification improves the rutting and fatigue resistance mostly through
enhancement in the recoverable, elastic component, G′ of the asphalt as seen in
Fig. 12-3. The elastic and loss moduli, G′ and G″ of the unmodified asphalt were
0.035 and 0.80 kPa, respectively with phase angle δu = 88° at 64 °C, resulting
G*/sin(δ ) = 0.80 kPa. G′ increased nearly 11× to 0.37 kPa upon modification with
3 % SBR latex but non-recoverable, viscous component, G″ showed only moderate
increase of 2.3× to 1.80 kPa, which gives the phase angle δm = 78° at the same tem-
perature. This resulted in G*/sin(δ ) = 1.91 kPa as shown in Tab. 12-2. The phase
angle δ alone makes only a limited contribution for determination of the rutting re-
sistance since sin(δ ) = 0.999 and 0.981 at δu = 88° and δm = 78°, respectively, for the
unmodified and modified asphalt.
10
G*
Unmodified
G" (Viscous Behavior), kPa
1 *
G
0.1 SBR Modified
δm Fig. 12-3 Complex modulus G* of

δu unmodified and 3 % SBR latex modi-
fied asphalt measured at 64 °C. The
0.01 polymer modification results in 11×
0.01 0.1 1
increase in the elastic component, G′
with moderate increase in viscous
G' (Elastic Behavior), kPa component, G″.
The bending beam rheometry (BBR) of the PAV residue was conducted to estab-
lish the low limiting temperature of the modified asphalt. The creep stiffness values
were 186 and 108 MPa, and the m-values were 0.298 and 0.364 determined at –24
and –18 °C, respectively (Tab. 12-2). Thus, S would be 300 MPa about at –29 °C and
m would be 0.300 at approximately –24 °C. Taking the higher value, –24 °C is the low
temperature limit of this asphalt determined at a condition of 60-s loading.
The desired value of creep stiffness was originally developed as a correlation be-
tween thermal cracking of in-service asphalt pavement and binder stiffness values
estimated at 2 h loading time. However, using the concept of time–temperature su-
perposition, it was confirmed that by raising the test temperature 10 °C, equal creep
stiffness could be obtained after a 60-s loading. Thus, –34 °C would be the low tem-
perature limit from the BBR measurement. We conclude that this asphalt meets the
PG64-34 specifications as shown in Tab. 12-1.
Improvement in both the rutting and cold fracture resistance of the asphalt with
the polymer modification are demonstrated in Tab. 12-3 where Superpave analysis of
unmodified and modified with 3 % Butonal NS175 for AAA-1 and AAK-1 (Boscan)
asphalt are compared. In addition to the Superpave analysis, values of conventional
measures of unmodified and modified asphalt, such as ductility (ASTM D113), pen-
etration (ASTM D5), softening point (ASTM D36) and absolute viscosity measured at
60 °C (ASTM D2171) are also included.
Tab. 12-3 Superpave analysis of unmodified and SBR modified asphalts.
Asphalt AAA-1 AAK-1

Properties
Unmodified Modified Unmodified Modified
Brookfield viscosity
at 135 °C (mPa s) 280 1100 560 2000
Temp. at G*sin(δ) = 1 kPa (°C) 58 67 63 79
Temp. at G*–sin(δ) = 2.2 kPa
after RTFO (°C) 58 69 65 78
Temp. at S = 300 MPa (°C) –21 –29 –14 –19
Temp at m = 0.30 (°C) –24 –24 –17 –14
Limiting high temperature (°C) 58 67 63 78
Limiting low temperature (°C) –31 –34 –24 –24
PG Grading 58–28 64–34 64–22 76–22
Ductility at 4 °C >150 >150 28 86
Penetration (mm) at 25 °C 16 11 6.7 4.5
Softening Point (°C) 44 56 49 63
Absolute viscosity at 60 °C (Pa s) 0.086 0.34 0.33 1.6
The results of modifying asphalt with additives are highly dependent upon the
concentration, the molecular mass, the chemical composition, and microscopic mor-
phology of the additive as well as the crude source, the refining process and the grade
of the base asphalt used.
Superpave binder specifications are successful in predicting the rutting resistance
and cold fracture resistance of the unmodified asphalt. A new DSR procedure is un-
der development for the better prediction of fatigue resistance. Integration of the
bending beam rheometry data and direct tension measurement in the near future
will provide a better description of the benefits of the polymer-modified asphalt.
One of the primary benefits of polymer modified asphalt binders is a reduced sus-
ceptibility to temperature variation [13]. Because many Performance Grade asphalt
specifications can only be met with polymer modification, it is expected that the use
of polymer modified binders will increase as these specifications are implemented
during the late 1990s and the early 2000s. A 1997 survey of state highway agencies
found that 35 agencies reported that they will be using greater quantities of modified
binders; 12 agencies reported they will be using the same amount of modified
binders; and no agency reported they will be using less modified binder [14].
Storage Stability
A polymer-modified asphalt is a two phase system, forming a continuous fine poly-
mer network, that is highly swollen with aromatic components in the asphalt. The
polymer is mixed in the asphalt and stored at elevated temperature, which could
cause chemical reaction within polymer chains and with some components in the as-
phalt. The degree of swelling, and thus the microscopic morphology of the polymer
phase, varies widely dependent on the crude source, the refining process and the
grade of the base asphalt [15–17].
When the chemical and physical properties of the polymer and asphalt are not
matched to each other, a polymer rich phase could develop near the surface of the
asphalt when stored at 160–170 °C for a few days without agitation as reported by
Brûlé et al. with SBS modified asphalts [16]. The asphalt composition in the polymer
rich phase is vastly different from the original asphalt.
One of their results with Asphalt E modified with 5 % SBS polymer is shown in
Fig. 12-4. The aromatic and saturate components preferentially partition to the poly-
mer phase, thus concentrating the asphaltenes and polar resin fractions in the as-
phalt phase. The majority of asphaltenes are retained in the asphalt phase, resulting
in an increase in the asphaltenes/aromatic ratio. This potentially leads to reduced
swelling of asphaltenes, which would have negative effects on low temperature flexi-
bility of asphalt.
Polymer phase
Original Asphalt E
Asphaltene
Resin Saturate
Asphalt phase
Aromatic
Fig. 12-4 Difference in asphalt composition among original asphalt and

the polymer rich and asphalt phases developed during storage.
The phase separation during storage can be visualized with hot stage optical mi-
croscopy, which allows us to observe changes in the polymer morphology at the mix-
ing and storage conditions. Here, the other MRL asphalt, AAB-1 (Wyoning Sour),
was modified with 3 % Butonal NS175. Photomicrographs shown in Fig. 12-5 illus-
trate the presence of a fine polymer network in the freshly mixed sample observed at
110 °C at ×200 magnification. The polymer phase transfers to macroscopic polymer
globules without agitation when the sample is slowly heated to 170 °C. These poly-
mer blobs migrate to the top due to the density difference.
Fig. 12-5 Photomicrographs of conventional SBR modified asphalt taken

at 110 and 170 °C.
Wegan et al. [17] reported observing similar macroscopic polymer globules and/or
a polymer layer surrounding the aggregate surface in the paved asphalt mixtures,
even though only fine structures existed in the modified binder observed at room
temperature using fluorescence microscopy, which is the traditional method of
studying polymer morphology [15–17].
The photomicrograph shown here (Fig. 12-5) demonstrates that polymer modified
asphalt behaves as a dispersion consisting of two immiscible fluids; a highly visco-
elastic fluid dispersed in a less viscous one. The dispersed phase elongates to fine
fluid columns under agitation. When the agitation is removed, these elongated
columns transfer to a series of spherical droplets as minimizing the total surface
area and thus the total energy.
Numerous inventions are reported in the literature to overcome the polymer in-
compatibility in the modified asphalt, which often involve introduction of a con-
trolled cross-link reaction in the polymer phase. Cross-linking reduces solvent
swelling and increases the visco-elasticity of the polymer phase. Butonal NX1129 is
an example of the new type of SBR latex. As shown in Fig. 12-6, a fine polymer net-
work remains even when the modified asphalt is observed at 170 °C for 10 min. Sta-
ble polymer structures of this latex also extend the low temperature limits of certain
modified asphalts, as determined by the direct tension measurement.
12.2.2
In-line Injection (Pump-in)
Pre-blending infers that the latex and asphalt have been mixed at a central location
using a batch process as discussed above. In-line injection (also known as pump-in)
implies that the latex and asphalt are blended immediately before being applied to
the aggregate at the hot-mix plant. This process eliminates potential separation of
Fig. 12-6 Butonal NX1129 maintains stable, fine polymer network even
at 170 °C.
polymer and asphalt during transportation and storage of incompatible materials,

and the need for an asphalt storage tank for the polymer modified asphalt, thus re-
ducing handling costs.
With the pre-blending process, polymer and asphalt are thoroughly mixed and the
binders can be tested and certified before application to the aggregates. Recent ad-
vancement in quality control at the mixing process guarantees adequate mixing and
performance of the asphalt produced by the in-line injection process. An optical pho-
tomicrograph demonstrating polymer networks in the asphalt prepared by the direct
injection process is shown in Fig. 12-7.
Fig. 12-7 Photomicro-

graph demonstrating
the presence of poly-
mer networks in the
asphalt prepared by
the in-line injection
(pump-in) process.
12.3
Paving with Asphalt Emulsion
Asphalt emulsions used in road construction and maintenance are either anionic or
cationic, based on the electrical charge of the asphalt particles, which is determined
by the type of the emulsifying agent used. The asphalt contents of these emulsions
are, in most cases, from 55 to 75 % and prepared using a high shear mechanical de-
vice such as a colloid mill. The colloid mill has a high-speed rotor that revolves at
1000–6000 rpm with mill-clearance settings in the range of 0.2 to 0.5 mm. A typical
asphalt emulsion has a mean particle size of 2–5 µm in diameter with distribution
from 0.3 to 20 µm. A photomicrograph and typical size distribution of an asphalt
emulsion are shown in Fig. 12-8. Asphalt emulsion properties depend greatly upon
the emulsifier used for their preparation.
Fig. 12-8 Particle size distribution and photomicrograph of a typical

asphalt emulsion.
A latex modified asphalt emulsion can be prepared using several methods: addi-
tion of the latex in the aqueous emulsifier solution, direct injection in the asphalt
line just ahead of the colloid mill or post-addition to the pre-manufactured emulsion,
as schematically shown in Fig. 12-9. Addition to the aqueous phase is the most com-
monly used method. The direct injection process often helps to produce an emulsion
with a desired high viscosity for chip seal application (Sect. 12.3.1). This is due to the
narrow particle size distribution of the asphalt emulsion produced with this process.
Asphalt emulsions are classified with their charge and on the basis of how quickly
the asphalt will coalesce, which is commonly referred to as breaking, or setting. The
terms RS, MS and SS have been adopted to simplify and standardize this classifica-
tion. They are relative terms only and mean rapid-setting, medium-setting and slow-
setting. An RS emulsion has little or no ability to mix with an aggregate, an MS
emulsion is expected to mix with coarse but not fine aggregate, and an SS emulsion
is designed to mix with fine aggregate. The emulsions are further subdivided by a se-
ries of numbers and letters related to the viscosity of the emulsions and the hardness
of the base asphalt cements. The letter “C” in front of the emulsion type denotes
Fig. 12-9 Schematic illustra-

Latex
tion for latex modified asphalt
emulsion production.
Water Asphalt
Emulsifier
Acid or
Base
Latex
Storage
Colloidal
Mill
Latex
cationic. The absence of the “C” denotes anionic. For example, CRS-2 is a cationic
rapid setting emulsion typically used for chip seal application.
ASTM and the American Association of State Highway and Transportation Offi-
cials (AASHTO) have developed standard specifications for the grades of emulsions,
shown in Tabs 12-4 and 12-5 for anionic and cationic emulsions, respectively. The
“h” that follows certain grades means that harder base asphalt is used. The “HF” pre-
ceding some of the MS grades indicates high-float, as measured by the Float Test
(ASTM D139 or AASHTO T 50). High float emulsions have a specific quality that
permits a thicker asphalt film coating on the aggregate particles.
12.3.1
Applications of Asphalt Emulsions
The Cold-mix recycling operation, which utilizes milled old asphalt pavement mixed
with asphalt emulsion, is gaining popularity for rehabilitating deteriorating road-
ways. In this method, the old asphalt pavement is crushed, often in place. An in-
place aggregate base can also be incorporated or new aggregates can be added to the
old materials and asphalt emulsion added. Then, materials are mixed together,
spread to a uniform thickness, and compacted. Slow setting SS and CSS asphalt
emulsions are used currently without polymer modification.
Surface treatments applied to an existing pavement for preventive maintenance
are the most significant application of polymer modified asphalt emulsion. They are
economical, easy to place, resist traffic abrasion and provide a long lasting water-
proof cover over the underlying structure. There are several types of surface treat-
ment, but in this chapter, we will limit our discussion to chip seal and slurry surfac-
ing. Detailed descriptions as well as recommended performance guidelines of vari-
ous paving technologies using asphalt emulsions can be found elsewhere [18, 19].
Tab. 12-4 Selected requirements for anionic asphalt emulsion (ASTM D977).
Test Rapid-setting Medium-setting Slow-setting
RS-1 RS-2 HFRS-2 MS-1 MS-2 MS-2h HFMS-1 HFMS-2 HFMS-2h SS-1 SS-1h
Test on emulsion
Viscosity, Saybolt Furol at 25 °C (s) 20–100 20–100 100+ 100+ 20–100 100+ 100+ 20–100 20–100
Viscosity, Saybolt Furol at 50 °C (s) 75–400 75–400 20–100 100+ 100+ 20–100 20–100
Minimum residue by distillation (%) 55 63 63 44 65 65 55 65 65 57 57
Test on residue from distillation

Penetration at 25 °C, 100 g, 5 s, (dmm) 100–200 100–200 100–200 100–200 100–200 40–90 100–200 100–200 40–90 100–200 40–90
Ductility, 25 °C, 5 cm min–1 (cm) <40 <40 <40 <40 <40 <40 <40 <40 <40 <40 <40
Float test, 60 °C (s) 1200 1200 1200 1200
Tab. 12-5 Selected requirements for cationic asphalt emulsion (ASTM D2397).
Test Rapid-setting Medium-setting Slow-setting
CRS-1 CRS-2 CMS-2 CMS-2h CSS-1 CSS-1h
Test on emulsion
Viscosity, Saybolt Furol at 25 °C (s) 20–100 20–100
Viscosity, Saybolt Furol at 50 °C (s) 20–100 100–400 50–450 50–450
Minimum residue by distillation (%) 60 65 65 65 57 57
Test on residue from distillation

Penetration at 25 °C, 100 g, 5 s, (dmm) 100–250 100–250 100–250 40–90 100–250 40–90
Ductility, 25 °C, 5 cm min–1 (cm) <40 <40 <40 <40 <40 <40
12.3 Paving with Asphalt Emulsion
315
Chip seal: This treatment involves spraying asphalt material (heated asphalt or as-
phalt emulsion) followed immediately by a thin (one stone thick) aggregate cover as
schematically shown in Fig. 12-10. The aggregate is immediately rolled with a pneu-
matic roller and a light brooming may be necessary to remove any excess aggregate.
Cutback asphalts have been used in the past for this purpose but asphalt emulsion is
now preferred due to environmental and safety (fire hazard) concerns associated
with cutback asphalt. A rapid setting RS, HFRS or CRS is usually used, though a
medium setting MS, HFMS or CMS asphalt emulsion could be used (ASTM D977
and D2397 for anionic and cationic emulsions, respectively). The cationic asphalt
emulsion often provides better asphalt adhesion to the aggregate. The polymer mod-
ified asphalt emulsion (2–4 % polymer by weight of asphalt) improves chip retention
and enhances pavement durability (Sect. 12.3.5).
Aggregate Particle Emulsion Residue
Fig. 12-10 Schematic diagram

illustrating chip seal paving.
Slurry seal: A slurry seal is a homogeneous mixture of well-graded fine aggregate,

asphalt emulsion, water and mineral fillers applied to a pavement as a surface treat-
ment. Slurry seal is usually applied in a thickness of 3 to 6 mm. A small amount of
mineral filler, hydrated lime, limestone dust, Portland cement or fly ash, aids in set-
ting the slurry. The Slurry comes directly from a traveling mixing plant into an at-
tached spreader box that spreads the slurry by a squeegee-type action as shown in
Fig. 12-11. The machine used for production of slurry seal is a self-contained, con-
tinuous-flow mixing unit. The asphalt emulsion used in the slurry mix may be SS-1,
SS-1h, CSS-1 or CSS-1h. Quick-setting (QS) asphalt emulsion is used when early
opening to traffic is necessary.
Microsurfacing: A new slurry technique, microsurfacing, takes advantages of poly-

mer modified asphalt emulsions. It can be applied at greater thicknesses than con-
ventional slurry seals, allowing its use for rut-filling and is maintains a friction re-
sistant surface throughout the service life. The microsurfacing mix has to set quickly
enough to accept traffic within 1 h after placement [20]. Polymer modified CSS-1h
asphalt emulsion (ASTM D2397 and AASHTO M208) is used with a minimum poly-
mer level of 3 %. The International Slurry Seal Association has established recom-
mended performance guidelines A105 and A143 for the slurry seal and microsurfac-
ing, respectively. A careful mix design (ISSA TB-139, TB-09, TB-114, TB-100, TB-
147A, TB-144 and TB-113) confirming compatibility of the aggregate, polymer mod-
ified asphalt emulsion, mineral filler, and other additives is essential for successful
slurry seal and microsurfacing operations.
Fig. 12-11 Schematic diagram of a typical microsurfacing paver.

Courtesy Akzo Nobel Asphalt Applications Inc.
12.3.2
Asphalt Emulsion Tests
Standard tests and procedures for testing asphalt emulsions are specified in ASTM
D244 and AASHTO T59. These include particle charge, viscosity, storage stability,
demulsibility and others. A distillation or evaporation test is used to recover the as-
phalt (emulsion residue) from the emulsion. In these tests, the asphalt emulsion is
subjected to a maximum of as high as 260 °C for the distillation method or 167 °C for
the evaporation. The most common tests run on the recovered residue include pene-
tration, softening point, ductility, elastic recovery and torsion recovery. These tests
are meant to be used as a quality control tool, (e.g. to confirm a designed polymer lev-
el in the modified asphalt), but are not designed to correlate the binder performance
for each application [21]. During the residue recovery process, excess heat applied to
the polymer modified asphalt emulsion causes formation of macroscopic polymer
globules that are as large as a few mm in diameter. A minor difference in the tem-
perature and length of the distillation would cause variation in the polymer mor-
phology, which explains the poor reproducibility reported by the AEMA Materials
Committee Round Robin Studies on emulsion residue characterization [22].
12.3.3
Polymer Honeycomb Structure in Cured Asphalt Emulsion
Modified asphalt emulsion with latex is not just an emulsion of polymer-modified

asphalt, but rather an emulsion containing dispersed latex particles in the aqueous
phase, as schematically shown in Fig. 12-12. Menisci of water containing latex parti-
cles (and Portland cement particles for microsurfacing) form among asphalt parti-
cles when water starts to evaporate from the asphalt emulsion. The SBR latex for as-
phalt modification is designed to create a polymer film without coagulum formation;
promoting early strength development. The majorities of latex particles migrate to-
gether with water and accumulate in the menisci, and thus act as “spot welding” of
asphalt particles to ensure maximum binding power, as shown in the right side of
Figure 12-12. To form the finest honeycomb structure the asphalt emulsion should
not break (coalesce) during the process.
Asphalt
Asphalt
Latex Film
Latex
Latex Modified Emulsion Cured Asphalt Emulsion

Fig. 12-12 Left: Schematic illustration of latex Right: Latex particles transform to a continuous
modified asphalt emulsion showing that latex polymer film surrounding asphalt particles,
particles remain in the aqueous phase. which cures to form the honeycomb structure.
Scanning electron microscope observation of the microsurfacing pavement con-

firmed the presence of the polymer honeycomb structure [22]. Here, a sample of the
freshly applied pavement sample was treated with OsO4 and the asphalt was extract-
ed with MEK (methyl ethyl ketone) solvent. The treatment with OsO4 makes the SBR
polymer insoluble to the organic solvent and also improves the contrast for the scan-
ning electron microscope, SEM, observation.
A series of SEM photographs of the fractured surface were taken and shown in
Fig. 12-13. These photographs, especially (b) and (c) demonstrate the honeycomb
structures of the SBR polymer formed around asphalt particles. Some latex polymers
are also adhering on the aggregate surface as seen in (c). It is important to realize
that the latex polymers should remain in the aqueous phase, not in the asphalt, and
transform to a continuous polymer film during the curing process. Since Portland
cement particles also remain in the aqueous phase, the flexible polymer-cement
complex creates these honeycomb structures. In contrast, the honeycombs made
only with Portland cement would also be very brittle and this would be the case when
the polymer is present in the asphalt phase.
(b)
µm
5µ
(a)
µm
25µ
(a) (b)
(c)
(c)
µm
10µ 1µm
Fig. 12-13 A series of scanning electron micro- mer honeycomb formed around asphalt parti-
scope photographs of the cured microsurfacing cles. (c) Some polymers also adhere on the
specimen demonstrating (a) and (b) SBR poly- aggregate surface.
Do these honeycombs strong enough to maintain their structure under repeated

poundings by heavy weight truck tires running at above 100 km h–1 throughout the
lifetime of the pavement? Pavement samples were taken from Texas State Highway
84 near Waco. This highway was treated with the microsurfacing in 1998. Samples
were taken from the wheel path as well as the shoulder of the pavement. As seen in
Fig. 12-14, the honeycomb structure with the SBR latex polymer-cement complex is
flexible enough to withstand repeated stresses after three years service at the high-
way condition. Advantages of this flexible honeycomb structure with SBR latex will
be discussed later in the emulsion residue characterization.
An optical microscope observation simulating chip seal was also conducted using
SBR latex modified CRS-2 emulsion [23]. When the emulsion is placed on sand par-
ticles, which are placed on the microscope slide glass, spontaneous formation of the
polymer network was observed as shown in Fig. 12-15.
12.3.4
Asphalt Emulsion Residue Characterization
The need for an appropriate residue recovery procedure for asphalt emulsion has
been recognized in both Europe and the US. The forced airflow drying method,
which dries the emulsion at ambient temperature, provides a sufficient amount of
residue samples within 3–5 h for the Superpave binder characterization [22]. An
example of estimating the rutting resistance temperature, Tr (temperature at
G*/sin(δ ) = 1 kPa) of microsurfacing emulsion residue is shown in Fig. 12-16. A typ-
5µm
Fig. 12-14 SEM photographs of microsurfacing pavement taken under

the wheel path; Texas State Highway 84 near Waco, paved in 1998, and
samples taken in 2001.
Fig. 12-15 Photo-

micrograph demon-
Latex Polymer strating spontaneous
Network formation of polymer
network upon curing
of the CRS-2 asphalt
emulsion modified
with 3 % cationic SBR
latex.
50µm
ical microsurfacing formulation consists of 100 g aggregates, 12 g of 65 % asphalt

emulsion containing 3 % latex polymer, 10 g water and 1 g Portland cement. The for-
mulation used for this study is the same but without the aggregate and 10 g water.
As seen in Fig. 12-16, the unmodified asphalt emulsion was made with a PG64 as-
phalt and the rutting resistance temperature increased slightly from 66 °C to 68 °C
after one month. The sample with Portland cement shows a gradual increase in Tr to
71 °C within three weeks. This increase in Tr is mostly due to stiffening of the as-
phalt as the phase angle of the residue increases from 82° to 88° at Tr. The value of Tr
showed a rapid increase to 76 °C within the first 3 days of curing when 3 % of the
SBR latex is also present in the mix. Two PG grades improvement in the rutting re-
sistance was achieved after two weeks of curing. The phase angle at Tr remained
nearly constant at 77–78° throughout the curing, confirming that SBR modified as-
phalt binder maintains the elasticity. Differences in the phase angle of these three
samples are also summarized in Fig. 12-16.
Fig. 12-16 The rutting resistance temperature, observed with the polymer-cement system,
Tr, of microsurfacing emulsion, emulsion plus which maintains elasticity of the residue as
cement and emulsion, cement and 3 % SBR seen with the low measured phase angle.
latex. Two PG grade improvement can be
To evaluate potential benefits on performance during its lifetime, an accelerated

curing test was also designed. Here, the emulsion was dried one day under the
forced airflow, and transferred into an oven at 60 °C, and so simulating pavement
temperature during the daytime.
Two different latex polymer levels of 3 and 5 % were studied. Three PG grades im-
provement (from PG64 of the unmodified asphalt) with 3 % latex polymer takes only
10 days of curing, as seen in Fig. 12-17, demonstrating the rut filling capability of the
microsurfacing system.
The European Standard for emulsions of pure and polymer modified bitumen in-
cluding a residue recovery procedure and characterization of the recovered residue is
currently under preparation.
12.3.5
Application Tests for Chip Seal and Microsurfacing
Microsurfacing: Jones et al. [24, 25] analyzed the performance of seven polymer-mod-
ified asphalt emulsions for microsurfacing application. The objective of their studies
was to examine effects of different polymers on microsurfacing performance. The
same asphalt, surfactant and aggregates were used to eliminate all other variables
Fig. 12-17 Accelerated curing

of the microsurfacing residues
at 60 °C after drying under
forced airflow for one day.
from the mix design. Results of the Wet Track Abrasion Test, WTAT, and Loaded
Wheel Test, LWT, are reproduced in Fig. 12-18.
60 15
Wheel Track Deformation, %
Wet Abrasion Loss, g/ft2
40 10
20 5
Fig. 12-18 The wet track

abrasion test and loaded wheel
0 0
test of cured microsurfacing
A
al
R
specimen prepared with five

en
EV
SB
SB
ur
pr
at
different polymers reported by

N
eo
N
Jones [23, 24].
The authors concluded that SBR latex continues to perform well in virtually all the
laboratory tests to which it has been subjected. They also recognized that the materi-
als which were received as latices, tended on average to outperform the solid poly-
mers. These conclusions, especially LWT results, can now be understood in the light
of the formation of the polymer honeycomb structure providing excellent rutting re-
sistance of the asphalt emulsion residue. This is demonstrated in Figs 12-13 to
12-16].
12.4 Eco-efficiency Analysis 323
Chip seal: Loose chips from a freshly paved road are the major safety concern for
chip seal operation, and several attempts were reported in the literature to develop a
laboratory procedure to simulate the field experience. A modified fretting test (also
know as the abrasion cohesion test Esso, ACTE) appears to be the most success-
ful [26, 27]. In this test, a known amount of CRS-2 asphalt emulsion and aggregates
are spread on a roofing felt, and then rolled with a 30 kg rubber roller. The sample is
subjected to the shearing action of a horizontal steam-hose, which is attached to a
Hobart sun and planet mixer, and the percentage of retained chips is recorded as a
function of curing time.
An example of the test results is shown in Fig. 12-19, which demonstrates early co-
hesion development with the latex modified asphalt emulsion [28]. Marchal et al. [27]
report that the maximum chip retention does not exceed 80 % even with a fully cured
asphalt emulsion, and approximately 50 % chip retention is considered to be strong
enough to be open to traffic. Use of a specially designed brush appears to reduce a
problem of chip build-up around the steam-hose [29].
80
Chip retention, %
60
Latex Modified
40
Unmodified
20
Fig. 12-19 Results of modified
fretting test demonstrating
0
advantages of the early chip
0 30 60 90 120
retention with cationic SBR
latex modified emulsion. Curing time, min.
12.4
Eco-efficiency Analysis
Recent study by Queiroz et al. [30] demonstrated a statistically significant relation-

ship between a country’s economical development and its road infrastructure
(Fig. 12-20). A well-developed and well-maintained highway system is credited for
improvements in access to goods and services, education and employment opportu-
nities. A person living in Australia has, on average, access to 27-lane meters of paved
road. In comparison, it is only 16-lane centimeters for people in China! Improve-
ment in cold mix technology to provide durable pavements would result in signifi-
cant impact on the well being of people living in these developing countries. A cold
mix plant, using asphalt emulsion, requires less initial capital investment and lower
energy consumption than a hot mix plant.
For developed countries, environmental focus has shifted from pollution preven-
tion to sustainable development. BASF developed a so-called eco-efficiency analysis,
as an internal decision making tool, to help in evaluating products and processes for
Fig. 12-20 A linear correlation with R2 = 0.76 PGNP = GNP/Capita in $ and paved roads
exists between a country’s economical well- in km/million inhabitants are plotted for 98
being and road infrastructure. Here, countries [30].
sustainable development. The eco-efficiency analysis takes equal account of both the
ecological and economic aspects and compares pros and cons of each choice. The
main goal of the eco-efficiency analysis is “To offer customers the best possible al-
ternatives with the least environmental impact at the best cost”.
It has been realized that preventive maintenance of existing roadways is the most
financially effective use of available resources [3, 31, 32]. The eco-efficiency analysis
was applied to compare three different paving methods of hot mix, polymer modi-
fied hot mix and asphalt emulsion based microsurfacing [33]. The study integrates
environmental impact analysis and economical consideration. The base study as-
sumes a 7-year life for the microsurfacing treatment (8–12 mm thick), a 10-year life
for the thin (4 cm) hot mix overlay and a 13-year life for the polymer modified hot
mix overlay.
The environmental impact analysis is based on the life-cycle analysis [34], which
evaluates environmental aspects and potential impacts throughout a product’s life
cycle (e.g., cradle-to-grave evaluation) from raw material acquisition through produc-
tion, use and disposal. For asphalt emulsion based paving, this analysis includes not
just for production of the asphalt emulsion and paving operations, it starts from the
crude oil production, refinery process, chemical additives and aggregate production.
It also includes waste production, recycling operation, and transportation and distri-
bution of all these activities.
These environmental impacts are classified into five parameters: raw materials
consumption, energy consumption, emission, potential health effects, and risk of
accident and misuse. When all factors were considered, microsurfacing had a lower
environmental “footprint” as shown in Fig. 12-21. The thicker hot mix layer let to a
greater use of natural resources, as well as higher energy consumption and emission
involved in its manufacture and transportation.
Energy
1,00
0,50
Raw material Emissions
0,00
Risk potential Potential health

effects
Fig. 12-21 Environmental profiles for microsur- Cold-mix microsurfacing

facing and thin hot mix overlays. Microsurfacing
Hot-mix asphalt
has a lower environmental “footprint” than two
other alternative treatments. Modified hot-mix asphalt
These environmental impacts were weighed according to how surveys said the
public viewed their relative importance. When this result is combined with the an-
nual costs of the treatments, the overall conclusion is that microsurfacing provides a
better balance between cost-effectiveness and environmental impact than does a thin
hot mix overlay as shown with the eco-efficiency portfolio of the preventive mainte-
nance in Fig. 12-22. Here, all costs and environmental impacts were averaged over
0,2
High eco-efficiency
Cold-mix
micro-
Environmental impact
surfacing
1,0
Modified
hot-mix
Hot-mix asphalt
Fig. 12-22 Eco-efficiency port- asphalt
folio combines environmental
impact with costs of treat-
Low eco-efficiency
ments. Results demonstrate
that microsurfacing is more 1,8
“Eco-Efficient” than hot mix 1,8 1,0 0,2
overlays. Costs (relative)
each year of the life of the treatment. The study also suggests that future improve-
ment in microsurfacing techniques could lead to additional cost and environmental
advantages [33].
12.5
Concluding Remarks
Asphalt roads account nearly 95 % (3 300 000 km) of the paved roads in the US Ad-
dition of as little as 2–3 % of polymers in the asphalt improves rutting resistance, and
prevents premature fatigue and cold fracture crack formation. The latex can be used
for both hot mix and emulsion based paving. Recent studies [33] on eco-efficiency
analysis clearly demonstrate economical and ecological advantages of the asphalt
emulsion based microsurfacing for preventive maintenance.
Latex, because it is an aqueous dispersion, is the ideal polymer for modification of
an asphalt emulsion. Commercial availability of the cationic form makes SBR latex
ideal for chip seal, slurry seal and microsurfacing applications, which are predomi-
nantly used for preventive maintenance.
Acknowledgement
The author is grateful to Glynn Holleran of Valley Slurry Seal Co., Drs Alan James
and Julia Wates of Akzo Nobel Surface Chemistry LLC, Dr. Per Redelius of AB
NYNÄS Petroleum, Jeremy Kissock of BASF New Zealand and Mike Taylor of BASF
Corporation for their valuable comments and advice.
References
1 The Asphalt Institute, The Asphalt 6 S. Shuler, J. A. Epps, Presented to the

Handbook, Manual Series No. 4 (MS-4). Rubber Division, American Chemical
2 Symposium of World Road Bitumen Society, Philadelphia, PA, 1982.
Emulsion Producers, Bordeaux, Septem- 7 D. C. Thompson, J. F. Hagman, Assoc.
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3 F. L. Roberts, P. S. Kandhal, E. R. 8 Construction of Hot Mix Asphalt Pave-
Brown, D. Y. Lee, T. W. Kennedy, Hot ments, Manual Series No. 22, 2nd edn,
Mix Asphalt Materials, Mixture Design Asphalt Institute, Lexington, KY.
and Construction, NAPA Research and 9 Use of Modified Bituminous Binders,
Education Foundation Textbook, 2nd Special Bitumens and Bitumens with Ad-
Edition, 1996. ditives in Pavement Applications, World
4 G. King, H. King, R. D. Pavlovich, A. L. Road Association (PIARC) Technical
Epps, P. Kandhal, Additives in Asphalt, Committee Flexible Roads (C8), Labo-
J. Assoc. Asphalt Paving Technol. 75th ratoire central des Ponts et Chaussées,
Historical Review and Index of Journals, September 1999.
1975–1999, 1999, 68A, 32–69,. 10 World Road Association,
5 T. Hancock, UK Patent No. 9952, www.piarc.icpc.fr
November 21, 1843.
References 327
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Series No. 1 (SP-1), Asphalt Institute, Proc. 2000, 1–17.
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12 D. A. Anderson, D.W. Christensen, Network Formation in the Emulsion
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13 W. Arand, O. Harder, B. Herr, Asphalt Meeting, Feb. 1989.
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15 L. H. Lewandowski, Polymer Modifica- 28 J. Wates, A. James, Akzo Nobel inter-
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18 AEMA Recommended Performance Guide- bilitation and Maintenance, ASTM STP
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Residues Recovered by the Forced Air-
13
Applications of Redispersible Powders
Hermann Lutz and Christoph Hahner
13.1
Introduction
The building/construction industry is the main industry for redispersible powders.

Over the years the usage of dry mortar technology has been developed dramatically
and modernized the way mortars are being used on a job-site. The invention of re-
dispersible powders enabled the industry for the first time to produce pre-packed,
polymer modified building materials that needed only the addition of water before
application. These materials, known as dry mortar mixes guarantee defined and con-
sistent performance of construction materials.
In the past up until to the 1950s mortars were exclusively used and applied as job-
site mixed mortars, where the mineral binder (mostly cement) and the aggregates
(mostly silica sand) were transported separately to the job-site. The aggregates and
the mineral binders were then mixed together by hand in the appropriate ratio and
were gauged with water in order to obtain the fresh mortar ready to apply.
During the 1950s and 1960s both in Western Europe and the US, but especially in
Germany, there was a fast growing demand in the construction industry for new
building materials and technologies. Several reasons, like shortage of skilled work-
men, the need of shorter construction time together with cost reduction, increasing
labor costs, the diversification of building materials suitable for specific applications,
the request for new materials and an increased demand for better quality of con-
structions were supporting a movement towards dry mix mortar technology.
The job-site mix mortar technology is not able to meet adequately all these re-
quirements. As a practical consequence, the development of the modern construc-
tion and building chemical industry in the countries of the West from the 1960s on-
wards was influenced mainly by two important trends, which can be seen nowadays
in the whole world. First there was a replacement of the job-site mixed mortars by
premixed and pre-packed dry mix mortars, which are more and more applied with
machines. Secondly mortars started to be modified with polymer binders in order to
improve the product quality and to meet the requirements of the modern building
industry. As a consequence the two-pack systems (mortar + dispersion) as well as
330 13 Applications of Redispersible Powders
ready to use products (liquid or paste) were substituted by one-pack systems, which
are modified with redispersible powders, pre-mixed and pre-packed dry mix mortars.
13.2
Manufacturing of Redispersible Powders
A redispersible powder is by definition a polymer in a powdered form that can be

redispersed by adding water to it. The resulting emulsion will fulfill the functionali-
ty of a polymeric dispersion binder, normally within a cementitious or gypsum based
system. Redispersible powders are manufactured by spray drying an emulsion
(Fig. 13-1).
Fig. 13-1Spray-dried
polymer particle.
Over 90 % of all industrial manufactured polymer dispersions are produced by

emulsion polymerization. The most important monomers, which are being used for
applications in the building/construction industry, are vinyl acetate, ethylene, versa-
tic acid esters, vinyl chloride, styrene and acrylics. Especially the use of ethylene as a
co-monomer offers some extraordinary advantages:
– environmentally safe,
– no saponification,
– UV-resistant (no yellowing),
– very hydrophobic,
– ideal for co-polymerization with vinyl acetate,
– very low glass transition temperature, Tg, of –93 °C,
– very flexible, and
– good adhesion to most of the substrates.
To guarantee the performance of a redispersible powder in its final application a
protective colloid is added to the emulsion before the spraying process. The colloid
protects the polymer particles from film forming during the spray drying process
13.2 Manufacturing of Redispersible Powders 331
and is also responsible for that the powder will redisperse in water again (Figs 13-2
and 13-3).
dispersion
particle concentration particle concentration
69 100 69
ppm % ppm
weight distribution curve
80
60
40
20
0
0 2 4 6 1 1 10
particle size (diameter)
redispersion
particle concentration particle concentration
92 100 92
ppm % ppm
weight distribution curve
80
60
40
20
0
0 2 4 6 1 1 10
particle size (diameter)
Fig. 13-2 Dispersion/redispersion – comparison of particle size distribution.
spray adding
drying water
drying
dispersion protective redispersible redispersion

colloid powder
Fig. 13-3 The spray-dry process.

Over the years poly vinyl alcohol (abbreviated PVOH or PVAl) proofed to be the
most preferred protective colloid for that purpose. In a cementitious environment
PVOH will be partly saponified and also absorbed of fine particles within a mortar,
i.e. cement and fillers. This results in a film forming of the dispersed polymer and fi-
nally the polymer film is not redispersible any more. Since the polymer film (acting
as a binder) is distributed throughout the cement matrix it improves dramatically the
adhesion, abrasion resistance, flexural strength, flexibility, water impermeability/wa-
ter repellency (hydrophobicity) and workability of a cementitious system.
13.3
Dry Mortar Technology
The invention of redispersible powders by Wacker-Chemie in 1953 made for the first
time the production of polymer modified dry mix mortars possible, which are nowa-
days referred to as one pack or one component system (“bagged” materials). New
construction methods and building materials, which had the need for more safety,
reliability, durability, efficiency and economy, have been achieved by using modern
methods like the dry mix mortar technology. As a consequence worldwide the “job-
site mix technology” and the modification of mortars with liquid polymers on job-
sites were and are substituted by polymer modified dry mix mortars. The product
characteristics are very well adapted to the requirements of modern construction
technologies, materials and climates.
Pre-mixed and pre-packed dry mix mortars not only increase significantly the pro-
duction performance and the productivity on construction sites, but guarantee also
that high and constant quality binder, aggregates, and additives are being mixed ex-
actly in the same ratio, thus ensuring a consistent high quality level within dry mix
mortars. Furthermore, dry mix mortars offer solutions to specific problems that are
precisely tailored to certain types of construction/material specifications. Especially
in the USA, the legal aspect of a reliable, properly conducted construction job is very
important to each manufacturer of construction materials.
The use of redispersible powders and therefore also the use of polymer modified
powdered mortars is already for many decades standard in the construction industry
in Europe and North America (predominantly in the USA). Other marketplaces all
over the world like South America, Asia, Africa and Australia are in the process fol-
lowing that example. More and more environmental reasons ask also for the usage of
dry mortars, since the recycling of buckets becomes more and more an issue. Dry
mortars are also easy to store, transport and do not require biocides.
Typically dry mortar mixes contain the components listed in Tab. 13-1 and are
defined according to German standard DIN 18557.
The application areas of dry mix mortars are:
– ceramic tile adhesive,
– tile grouts,
– E.I.F.S. (exterior insulation and finish systems)/E.T.I.C.S. (exterior thermal insu-
lation compounds),
Tab. 13-1 Dry mortar mixes.
Mineral binders Aggregates fillers Polymer binder Additives
Portland cement
(OPC) Silica sand Redispersible powder Cellulose ether
High Alumina
Cement (HAC) Hydrated lime Pigment
Special cement Dolomite sand Defoamer
Hydrated lime Marble sand Air-entraining agent
Gypsum, Lightweight fillers Retarder
anhydrite Special and functional fillers Accelerator
Thickener
Hydrophobing agents
Plasticizers
– self-leveling over- and underlayments, screeds,

– stucco, skim coat,
– topcoat/finish coat,
– patch and repair mortar,
– adhesive mortars (for all kind of substrates),
– crack isolation membrane,
– powder paints,
– gypsum based compounds (joint fillers),
– waterproof membranes/sealant slurry,
– pool decking, and
– stamped concrete.
The following paragraphs will describe the most important and most developed
application areas for redispersible powders as they are ceramic tile adhesives/ tile
grouts, thermal insulation systems (E.I.F.S.), self-leveling underlayments, patch and
repair mortars, as well as water proof membranes (sealant slurries).
13.4
Markets and Application Areas of Redispersible Powders
To meet today’s technical requirements, almost all dry mix mortars require polymer
modification. Many cementitious mortars contain cellulose ethers as an additive to
improve water retention and workability. However, after setting and drying they will
adhere poorly or not at all to most of the substrates used in modern construction
technology such as polystyrene panels, fiber panels, wood panels, closed and non-ab-
sorbent substrates or old tiles. In addition, cementitious mortars are very hard, brit-
tle and inflexible materials, whereas for many applications flexible and deformable
cementitious materials are essential. As a consequence for almost all applications in
modern construction, the modification of cementitious mortars with polymers is a
must. In dry mix mortars the mineral binder, cement, and the polymer binder, re-
dispersible powder, are ideal partners. The combination of both in a dry mix mortar
provides outstanding synergistic properties and characteristics, which cannot be

achieved by either of the binders alone.
13.4.1
Adhesives for Ceramic Tiles
Ceramic tiles as well as natural stone were previously installed exclusively by using
the thick bed mortar technique. Silica sand and cement were mixed together on the
job-site, in order to produce a simple cement mortar with a cement/sand ratio of ap-
proximately 1:4 to 1:5. In some countries only cement is still used in order to set
tiles. After having applied (“buttered”) the mortar at a thickness of 15 to 30 mm (0.6
to 1.2 inch) on the reverse side of the water-soaked or pre-wet tile, the tile is pressed
into the pre-wet surface. The tiles have to be tapped to ensure uniformity and flat-
ness of the tile surface, thus obtaining a final mortar bed of 10 to 25 mm (0.4 to 0.8
inch). This procedure causes not only compaction of the mortar, but leads in addi-
tion to the migration of the fine cement particles into the porous back side of the tiles
and the porous substrate as well. This process assures the mechanical fixing of the
tile in the mortar bed. This type of mortar has no slip resistance. Therefore tiling of
a vertical substrate has to be started at the bottom and distance splinters become
necessary. The described procedure shows very clearly that the thick bed method is a
very time, cost and material consuming process. More significantly, there are tech-
nical restrictions using this technique. One of the examples is that only small,
porous tiles can be applied over porous, solid and strong mineral surfaces. The ap-
plication of tiles over wood would be almost impossible, since a mortar without any
polymer modification would not only be not flexible enough to withstand the move-
ment of a wood substrate over an extended period of time, it would also have no suf-
ficient adhesion to the substrate. Consequently severe damage could occur and
therefore the thin bed mortar technique has replaced the thick bed mortar technique
in most industrial countries.
It started in the USA in the early 1950s by adding a polymeric binder in form of a
liquid latex dispersion to a job-site mixed mortar (see Chapter 8). Nowadays dry mix
mortars modified with redispersible powders dominate this market segment more
and more. After gauging the polymer modified dry mix mortar with water, it can be
applied with a notched trowel, producing a ribbed mortar bed of uniform thickness.
Due to the good water retention capacity of the thin bed mortar, neither the tiles nor
the substrate have to be pre-wet. The tiles are pressed into the thin layered mortar
with a slightly twisting movement of the tile. An anti-sag ceramic tile adhesive allows
installing tiles on vertical substrates without using distance splinters between the
tiles. The tile installer can also start from the top of the wall instead of the bottom.
The mortar bed, which fixes the tiles, has a thickness of approximately 2 to 4 mm (up
to 0.25 inch). Since this method clearly uses less material, it is more cost effective,
can be used more universally; its execution is clearly simpler, faster and safer. The
clear advantages of dry mix mortars modified with redispersible powders, which ap-
ply also for tile grouts, are:
– good workability, fast and easy to use, creamy consistency,

– good water retention, which results in a long open time and good adjustability
even at high temperatures, and
– substantial anti-sag properties, if required.
As far as the formulations for ceramic tile adhesives go there is a high variety of
mortars offered in the market place in order to meet all the specific requirements. A
major difference, for example, between Europe and the United States is the usage of
wood as a substrate in the USA. Differences in the formulation are also determined
by requirements of specifications or application circumstances like interior or exteri-
or, wall tile or floor tile, vitrified tile or more porous tile, fast setting or regular
setting, flexible or even highly flexible. The availability of certain raw materials i.e.
silica sand determines very often how a formulation will perform.
The two most important specifications worldwide are the European Norms “EN”
and the American Standards ANSI 118.1-1999. The biggest difference between the
two standards is the principal test setup. The European Standards require mostly
tensile bond adhesion testing where else the American Standard uses shear bond
testing. The other difference is clearly the storage conditions for the specimen before
testing. A listing of both standards is shown in Tab. 13-2.
Tab. 13-2 EN and ANSI standards for CTAs.
European standards
EN 12004 Definitions and specifications
EN 1308 Anti-sag
EN 1347 Wetting capability (coverage)
EN 1346 Open time
EN 1348 Tensile adhesion testing, including heat and freeze-thaw storage
EN 1324 Shear-strength for mastics
EN 12002 Deformability of cementitious CTA
US standards
ANSI A 118.4 Specifications for Latex Portland cement mortar
ANSI A 118.11 Specifications for EGP (exterior glue plywood) Latex–Portland cement mortar
Cement-based standard tile adhesives can be classified in very simple (low quality)
tile adhesives, which do not contain any polymeric binder. They do not meet Euro-
pean or American Standards. Such tile adhesives, providing a pure mechanical fixa-
tion can only be used for fixing small, very porous tiles. The substrate is supposed to
be dimensionally stable, sound and solid as well as not showing any shrinkage or
movement. If exposed to higher temperature or frost, there is a higher risk of failure.
Non-modified mortars show for the most part no long-term performance.
Simple tile adhesives have already a polymer modification of 1 to 1.5 % of a redis-
persible powder (calculated on total formulation). Such tile adhesives meet some
parts of the mentioned national standards, but usually fulfill not all requirements.
Only the usage of tiles with a medium porosity and small size could result in accept-
able results with these types of adhesives.
Standard ceramic tile adhesives of good quality need approximately 1.5 to 3 % of

redispersible powder on total dry mix. They meet the new European Norm for tile ad-
hesives (mostly only C1 level) and pass also the ANSI specification 118.4 and 118.11.
Larger formatted tiles can be applied with these materials over porous or less porous,
dimensionally stable substrates. They are suitable for interior as well as exterior ap-
plication. For standard applications these modified mortars provide higher quality
security and a certain long-term stability, very much depending on the factors like
climate conditions, weight traffic etc.
Finally flexible (5 to 8 % of redispersible powder) and very flexible ceramic tile
mortars with a polymer modification beyond 8 % up to even 25 %, guarantee the best
performance over all, very good adhesion on all types of substrates with all types and
sizes of tiles. These adhesives are used more universally and offer a much greater ap-
plication variety, safety, as well as long-term durability and reliability. Nowadays
these mortars are more and more used to fix the very popular highly vitrified tiles
(water absorption <0.1 %) and natural stone tiles (like marble) in any format. The
substrate can be non-porous and inorganic as well as wood. Even if the substrate still
shows to a certain degree of shrinkage or expansion, including other types of move-
ments or vibrations, these quality adhesives could be used to set tiles in a safe and
durable way. Typical application examples for flexible ceramic tile mortars are:
– floor heat system within the substrate,
– to heat exposed surfaces, like i.e. tiles on a porch exposed to sunlight,
– tiles over tiles,
– over gypsum boards,
– over backer boards,
– over wood,
– on water proof membranes,
– on thermal and sound insulation panels, and
– on light-weight concrete blocks.
Tests conducted by international research and test institutes have proved that it is
of high importance that cementitious adhesives provide a sufficient deformability
and a certain degree of plasticity [1–4]. Only in that way, long-term durability and
functionality can be guaranteed. Adhesive mortars have to be able to absorb stresses
that occur between two materials as tiles and substrate in order to prevent damages.
Typical damages are cracking or even delaminating of the tiles. Irreversible differen-
tial movement, such as shrinkage causes always stress between tile and substrate
(fresh concrete is always likely to shrink). Reversible movements of the substrate like
vibrations and thermal movements due to heat or cold are also sources of stress be-
tween substrate, adhesive and tile. The different modulus of elasticity of tiles and
substrate is also enhancing the stress within a ceramic tile mortar (Fig. 13-4).
European Norm EN 1348 addresses this issue in a heat test as well as in a freeze/
thaw test. Shear stress between substrate and tile normally concentrates in the pe-
ripheral zones of a tile. That means, the bigger the tile the higher the flexibility of the
adhesive has to be in order to avoid cracking or delaminating of the tile. The flexibil-
ity (deformation capability) of a ceramic tile adhesive depends on the polymer/ce-
ment ratio. It is one of the two most important ratios to be determined in a ceramic
tiles tiles
deformable
adhesive mortar
substrate substrate
eg. concrete eg. concrete
initial initial
dimension dimension
shrinkage of substrate expansion of tiles

eg. shrinkage of concrete eg. thermal expansion
tiles tiles
rigid, non-deformable
adhesive mortar
substratre substrate
eg. concrete eg. concrete
initial initial
dimension dimension
Fig. 13-4 The stress between substrate and tile.
tile mortar (the other one is the water/cement ratio). The German test DIN 18156/3,
as well as EN 12002, measures the flexibility of ceramic tile adhesives. As a result of
these tests it can clearly be shown, that the higher the polymer/cement ratio the
higher the flexibility of a mortar system (Fig. 13-5).
Fig. 13-5 The flexibility of ceramic tile adhesives.
It is very important to mention that the deformation capability of a given cementi-

tious system also depends to a large extent on the degree of hydration of the cement.
Consequently, the flexibility of different adhesives can only be compared at identical
degrees of hydration of the cement. Unfortunately this is very often not considered
within the storage conditions of different standards, that deal with the testing of flex-
ibility (Fig. 13-6).
16.0
14.0
12.0
Flexion/deformation [mm]
10.0
8.0
6.0
4.0
2.0
0.0
50% Portland Cement 40% Portland Cement 35% Portland Cement 30% Portland Cement
Traverse deformation test according to EN 12002 - 5% polymer modification at
different cement levels
standard conditions water storage (full hydration) 7d sc/ 14d in water/ 21d sc
Fig. 13-6 EN 12002 results on flexibility.
The relative humidity of approximately 95 % at the beginning is not kept constant

during storage and is not sufficient for a full hydration of the cement. Over the time
cementitious adhesives will reach their full hydration thus resulting in sometimes
very low flexibility of the mortar. For example, the use of additives and/or polymers
with a strong retardation effect on the cement will cause an incomplete hydration of
the cement and will lead temporarily to a higher polymer-to-cement ratio. The flexi-
bility measured at this point will not reflect the real flexibility of the system after full
hydration of the cement phase. After complete hydration of the cement, “soft” poly-
mers (lower glass transition temperature, Tg) will perform at an appropriate dosage
level better compared to polymers with a higher Tg, especially if used and tested at
lower temperatures (Fig. 13-7). (The glass transition temperature describes the flexi-
bility of a polymer. The “rule of thumb” is the lower the Tg the higher the flexibility.
Tg is determined from the ratio of different monomers and their individual Tg in a
polymer, by use of the Fox equation [5]).
The adhesion of tiles to the substrate is certainly as important for a ceramic tile ad-
hesive as the flexibility. The European Norm uses a “pull off test” to determine the
adhesion, where as the US standard ANSI 118.1 – 1999 prefers the shear bond test.
A simple ceramic tile mortar with no polymer modification will fail in the adhesion
test especially after heat aging or over wood (ANSI 118.11 – 1999). The same mortar
modified with only 2 % of redispersible powder will pass both tests. With the pull-off
Fig. 13-7 Flexibility at lower temperatures.
test, it can be demonstrated that a ceramic tile adhesive without polymer or with a
low polymer level will only be able to pass, if wall tiles (very porous, high absorptive
tiles) are used. In addition, it can be demonstrated that only a sufficient amount of
redispersible powder provides a significant adhesion on critical substrates like PVC,
wood or tiles (Fig. 13-8).
A sufficient high polymer modification of the ceramic tile adhesive is necessary es-
pecially when non-porous, highly vitrified tiles (low to no water absorption) are used.
In this case, there will be no mechanical anchoring like described earlier for porous
tiles. The redispersible powder (chemical bonding), in this case, only provides the ad-
hesion. This is, besides the outlined reasons for sufficient flexibility, another impor-
tant factor for a higher polymer modification.
A ceramic tile adhesive that performs very well over almost all substrates, with all
types of tiles (size, water absorption) should contain at least 6 % of redispersible
powder and the cement content should be limited to 30 to 35 %. An adhesive formu-
lation that considers these two important components at the right amount is very
likely to pass all international standards. However, in an adhesive formulation has
more to be considered than only the polymer and cement level.
Fig. 13-8 Adhesion of ceramic tile adhesives to different substrates.
13.4.2
Tile Grouts
Tile grouts, which are used to fill the joints in between the tiles, are very similar to ce-
ramic tile adhesives in their formulations. They are expected to be water repellent
(hydrophobic), to have good adhesion to the substrate and the edges of the tile, suffi-
cient hardness, a low tendency for staining, cohesion strength, abrasion resistance
and flexibility. In the USA the field of tile grouts is much more diversified than, for
example, in Germany, because US manufacturers offer a much greater variety of col-
ors. Therefore, color consistency is of high importance as well. Redispersible pow-
ders with a hydrophobic effect are normally used to achieve all requirements of a tile
grout. They reduce the risk of efflorescence as well as staining of the grout. The stan-
dards in the US and Europe are summarized in Tab. 13-3.
The fields of ceramic tile mortars and tile grouts are certainly the most developed
for redispersible powders in cementitious applications. The use of redispersible
powder improves adhesion bond strength to all types of substrates, the deformabili-
ty (flexibility), the cohesive and flexural strength, the open time the wetting capabili-
ty as well as the workability within dry mix mortars.
Tab. 13-3 EN and ANSI standards for tile grouts.
European standards*
EN 12808-1 Determination of chemical resistance
EN 12808-2 Determination of abrasion resistance
EN 12808-3 Determination of flexural and compressive strength
EN 12808-4 Determination of shrinkage
EN 12808-5 Determination of water absorption
EN 12002 Determination of deformability
US standards
ANSI A 118.6 Specification for standard cement grouts for tile installation
ANSI A 118.7 Specifications for polymer modified cement grouts for tile installation
* There is also a draft of “Tile grout mortars for tiles, definitions and requirements”
13.4.3
Exterior Insulation and Finish Systems and Top Coats
With the beginning of the 1970s exterior insulation and finish systems (E.I.F.S) were
used in Germany. (E.I.F.S. is predominantly used in North America. The abbrevia-
tion used in Europe is ETICS – exterior thermal insulation compounds.) The first oil
crisis in Germany 1973 together with financial support of the government for home-
owners had helped tremendously to promote the system. Some of the advantages of
E.I.F.S. are saving energy, healthier climate condition inside the house, less dam-
ages of facades and possible savings at the over all building costs. Between 1973 and
1993 approximately 300 million square meters of E.I.F.S. were applied on facades in
Germany. As a consequence more than 18 billion liters of oil were saved (approxi-
mately 113 million barrels). This also means considerably less CO2 was released into
the atmosphere, that also emphasizing a positive environmental aspect of E.I.F.S.
After Germany, the country with the most usage of E.I.F.S. is the United States.
However, the use of E.I.F.S. in the past within the United States has been more for
optical reason. Recently more and more the energy saving aspect of the system has
become a more considered aspect for homeowners. In both countries, organizations
exist representing the E.I.F.S. industry and its interest: representative of Germany is
the “Fachverband Waermedaemm-Verbundsysteme” and of the USA the “Exterior
Insulation Manufacturer Association, EIMA”.
The technology used in both countries is predominantly based on the usage of
polystyrene as an insulating material. In the early 1970s, the materials for E.I.F.S. of-
fered in Germany were shipped to a construction site as ready to use systems (pasty
consistency). They had to be mixed with cement before usage. Mistakes occurred by
not meeting the polymer cement ratio according to the manufacturers’ requirement,
resulting in damages and complaints. The industry shifted almost completely to dry
mix systems in order to avoid the mentioned problems. The use of machines also
promoted dry mix mortars modified with redispersible powders. The time and cost
savings remain tremendous. In the US, reliability and control over the formulation
out of production as well as time and cost savings of machine applicable systems,
has clearly set the trend over the last 5–10 years towards more and more usage of the
dry mortar technology and, therefore, towards redispersible powders/polymers.
Because of the use of redispersible powders, the application of E.I.F.S. has reached
such a high level of reliability and quality consistency that manufacturers in Ger-
many normally allow a 30-year warranty for their systems. So far this level of war-
ranty is not yet achieved in the US.
In Europe, as well as in the US several technical tests are conducted in order to
prove the performance of E.I.F.S. under different test conditions. The testing of such
systems is very severe. Some of the most important types of tests conducted on an
E.I.F. system are:
– stability and flammability,
– insulation properties,
– adhesion of cementitious materials on polystyrene,
– water absorption,
– impact resistance, and
– flexural and compressive strength.
Most of the tests are still very much depending on the country (Europe). In the US
there are different authorities (regional and city codes) like the “American Society for
Testing and Materials – ASTM”, the “Building Officials and Code Administrators –
BOCA”, the “International Conference of Building Officials – ICBO” and the “South-
ern Building Code Congress – SBCC”. Information on test procedures is also avail-
able through EIMA. More specific information can be gathered through the different
organizations. In Europe the entire E.I.F. system needs even a technical approval
granted by testing institutes according to the “European Organization for Technical
Approval, EOTA”. The principle layers of an E.I.F. system are shown in Fig. 13-9.
1. Substrate
2. EPS-Adhesive
3. EPS-Board
4. Base Coat
5. Top Coat/Finish
Fig. 13-9 The principle structure

of an E.I.F. system.
Substrates might vary. In the US it is normally plywood. Normally one will find
concrete/brick as a substrate. Right on top of the substrate the insulation board is
glued with an adhesive. In addition sometimes mechanical fasteners are use as well.
85 % of the insulation material used in Germany is Extruded Polystyrene “EPS”. The

EPS adhesive is normally the same material as the base coat. The functionality of the
base coat is protection and reinforcement of the EPS panel. Without polymer modi-
fication there would be no adhesion of the EPS to the substrate and no adhesion of
the base coat to the EPS panel. Besides adhesion, the right polymer modification be-
comes also very important when impact resistance, water absorption or deformation
capability (flexibility) is tested. The base coat has an important functionality within
the entire system. The right modification of the base coat with at least 3 to 6 % redis-
persible powder will finally guarantee good performance values and as a conse-
quence contribute to an excellent weather stability of the entire system. The integrity
of the base coat, meaning a crack free base coat, is a precondition for good technical
performance. For that purpose the polymer-to-cement ratio should be as high as
possible. This is one of the main differences between Europe and US . Normally the
cement content in US systems is higher than in Europe. Assuming the polymer
content is very similar, this results in a higher polymer-to-cement ratio in European
systems compared to US systems. This has to do with the fact that the preference in
Europe is towards more flexible system where else in the US a hard surface appear-
ance of the base coat is preferred by contractors.
Certainly as important as the base coat is the topcoat for the entire system. Here
we find probably the biggest difference between, for example, Germany and the
United States. In the US cementitious topcoats are almost not used at all. They are
synthetic, cement free systems that are very often ready to use and based on emul-
sion technology. In Europe, as with Germany, topcoats are cement based as well.
Top/finish coats must meet certain critical physical and technical requirements.
These include:
– good adhesion to the substrate (tensile adhesion strength),
– low water absorption or water repellency (hydrophobicity),
– good drying characteristic (high water vapor permeability),
– low susceptibility to cracking (good relaxation properties, flexibility),
– the modulus of elasticity of the top coat should be lower than the modulus of elas-
ticity of the substrate (layer below),
– resistance to weathering,
– mechanical stability (high impact resistance),
– low dirt pick up,
– very low flammability.
(Finish or topcoats can also be named render, plaster or stucco. Normally slight
differences apply, for example in thickness of the coating depending on the technol-
ogy used. As far as the use of redispersible powder is concerned, they can be consid-
ered equivalent.)
The addition of organic polymeric binders in form of redispersible powders to
mineral plasters and stuccos can significantly enhance certain properties, such as
adhesion to the substrate, mechanical resistance, low water absorption (hydrophobic
effect by using special redispersible powders) and long-term durability. In order to
meet these requirements the preferred redispersible powders used in topcoats are
vinyl acetate/ethylene copolymers. Especially when it comes to flammability vinyl
chloride containing systems perform the best closely followed by vinyl acetate ethyl-
ene containing polymers. Topcoats/E.I.F.S based on acrylics and acrylates, like
styrene acrylics, perform the worst in this respect.
The addition of approximately 0.5 to 2 % special hydrophobic redispersible pow-
ders to dry mortars additionally imparts uniform water repellency throughout with-
out effecting the water vapor permeability.
Mineral topcoats are composed of lime and cement as mineral binders, aggregates
(fillers like silica sand), pigments and additives, such as cellulose ethers, starch
ethers, lightweight fillers, fibers, thickener, hydrophobic agents, wetting agents and
sometimes even surfactants. With the exception of any mineral binder this list
applies also to synthetic topcoat which are almost exclusively used in the US. Table
13-4 shows some of the specifications for topcoats in Europe (Germany) and the US.
Tab. 13-4 Specifications for topcoats.
German-US standards
DIN 18555/ASTM C 109 Compressive strength
DIN 18555-6/* Tensile bond adhesion
DIN 52617/ASTM C 413 Water absorption
DIN 52615/ASTM E 96 Water-vapor permeability
DIN 18555/ASTM C 231 Air content
DIN/EN 196/ASTM C 580 Flexural strength
* ASTM E 2134-01 for E.I.F.S.
One aspect that is very important to the E.I.F.S. industry as well as to topcoat man-
ufacturers is certainly the hydrophobicity of their base coats and/or topcoats.
What is the mechanism behind a hydrophobic effect achieved by using a hy-
drophobic redispersible powder?
When water is added to the dry mix topcoat, the polymeric binder in the form of a
redispersible powder is very quickly redispersed. Then the polymer particles accu-
mulate mainly in the pores, forming a film that coats the pores without actually
blocking them [6–8]. Because the pores (capillaries) are coated with a water repellent
polymer film with good adhesion to the cement, the capillary water absorption is re-
duced. Thus a permanent effect is achieved throughout the mortar. If the amount of
redispersible powder stays within 3 to 6 % there is no loss of water vapor permeabil-
ity. This, of course, depends also very much on the hydrophobicity of the used redis-
persible powder. Because of the mentioned adhesion of the polymer to the cement
pores the adhesion as well as the flexural strength and toughness of the material is
improved also. Scanning electron micrographs are shown in Fig. 13-10 and demon-
strate the formation of the polymer film within the cement matrix.
The SEM technology was also used to demonstrate that the redispersible powders
continue to fulfil their functionality over an extended period of time. This is also
shown by experiments to determine physical factors such as water absorption and
water vapor permeability on defined test specimen after long-term exposure to out-
door weathering conditions. Figure 13-11 shows the capillary water absorption of test
specimen after up to 6 years outdoor exposure at different polymer levels.
Fig. 13-10 SEM of polymer

film in cement matrix.
Capillary water absorption of mineral topcoat - long term exposure

4
3.5
3
water absorption coefficient
according to DIN 52617
2.5
1.5
0.5
0
0.5% 1.0% 2.0% 3.0% 3.5%
percentage redispersible powder on total formulation
21 days standard conditions 1 year outdoor exposure 6 years outdoor exposure
Fig. 13-11 Long-term performance of cementitious topcoats.
13.4.4
Self-leveling Underlayments
The area of self-leveling underlayments (SLU) is out of a technical perspective prob-

ably the most complex one if it comes to applications of redispersible powders. On a
given uneven substrate (i.e. screed or surface to be refurbished), self-leveling mor-
tars have to provide a suitable, smooth and solid substrate in order to apply all kind
of flooring materials like carpets, wood parquet, PVC, tiles etc. Self-leveling under-
layments should be applicable in an easy and efficient manner, even for large areas.
Therefore, the SLU material has to have very good flow characteristics, self-leveling
and self-smoothing properties. In addition, it should perform fast setting/drying,
saving time and thus the floor surface can be applied after only a few hours. The SLU
material should adhere to all kind of substrates, provide low shrinkage, high com-
pressive strength and abrasion resistance.
The technical requirement of a SLU reaches from very simple to highly sophisti-
cated products. They vary in thickness from a very thin layer of 1–10 mm (1/25–2/5
inch) (feather finish, self-leveling/troweling mortars and underlayments), up to 60
mm (approx. 2.5 inch) for self-leveling screeds, which are always applied by ma-
chines (mixing and pumping in one set up). The set time (“walk over time”) of these
materials changes from normal/regular setting to very fast setting products. Nor-
mally this is a question of the requirement of a specific job, allowing putting down
the floor above the SLU in a certain time frame. The shorter the setting/drying time,
the thicker the mortar is applied, the more complicated and expensive the formula-
tion becomes. Self-leveling compounds (underlayments and screeds) are based on
special hydraulic binders like Portland cement (OPC), high alumina cement (HAC)
and gypsum (anhydrite), in order to achieve fast curing and drying by avoiding ex-
cessive shrinkage or expansion.
So far there are no standards on self-leveling underlayments (SLU) in Europe or
the U.S. However, the techniques and the application is very well known for many
years. Polymer modification is absolutely necessary within this technology, since the
requirements are very sophisticated. According to their use and the specific require-
ments, SLUs are polymer modified by 1–10 % of redispersible powder calculated on
total formulation. Standard products are normally modified between 2 and 4 %,
highly modified mortars are mainly used for refurbishment of wooden floorings
with self-leveling compounds. The redispersible powder increases the adhesion to all
kind of substrates, decreases the internal stresses (reduced crack formation and high
abrasion resistance), improves the flexural strength, elasticity and the abrasion re-
sistance. Special powder grades will also support the self-leveling and self-flowing
characteristics of the mortar. Figure 13-12 shows the results of an abrasion test for a
self-leveling compound with and without modification with a redispersible powder.
Depending on the dosage of the redispersible powder, the abrasion resistance can be
reduced significantly. This becomes especially than very interesting, when the SLU
is also used as a wearing surface in an overlayment application.
13.4.5
Patch and Repair Mortars
Concrete is a very versatile, long-lasting and durable building and construction ma-
terial if it is applied according to the state of the art. In the past, and even today,
unfortunately, repeated disregard of the fundamental principles of concrete and
structural concrete application has lead, and, in many cases, still leads to severe and
serious damage in the building industry. The cost of the repair of concrete structures
has dramatically increased over the last 30 years in all industrial countries. In Ger-
Fig. 13-12 Abrasion resistance with and without redispersible powder.
many approximately 20 % of the cost of the volume of structural concrete work is at-
tributed to the repair and maintenance of existing buildings and structures.
The degradation of structural concrete is caused by corrosion of the steel rein-
forcement due to chemical processes, which often occur over a long period of time.
One of the main reasons is the carbonation of concrete. Acidic carbon dioxide (CO2)
from the atmosphere and other aggressive media (such as SO2, acid rain) neutralizes
the alkalinity of the concrete. Once the alkaline environment of the steel reinforcing
no longer exists, the steel starts to corrode and, due to its volume increase, causes
splitting of the concrete on top of the steel reinforcement. A secondary cause of cor-
rosion is the penetration of free chloride ions into the concrete, leading to chloride
ion attack on the steel.
In the construction industry concrete repair work can be classified in two types:
– concrete repair, which does not contain steel reinforcement and which does not
have load-bearing functions. The repair is normally done for aesthetic reasons
(cosmetic repair work) only, with namely patching mortars/compounds
– repair and reconstruction of damaged reinforced and load-bearing concrete struc-
tures, in order to maintain and reconstitute their structural stability. This is done
in stages with different kind of mortars, which are part of a “concrete rehabilita-
tion system” (typical applications: repair work and rehabilitation of bridges, park-
ing decks, tunnels, etc).
Patching mortars for re-profiling and cosmetic repair are mainly based on dry mix
mortars and are not part of an entire repair or rehabilitation system. Usually, ce-
ment-based mortars are used for indoor and outdoor applications, whereas gypsum-
based products are only used for some specific indoor applications (cosmetic repair).
Patching mortars are used to repair defective or damaged areas of mineral surfaces
without taking on a load bearing function, i.e. for filling small holes, voids, cracks
and cavities in order to restore the original dimension. Typical applications are
patching mortars for walls, ceilings, floors, steps of staircases, etc. These mortars
must have the following characteristics:
– good workability,
– easy to apply,
– good adhesion to all construction substrates,
– high durability and abrasion/wear resistance, if exposed to direct wear/load,
– sufficient flexibility to reduce the risk of crack formation,
– low shrinkage, and
– water repellence for outdoor applications.
To meet the required technical criteria, these patching mortars are applied as a
polymer modified pre-packed dry mix mortar. Polymer modification with redis-
persible powder will – depending on the dosage – improve the:
– workability of the mortar,
– wetting capability of the substrate,
– adhesion to all kind of substrates,
– flexural strength,
– abrasion resistance,
– flexibility (lower modulus of elasticity than substrate),
– durability, and
– water repellent effect by using special grades of hydrophobic redispersible pow-
ders.
To be able to guarantee the durable and reliable repair of structural concrete, three
main fundamental requirements of a concrete rehabilitation system must be ful-
filled simultaneously:
– restoration of the corrosion protection of the steel reinforcement (alkaline envi-
ronment),
– restoration and re-profiling of the concrete structure including its load-bearing
functions, and
– restoration of the durability of the whole construction (protection against weather-

ing and environmental damage caused by CO2, SO2, Cl2, salts, etc.).
Today, polymer modified cement concrete (PCC) mortars, which can be applied by
hand, in a wet or even a dry spraying process, are usually used for the rehabilitation
of concrete structures. Different kind of mortars with different characteristics and
functions are used as the components for concrete rehabilitation systems:
– primer and adhesion promoter for the reinforced steel (polymer modified cemen-
titious slurry or epoxy based coating materials),
– adhesion promoter slurry (primer or key-coat) for the concrete to be repaired (poly-
mer modified cement based slurry),
– restoration and re-profiling mortar (polymer modified cement based mortar),
– fine stopper or smoothing mortar (polymer modified cement based mortar con-
taining fine aggregate), and
– protection and finish coat (dispersion paints, crack over bridging paints, cementi-
tious waterproofing sealing slurries, etc.).
The improvement of adhesion to concrete and steel, using a polymer modified re-
profiling mortar, with and without applying a cementitious primer, is demonstrated
in Fig. 13-13; Fig. 13-14 shows the improvement in flexural strength of a typical re-
profiling mortar applied by hand with and without different grades of redispersible
powder.
Tensile bond adhesion after 28 d standard conditions
polymer/cement ratio = 0.07
3
2.5
Tensile adhesion [N/mm2 ]
1.5
0.5
0
over concrete over steel
without primer with primer
Fig. 13-13 Adhesion to concrete and steel with and without primer.
The flexural strength of the mortar is already significantly improved by adding

only 2 % of redispersible powder without affecting the compressive strength too
much.
Flexural strength of repair systems modified with different

redispersible powders and applied by different techniques
14
12
Flexural Strength [N/mm2 ]
10
0
shotcrete spray applied hand applied
no polymer redispersible powder 1 redispersible powder 2 redispersible powder 3
Fig. 13-14 Flexural strength improvement by use of redispersible powders.
Almost the same improvements are obtained by applying the repair mortar
through a dry shotcrete process. Within this process the water is mixed with the dry
mortar only in the jet. After that the mixed mortar is immediately sprayed onto the
surface. Despite this extremely short mixing and almost no slake time, the redis-
persible powder redisperses quickly and completely enough in order to improve the
tensile adhesion strength and the flexural strength in almost the same magnitude
compared to a conventional application by hand.
13.4.6
Waterproof Membranes
Water in liquid or in vapor form is the most destructive weathering element for
building constructions, like concrete, masonry, and natural stone structures. Water-
proofing and damp-proofing techniques are used to preserve a structure’s integrity,
functionality and usage throughout its lifetime. For preventing all possible water in-
trusions, the exterior of a building has to be protected form top to bottom with wa-
terproofing materials. Exterior parts of a building could be classified in roof coating,
below-grade waterproofing materials, which are materials to prevent surface- and
ground water or water under hydrostatic pressure from entering into a structure.
Typically metal and plastic films, cementitious waterproofing sealing slurries and bi-
tuminous waterproofing systems are used for that type of application. Above-grade
waterproofing materials, which prevent water intrusion into exposed structure ele-
ments, could be categorized into:
– decorative and finishing barrier systems, i.e. all kinds of paints;

– mineral topcoats (renders, plasters);
– damp-proofing materials, which reduce or prevent water vapor transmission
through building materials and are not subjected to weathering or water pressure
(water vapor barrier foils); and
– flashings, materials or systems installed to direct water entering through the wall
cladding back to the exterior like metal foils in walls to prevent capillary water up-
take.
All waterproofing has to be part of a whole system and must interact integrally to
reach complete effectiveness and to prevent water infiltration. In case one of these
system parts fails or does not perform with all other protection systems, leakage will
occur. Adequately controlling groundwater, rainwater and surface water, as well as
the transport of humidity in the form of water vapor will avoid unnecessary repairs to
building’s exterior or its damage or even destruction (deterioration). Apart from pro-
tecting the exterior of building constructions, there is a multiplicity of waterproofing
materials for interior use. Some of the waterproofing materials are used to protect
against the detrimental action of aggressive substances like salts and acids transport-
ed by the water.
Traditional sealing and waterproofing systems, i.e. according to the German stan-
dard DIN 18195, include bituminous materials, plastic waterproofing foils and met-
al tapes for interior and exterior applications. Different types of materials can be
used in order to seal and protect the surface of buildings or its structural compo-
nents against the intrusion of dampness and water. Nowadays products for that pur-
pose are based on reactive resins like epoxy and/or polyurethane, dispersions
(paintable waterproofing membranes) and mineral binders like cement, which are
known as waterproofing membranes or sealant slurries.
Cementitious waterproofing membranes have been successfully used for more
than 40 years in Europe for protection of a wide range of building structures and
structural components. The structures were either exposed to periodically or long-
term wettings (surface water, seepage water), low hydrostatic pressure (soil damp-
ness) or in combination with appropriate engineering even high hydrostatic pres-
sure. Cementitious membranes (slurries) are used to waterproof wet rooms and
water tanks, and due to their excellent weathering resistance they are also used for
exterior surface protection. Further typical applications are the sealing and water-
proofing of basement walls, swimming pools, walls and floors, in bathrooms, on bal-
conies and porches (as a waterproofing layer to be tiled over). Especially in the case of
a tile application these slurries can also act as crack isolation membranes. In addi-
tion, flexible, cementitious waterproofing membranes are often used as a protective
surface-coating system for structural concrete (i.e. protection of reinforced structural
concrete within new structures as well as for concrete structures after restoration). It
is applied for the protection against penetration of water, chlorides and free carbon
dioxide in order to avoid corrosion of the reinforcing metal and can provide a protec-
tive layer to a building against aggressive chemicals (sulfates, acids, i.e. in waste-wa-
ter drains). Some of the advantages of cement-based waterproofing membranes are:
– excellent resistance against water, even if exposed permanently;

– excellent resistance against long term weathering;
– good scratch resistance;
– good load-carrying capacity; and
– much higher water vapor permeability compared to most of the other systems.
Consequently there are no problems with blistering since water vapor passes
through the membrane.
Cement-based waterproofing slurries are easy to use, non toxic, provide a fully
bound and monolithic surface without joints and can be easily applied on substrates
with complex surface shapes. In contrast to other systems, cementitious waterproof-
ing slurries can even be used on damp and wet mineral surfaces. Their physical
properties are also less temperature dependent compared to bitumen based materi-
als.
Simple, non-polymer modified cement based slurries are still used for the protec-
tion against surface water, but they are not suitable to seal against water under hy-
drostatic pressure. In order to improve the poor adhesion, the poor water tightness,
and the extremely low deformability or flexibility of these non modified systems,
polymers are added in form of liquid dispersions on the job-site or in form of a re-
dispersible powder already mixed in the dry mix mortar. The use of special additives
in the dry mix mortars like water retention agents, thickening agents and rheological
additives in combination with the polymeric binder, the redispersible powder, pro-
vide an excellent workability and make sure that there is no need for a post water-
treatment of the applied slurry.
Today, in principle, two different systems of cementitious waterproofing mem-
branes or slurries are available:
1. Standard or rigid mineral waterproofing slurries, which are polymer-modified,
pre-packed dry mix mortars containing approx. 3 to 6 % of redispersible powder.
They are used for mineral substrates, which are stable, sound and solid. There
should be no risk for crack formation, movements or dimensional changes like
shrinkage.
2. Flexible and highly flexible cementitious waterproofing slurries (as two-compo-
nent or one-component systems).
In addition to the traditional, rigid waterproof membranes, developments in the
late 1970s led in Europe to flexible waterproofing slurries, which are to a certain ex-
tend capable to over-bridge small cracks (up to approx. 1 mm) in the substrate. The
flexibility of such products strongly depends on the polymer/cement ratio and cer-
tainly also on the flexibility of the polymer itself. Flexible and highly flexible water-
proofing cementitious slurries are used on substrates still undergoing shrinkage, vi-
brations, movements, stresses, crack formation and on substrates difficult to be coat-
ed like wood, steel, aerated light weight blocks and gypsum. Due to their high poly-
mer content (up to 25–40 % on total formulation), they are diffusion and chemically
resistant against chloride, sulfate ions and carbon dioxide or other aggressive mate-
rials.
Thus far these flexible cement based waterproofing, sealing slurries have been
mainly used as two-component systems (liquid dispersion/emulsion added to the
13.5 Summary 353
pre-packed dry mix). But due to the many disadvantages of modifying mortars with
liquid dispersions on a job-site, in modern construction technique more and more
the one-component, flexible cementitious slurries, modified with high dosages of
special redispersible powders are used. These one-component, premixed polymer-
modified dry mix mortars are offering advantages as they were already discussed
within this chapter.
13.5
Summary
The need for new construction methods and building materials, that are safely, reli-
ably, efficiently and economically to apply, promotes modern technologies like the
“dry mix mortar technology”. Redispersible powders make the production of com-
plete pre-manufactured high quality mortars (“bagged mortars”) possible. As a con-
sequence, job-site mix technology and job-site modification of mortars with liquid
polymers is being replaced all over the world. Especially since product characteristics
can be specifically designed for modern construction requirements and climate con-
ditions by using dry mix mortars.
Dry mix mortars modified with redispersible powders provide a significantly im-
proved productivity on the construction site. They allow a high degree of rationaliza-
tion coupled with an easy, rapid, more efficient and safer handling and processing of
the product. This eliminates onsite mixing errors and ensures, consistently, excel-
lent results. The quality of the workmanship is consistent on a high level thus im-
proving the warranty status of a construction job dramatically.
Dry mix mortars, mainly based on cement but also on gypsum, that are modified
with redispersible powders have been successfully used for many decades all over
the world. The most typical applications are:
– ceramic tile adhesives,
– tile grout mortars,
– mortars for the thermal insulation systems,
– stuccos, skim-coats and finishing renders,
– patch and repair mortars,
– self-leveling under- and overlayments,
– waterproofing sealing slurries (membranes),
– joint compounds, and
– powder paints.
The modification of dry mix mortars with dry polymers in the form of redis-
persible powders also significantly improves the technical performance of the mor-
tars. The combination of the mineral binder with a polymeric binder in the form of
an redispersible powder in dry mix mortars guarantees outstanding synergistic prop-
erties and characteristics, which cannot be achieved by either of the binders alone.
The sufficient modification of mineral dry mix mortars by redispersible powders will
improve workability, adhesion to various substrates, flexibility and deformability of
the mortars, abrasion resistance, density (impermeability), flexural and cohesive

strength and the long-term durability.
Manufacturers, contractors, applicators and end-users (“Do it yourself” market) all
benefit significantly from dry mix mortars modified with redispersible powders.
That technology almost exclusively makes machine applications, which become
more and more popular with all kinds of construction materials, possible.
References
1 Research report No. 13 of “Vereinigung 4 Rapport “Lim for keramiske fliser;

von Systembouwers van de Werkgroep methode for proving av even tile
SA 5, Tegels, Het vermijden van Schade aoverfore relative bewegelser mellom
aan gelijmd Wandtegelwerk”; March underlag og fliser (flexksibilitet)” von
1975, Vereinigung von Systembouwers, BYGGFORSK, Norwegisches Baufor-
Gravenhage, Netherlands. schungsinstitut, Forskningsveien 3 b;
2 Publications of G. Wesseling (TNO Insti- Postboks 123 Blindern, 0314 Oslo 3,
tute, Netherlands); in Tonindustrie Projekte E 3593, Trondheim
Zeitung No. 8 1971, 95, 211. 04/08/1992.
3 Research report B II 5 – 800177-118; 5 Fox T.J.; Bull. Am. Phys. Soc. 1956, 1, 23.
“Ermittlung des Verformungsverhaltens 6 Schulze, J.; Tonindustrie-Zeitung 1985,
von Duennbettmoerteln bzw. Klebstof- 109, 698.
fen fuer keramische Fliesen”; August 7 Schulze, J.; Beton 1991, 5, 232.
1979 von Prof. Dr. Kirtschig; Technische 8 Adler, K.; Schweizer Baublatt 1988, 31,
Universitaet Hannover. 44.
14
Applications for Modification of Plastic Materials
Chuen-Shyong Chou and Jane E. Weier
14.1
Introduction
The global plastics industry is growing rapidly with an annual average rate of 4–6 %.
This is primarily due to the fact that plastics continue to replace traditional materials
such as metals, wood, and minerals. In a very dynamic market such as building and
construction, the compounded annual growth rate (CAGR) of plastics was about
7–8 % between 1992 and 1997. In the same period of time, PVC poly(vinyl chloride),
accounted for more than half of the plastics consumption in the segment, achieving
CAGR of 9 % [1]. The successful application of plastic materials has substantially en-
abled the incorporation of additives to the resins. Amongst the numerous additives
used, polymeric impact modifiers and process aids provide some of the most unique
and valued performance and processing enhancements [2, 3]. Toughening, rheology
control, aesthetics, processing, and economics are the major performance attributes.
These additives have been around for many years, and they have evolved over that
time into a broad array of product offerings. A key reason is the versatility of emul-
sion polymerization, which enables scientists to design proper polymer composi-
tion, polymer structure, polymer morphology, and polymer molecular weight/
molecular weight distribution. Emulsion polymerization is commercially attractive
because of the low manufacturing cost and ease of isolation for the resulting latex
products.
The first polymeric additives produced using emulsion polymerization technology
were core-shell impact modifiers made of methacrylate–butadiene–styrene (MBS),
which were introduced in 1956. These were followed by all-acrylic process aids and
acrylic impact modifiers [4, 5]. The additives were originally aimed at improvements
in PVC processing capability and toughness. Nevertheless, the application has been
extended to polyolefin and many engineering resins such as nylon, polycarbonate,
and polyesters. In addition to toughening of thermoplastic matrices, core-shell im-
pact modifiers were also applied to fracture toughening of thermoset resins such as
epoxy and unsaturated polyesters [6–11]. Processing aids are mainly applied to a PVC
compound for fusion promotion, melt strength, dispersion and surface quality. Ultra
356 14 Applications for Modification of Plastic Materials
high molecular weight processing aids are critical components in foamed PVC. With
the help of the processing aid, more uniform cell structures with less rupture and
lower foam density can be achieved. Lubricating type processing aids prevent the
melt plastic from sticking to metal surface, improve surface quality, and increase
productivity. In addition to PVC, polymeric processing aids are becoming popular in
other thermoplastics for certain limited applications.
In addition to impact modifiers and processing aids, a number of polymeric mod-
ifiers have been promoted for controlling gloss, improving heat distortion tempera-
ture (HDT), enhancing compatibility in polymer alloys, broadening the thermoform-
ing window, controlling light diffusion and optical properties, and improving the
plastic and cellulose composites processing. These polymeric modifiers offer some
unique properties and many of the developments are also tied closely to emulsion
polymerization technology.
14.2
Emulsion Polymerization and Isolation Technology
A comprehensive description of emulsion polymerization chemistry can be found

in books written by Gilbert [12] and Lovell and El-Aasser [13] and Blackley [14].
Although the process appears straightforward, the technology is extremely compli-
cated. Several possible polymerization loci can be present simultaneously including
the aqueous phase, micelles, monomer droplets, particle-water interface, and latex
particles. Emulsion polymerization techniques are in wide commercial use because
of their many advantages; however, the process is not without its drawbacks. The
major advantages include:
– The rate of polymerization is usually considerably greater than in a bulk process.
– An emulsion polymerization can easily achieve a relatively high conversion of
monomer to polymer; hence any problems with residual monomer are minimized
and monomer consumption is maximized.
– The polymer usually has a considerably higher average molecular weight than that
from a solution polymerization or bulk process, and has a different molecular
weight distribution. The polymer molecular weight can be controlled with appro-
priate initiator and reaction conditions.
– Because the molecular weight is very high in the absence of chain-transfer agents,
molecular weight is easily controlled by the addition of chain-transfer agents, and
allows for additional control of the properties.
– Various polymer morphologies with different molecular structures and molecular
weights can be achieved with a multiple-stage process. It is possible to control the
morphology of the system with layers, lobes or isolated domains of specific com-
position.
A core-shell impact modifier is probably the best model to illustrate the utility of
emulsion polymerization technology. The core polymer is based on a low glass tran-
sition temperature (Tg) rubber and is surrounded by a hard polymeric shell (high Tg
material). The core rubber is made in the first stage of the emulsion polymerization,
14.2 Emulsion Polymerization and Isolation Technology 357
and serves as the part of the modifier that promotes impact. It is typically made with
monomers such as butyl acrylate (BA) and/or butadiene (Bd). The monomers used,
the polymer molecular weight, and the internal structure of the rubber core affect the
impact performance. The shell of the particles, occasionally referred to as the outer
or hard stage, consists of a polymer that is chemically grafted onto the core. Typical
commercial examples of polymers used in the outer stage are poly(methyl methacry-
late), polystyrene, and styrene-acrylonitrile (SAN) copolymers. The shell polymer
provides ease of isolation and/or handling and facilitates dispersion and interaction
with the matrix.
Polymeric processing aids are generally high Tg copolymers and contain a large
fraction of methyl methacrylate (MMA) or styrene-acrylonitrile. Products with a
wide range of weight average molecular weights, from about 100 000 g mol–1 to over
6 000 000 g mol–1, are commercially available. Ultra high molecular weight polymers
can only be achieved by an emulsion polymerization process. The polymeric pro-
cessing aids can be grouped by their specific function and/or application. The refer-
ences shown in Tab. 14.1 provide additional details on the emulsion polymerization
process for specific type of polymeric modifiers.
14.2.1
Isolation Technology
Free-flow powders, granules or pellets are the common product forms used in the
plastic industry. Isolation of the emulsion is therefore an important part of commer-
cial processes. The product form can have a significant effect on its ease of handling,
compounding and incorporation into the matrix. It also affects the powder storage
stability such as compacting tendencies. The three most common approaches to iso-
lation are contrasted below:
Spray dryer Fluid-bed dryer Flash dryer
Feed Emulsion Wet cake Wet cake

Residence time in dryer 5–100 s 1–300 min 1–5s
Powder particle size (µm) 10–500 10–3000 10–300
Spray drying is an attractive approach as long as the polymer solids content is

high, thus requiring less water removal. Spray drying involves injecting the emul-
sion with hot air and forcing it rapidly through a rotating nozzle, to evaporate the wa-
ter quickly [74]. Although highly efficient, this method results in the retention of
non-volatile elements added during the polymerization, such as emulsifier and inor-
ganic salts, which might affect the resin. To this end, a full range of technology has
been developed around controlled coagulation of the emulsion, followed by filtration
of the aqueous phase and final drying of the resulting wet-cake. A much cleaner
product can be produced in this manner. Details of these methodologies have been
published extensively [75–78].
Tab. 14-1 Polymeric modifiers classified by function.
Type General Composition Function/Application Refs
General purpose MMA/BA, EA, BMA Promote PVC fusion, improve 15–53
PVC processing aids MMA/Sty, SAN, melt elasticity and strength,
SAN/MMA reduce melt fracture, and
improve surface quality
Lubricating BA/Sty/MMA, Promote PVC fusion, prevent 54–59
processing aids BA/MMA, EVA polymer melt from sticking to hot
surface, assist mold release,
improve surface quality and
throughput
Foamed PVC MMA/BMA, EA, BA Promote PVC fusion, reduce 51, 60–62,
processing aids SAN/MMA, SAN foam density, improve surface 157–183
quality, provide good cell
uniformity, increase process
flexibility
Melt rheology Methacrylate-based Lower melt viscosity in PVC and 63–70,
modifiers polymer ABS, improve melt strength 146
in polyolefin and engineering
resins, improve mixing and
homogeneity in ABS/SAN blend
PVOH processing MMA/NVP/ Enable melt processing, maintain 71–73
AIDS methacrylic acid rigidity and barrier properties
of the polymer
Acrylic impact BA//MMA, Toughen PVC, engineering resins, 115–118,
Modifiers 2-EHA/MMA epoxy and other thermoset resins., 122, 123
weatherable
MBS impact Bd//MMA/Sty, Toughen PVC, engineering resins, 130–134,
modifiers Bd/Sty//MMA/Sty epoxy and other thermoset resins, 141, 144
clear or opaque application
HDT modifiers α-Methylstyrene/ INCREASE service temperature, 147–153
AN, MMA improve melt strength and grain
retention
Flatting agent/ MMA, BA, Sty Reduce surface gloss, diffuse light 154–155
light diffuser in polycarbonate
14.3
Processing Aids
Many plastic materials have limited applications due to either undesirable physical
properties or poor processing capability. Processing aids were developed to enhance
melt processing, increase throughput, reduce downtime, and provide better product
quality [79]. The first commercial processing aid product was introduced by the
Rohm and Haas Company for processing rigid PVC in the 1950s [4]. This unique
technology was well acknowledged and led to the surge of the PVC industry. Similar
development efforts have been applied to other thermoplastic materials and polymer
blends since the 1980s. Although processing aids are generally added to PVC and
other thermoplastics in small quantity (0.5–5 %), they dramatically alter the process-
ing characteristics without a substantial effect on other application properties. Pro-
cessing aids can be classified by functions such as fusion promotion, melt rheology
modification, lubrication, and dispersion promotion. Each processing aid may
provide more than one function. The function and performance of a specific type of
processing aid is affected by the chemical composition, polymer architecture, poly-
mer molecular weight, and the matrix type.
14.3.1
Processing Aids for PVC
In a thermoplastic resin, to the mechanical properties of the final product are related
to the homogeneity of the polymer melt during the conversion process. Unlike the
majority of other thermoplastic resins, rigid PVC is not processable due to its inher-
ent particulate structure. It requires a long processing time at high temperatures
which leads to thermal degradation. The history and development of processing aids
for PVC, as well as the proposed mechanism are well documented [3, 5]. Processing
aids offer several benefits to a PVC formulation, mainly related to the fusion and
melt rheology during processing [3]. Processing aids help to increase cohesion and
homogeneity of the melt, melt strength, melt extensibility, and elasticity. The com-
position and the polymer structure of the processing aid affects the compatibility
with PVC and alters properties such as fusion promotion and lubrication. On the
other hand, the molecular weight and molecular weight distribution play the major
role in controlling the melt rheology. The most common processing aids are methyl
methacrylate based polymers. PMMA based polymers have a high glass transition
temperature (Tg) and are also extremely compatible with PVC [80, 81], which help to
create and transfer localized shear heat to melt the PVC during fusion process.
Improving melt rheology, increasing dispersibility, improving efficiency, and
enhancing the overall balance of properties, (especially melt strength versus viscosi-
ty) have been the major goals of new processing aid development [82]. This has led to
the ability to get equal performance from lower levels of process aid, and, in the case
of clear applications, materials that disperse more rapidly with greater clarity.
Fusion promotion and melt homogeneity

The most common approach to characterize the PVC fusion process employs the
Brabender® Plasticorder or Haake Rheometer, which consists of a mixing head with
two rolls. Figure 14-1 shows the PVC fusion process as reflected in the curve of
fusion torque vs. time. The melt temperature in each stage can also be recorded.
Point “A” is referred as the “compaction” peak and corresponds to compression and
densification of the powder. Point “B” refers to the beginning of melting, followed
by the appearance of the fusion peak. Point “C” occurs as PVC fuses into melt. The
difference in time between A and C is called “fusion time”. The torque observed at
point “C” is called the “fusion torque”. PVC is not completely melted at this stage
and the majority of melt is in the form of sub-microscopic particles. The fusion con-
tinues to occur as the torque drops down to an approximately constant value at point
“D”, which is referred as the equilibrium torque. The equilibrium torque can be in-
terpreted as a rough estimate of melt viscosity. As the heating and shearing contin-
ue, dehydrochlorination and cross-linking of PVC chains can occur, producing the
torque increase at point “E”. The difference in time between A and E is called the
“degradation time”. The fusion curve is strongly influenced by the formulation type,
processing temperature, shear rate, and loading level.
C
Torque
D E
Fig. 14-1 Torque

rheometry of
a PVC compound,
Time torque versus time.
Faster fusion time does not indicate complete breakdown of the PVC particulate
structure, and does not correlate well with good melt homogeneity. However, the
smoothness of rolling bank in the roll mill can provide a rough estimate. With only
2 % acrylic processing aid in a tin-stabilized PVC (K-value = 61) at 180 °C. 180 °C pro-
cessing temperature, the stock on the roll is clear, smooth, and homogeneous, and
the rolling bank is also smooth. In contrast, a non-homogeneous melt on the roll and
a badly fractured rolling bank can be observed when no processing aid is added. The
resulting sheets of both processes are shown in Fig. 14-2. With processing aid, the
sheet is strong, free of pinholes, and has no air streak and melt fracture. The
unmodified PVC film tears, crumbles, and loses its integrity. The PVC melt homo-
geneity can be examined under a transmission electron microscope. A Differential
Scanning Calorimetry (DSC) method can help to assess the degree of PVC fusion.
This technique provides the level of gelation and is related to the fusion of the PVC
specimen [83].
Fig. 14-2 A tin-stabilized PVC (K = 61)

formulation was processed at 180 °C for 4 min.
(A) Without the addition of processing aid,
(B) With 2 phr of Paraloid K-125. The sheet (A)
is hazy and has no film integrity. The sheet (B)
is clear, strong and has a smooth surface.
Melt strength, extensibility, and elasticity

Melt strength is a phenomenon reflecting both elasticity and elongational viscosity.
Extensibility describes the PVC melt’s ability to undergo large elongation or stretch-
ing deformation without rupture. Elasticity is related to the tendency to return to its
original state when stresses are removed. It is difficult to separate these rheological
properties. A combination of tensile strength, elongation, and elasticity defines the
“toughness” of a melt. Without polymeric processing aid, PVC would not withstand
high stress or extension. The acrylic copolymers that are typically used as processing
aids are generally compatible with PVC, and with their long chains, interact to pro-
duce a stiffer and more elastic melt. Increased rupture stress and extensibility helps
the PVC become far more resistant to rupture-induced defects.
Although the practical effects of melt strength are abundantly clear to the proces-
sor, measuring the melt strength quantitatively is usually difficult. The Gottfert
Rheotens is a device that uses a gear-like strain gauge – instrumental “puller” to
draw a fully fused melt from a right-angled (vertical drop) extruder. While the ex-
truder output rate is stabilized, the geared take-off accelerates until the melt (extru-
date) breaks. Therefore, the rheological properties of the PVC melt can be recorded
quantitatively. Die swell is another method for measuring melt elasticity. When a
polymer is deformed, it tends to return to its original form after external force is re-
moved. This behavior is commonly observed as the swelling of an extrudate as it ex-
its the die. The degree of swelling is related to the polymer recoverable strain or elas-
ticity and is normally expressed as swell ratio (extrudate diameter/die exit diameter)
or by the comparison of the weight of a fixed length of extrudate. As shown in
Fig. 14-3, the extrudate weight is dependent upon the concentration of processing
aid. As predicted, the die swell is related to the polymer molecular weight. Melt elas-
ticity is an important factor in establishing melt stability as the melt enters and pro-
50
Extrudate W eight (g)

A : Mw = 1.5 million
45 B : Mw = 2.5 million
C : Mw = 3.5 million
D : Mw = 6 million
40
35
30
25
0 1 2 3 4 5 6
Processing Aid Level (phr)
Fig. 14-3 Effect of Processing Aid Molecular Weight and Concentration

on Extrudate Weight. PVC formulation was based on 100 phr PVC (K = 57),
1.5 phr Advastab TM-181, 0.5 phr ALDO MS and 0.2 phr OP Wax.
ceeds through the die in extrusion. The higher die entry pressure observed when
processing aid is present is also a good indicator of higher melt elasticity [79].
One of the more recent advances in processing aids has been the development of
ultra high molecular weight materials specifically designed for use in PVC foam ap-
plications [84, 85]. With the help of a proper processing aid, the cell structure of an
extruded foam is more uniform with lower rupture tendencies [86, 87]. The PVC
melt can withstand great extension before it breaks [88]. Therefore, a low density
foam with fine cell structure and good surface quality can be achieved. As shown in
Fig. 14-4, an ultra high molecular weight processing aid with Mw = 8 × 106 is about
30 % more effective in terms of foam density, cell uniformity, and surface quality
compared with a similar processing aid with the Mw = 6 × 106. Without a proper pro-
cessing aid, the foam can have large cells, poor surface structure, and gas contain-
ment can be low (blow out). The effect of processing aid level on the surface quality
of a PVC foam rod is shown in Fig. 14-5.
Melt viscosity
Many thermoplastic resins have excellent physical properties and high service tem-
perature, which are often accompanied by high melt viscosity. High melt viscosity
makes processing more difficult and often decreases productivity as well as product
quality. Especially in injection molding, it is a major challenge for any material to fill
thin walls, long flow paths, and/or complex shapes. Most high molecular weight pro-
cessing aids increase the melt viscosity. However, it has been demonstrated that a
low level of standard acrylic processing aid does not have a noticeable effect on melt
viscosity [44, 89]. On the other hand, a combination of multi-function processing
aids can balance the melt rheology and melt homogeneity. Rigid PVC compounds
Processing Aid Level (phr) 6 4.5 4.5

Processing Aid Molecular Weight (x106) 6.5 6.5 8.0
Foam Density (g/cc) 0.38 0.5 0.37
Surface Quality Excellent Good Excellent
Fig. 14-4 Effect of processing aid molecular tin stabilizer (TM-950F), and azodicarbon-
weight on PVC foam extrusion, based on a amide as blowing agent.
free foam formulation with PVC (K = 62),
Fig. 14-5 Effect of

processing aid level on
the surface quality of
free foam rods. The
formulation is based
on PVC (K = 62), tin
stabilizer (TM-950F),
and azodicarbonamide
as blowing agent and
different level of
Paraloid K-400 as
processing aid.
(A) 2 phr, (B) 3 phr,
(C) 4 phr, (D) 5 phr,
(E) 6 phr. (A) (B) (C) (D) (E)
have successfully met the challenge. Many appliance parts, business equipment,
electronic enclosures are made from PVC compounds formulated with processing
aids and impact modifiers. As mentioned earlier, equilibrium torque as measured in
a Haake Rheometer can serve as a rough estimate of melt viscosity provided a prop-
er control is used. The melt viscosity can also be measured by many modern analyti-
cal rheometric instruments including capillary rheometers.
Effect of melt rheology on conversion process

The processing of polymeric materials such as plastics is characterized by a wide
variety of distinct methods or techniques. Each technique has a different set of melt
rheology requirements that are dictated by the processing mechanism and the equip-
ment design. A qualitative assessment of the effect of major melt rheology properties
on selected conversion processes is shown in Tab. 14-2.
Tab. 14-2 Qualitative assessment of major melt rheological properties versus selected conver-
sion processes.
Melt homo- Melt Melt Melt Melt

geneity strength extensibility elasticity viscosity
Calendaring Smooth Higher take- Higher take- Reduced melt Can generate
rolling bank off speeds off speeds fracture, but air bubbles
Uniform Better thermo- Bi-orientation can give flow if too high
thickness formability Deep draw lines
thermoforming
Blow- Uniform melt Reduced Uniform wall Reduced melt Can reduce
molding flow, enhanced parison sag thickness fracture at output if
physical Bi-orientation high output too high
properties rates
Extrusion Uniform melt Higher take- Higher take- Reduced melt
flow, enhanced off speeds off speeds fracture
physical Foam density Surface finish
properties Foam cell
structure
Injection Uniform melt Reduce gate Reduced Can reduce
molding flow, enhanced blush jetting flow lengths
physical if too high
properties
Lubrication
Lubricants are used to prevent plastic melt from sticking to metal surfaces during
processing. A number of disadvantages are associated with non-polymeric lubricants
including plate-out, clarity, migration, and delay fusion. Lubricating processing
aids [90, 91] were developed to help metal release, reduce plate-out, improve melt ho-
mogeneity, and minimize delays in fusion. Lubricating processing aids combine
both lubricants and processing aid functions. Compared with conventional process-
ing aids, this family of processing aids is less compatible with the matrix polymers.
Therefore, significant haze is developed due to the immiscibility with the resin.
However, the haze can be corrected with proper adjustment of refractive index [92].
The commercial lubricant processing aids for PVC, such as Paraloid K-175, help to
reduce melt fracture and shear stress and improve surface quality and do not affect
the clarity of the matrix polymer.
Processing aid type

Commercially available processing aids can be divided into four types – general pur-
pose, high efficient, high melt strength, and lubricating. The performance attributes
of different types of processing aids are shown in Tab. 14-3.
General purpose processing aids provide a balance of melt strength and melt vis-
cosity. They help to promote PVC fusion and have excellent dispersibility under low
shear conditions. An optimum balance of efficiency and clarity can be achieved us-
ing selected polymers such as Paraloid K-120ND and K-130D (Rohm and Haas),
Tab. 14-3 Processing aid type versus performance attributes.
Processing Aid Type General High High melt Lubricating

purpose efficiency strength
Molecular weight (Mw × 106) 1–3 3–5 6+ <1

Melt homogeneity ++++ ++++ ++++ ++
Melt strength (increase) ++ +++ ++++ +
Melt elasticity (increase) ++ +++ ++++ +
Melt extensibility ++ +++ ++ +
Melt viscosity (increase) + +++ +++ +
Fusion time + ++ +++ +
Dispersion (under low shear) ++++ ++ + ++++
Clarity in PVC +++ +++ ++ ++++
Stress whitening resist. ++++ ++++ NA ++++
Hot metal release/lub. + + + ++++
+ = least, ++++ = greatest
Kane Ace PA-20/30 (Kanegafuchi), Metablen P501(Atofina/Mitsubishi Rayon) and

Barorapid 3F(Barlocher). High efficiency processing aids produce even higher melt
strength than the general purpose type. This is attributed to their higher polymer
molecular weight. In addition to higher melt strength. This type of processing aid
improves melt homogeneity and processing rate, and provides better surface quality
dimensional control in the finished product, even in a highly filled system such as
pipe formulation. The most common high-efficient processing aids are Paraloid K-
125 (Rohm and Haas), Metablen P550/P551 (Atofina/Mitsubishi Rayon), Vestiform
R315 (Huls), and Vinuran 3833 (BASF). As mentioned in the previous section, melt
strength processing aids are mainly used in PVC foam applications, including pro-
file, foam core pile, and foam sheet. These processing aids provide low foam density,
high surface quality, and a consistent processing. The recommended processing aids
are Paraloid K-400/K415/K-435 (Rohm and Haas), Metablen P530 (Atofina/Mit-
subishi Rayon), Kane Ace PA-40 (Kanegafuchi), Baroropid 10F/20F/30F (Barlocher).
Polymeric lubricants that improve melt processing, hot metal release, melt fracture,
and process efficiency are defined as lubricating processing aids. The common lu-
bricating processing aids include Paraloid K-175 (Rohm and Haas), Kane Ace PA-
101 (Kanegafuchi), Metablen P710 (Atofina/Mitsubishi Rayon), Vestiform R450
(Huls), and Vinuran 3833 (BASF).
It is very common that a PVC compound is formulated with more than one type of
processing aid. Historically, the combination of different types of processing aids
could provide the converters with optimum processing. The combination of a lubri-
cating processing aid such as Paraloid K-175 with other types of processing aids,
such as Paraloid K-120ND, K-125, or K-130D, is commonly applied to applications
such as blow-molded containers, calendered or extruded sheet, siding, profile extru-
sion, high-flow injection-molded parts, pipe fittings, conduit, etc. The balance of
melt rheology, melt homogeneity, and hot metal release affects the aesthetics, as
well as the productivity. A proper level of each ingredient is critical and can affect
the product quality. As shown in Fig. 14-6, an optimal level of Paraloid K-130D with
K-175 helps to improve optical clarity as well as to eliminate flow-line and air marks
in a rigid clear PVC calendered sheet.
(A) (B) (C)
Fig. 14-6 Effect of processing aid on flow lines and air marks of calen-
dered sheet. Clear and rigid PVC formulation (A) 1.5 phr Paraloid K-130D
and 0.75 phr Paraloid K-175, (B) 1.5 phr Paraloid K-130D and 0.25 phr
Paraloid K-175, (C) 1.5 phr Paraloid K-125 and 0.25 phr Paraloid K-175.
The film thickness is approximately 0.5 mm.
14.3.2
Processing Aids for Other Resins
The use of processing aids to improve melt processing behaviors in resins other than
PVC has increased in the recent years. Some of the polymeric processing aids are
manufactured by emulsion polymerization but some of them are not. Acrylic pro-
cessing aids were found to improve melt strength and melt homogeneity in thermo-
plastics such as polyolefins, polyesters, polycarbonate, and ABS/SAN blends [63–70].
Methacrylate based polymers are reported to enhance the mill-processing of polyeth-
ylene. The higher alkyl methacrylates based processing aids improve the melt
strength of polypropylene and are useful in thermoforming operations to produce
containers and appliance housings. Lower molecular weight methacrylate based pro-
cessing aids were applied as rheology modifiers in ABS to lower melt viscosity and to
facilitate melt processing [93]. Addition of an extremely low level of fluorocarbon
processing aid reduces melt viscosity and eliminates melt fracture in a film extrusion
of linear low density polyethylene [94]. Poly(vinylidene chloride), also known as
PVDC, is used in packaging applications, especially multilayer film and sheet, due to
its high strength and barrier properties. However, PVDC is significantly less stable
than PVC and would normally degrade rapidly at the temperature required for pro-
cessing. Acrylic based additives reduce the thermal degradation and preserve the ma-
jority of important properties [95]. Poly(vinyl alcohol), PVOH, is another thermo-
plastic with excellent barrier properties but poor processability upon heat and shear
stress. The use of high molecular weight polymers as processing aids for PVOH en-
ables a smooth melt processing without compromising the rigidity and barrier prop-
erties [71–73]. The melt strength and melt viscosity of aromatic polyesters such as
poly(ethylene terephthalate), PET, can be increased substantially by the addition of a
low level of processing aid [69].
14.4
Impact Modifiers
Impact resistance, or toughness, refers to the ability of a material to withstand high

rates of applied loads, and thus high energy absorption, without undergoing cata-
strophic failure due to fracture. Many plastics suffer from inherent brittleness, and
even those commonly thought to have relatively high ductility, such as polycarbon-
ate, may become embrittled at very cold temperatures, by physical aging or through
high stresses or flaws introduced into the material.
The key to improving the impact resistance of a plastic is to enable the polymer to
absorb larger amounts of mechanical energy, while at the same time avoid plasticiz-
ing or softening the polymer, which can lead to large tradeoffs in other mechanical
properties, such as tensile or flexural modulus. The most common solution to this
dilemma is the introduction of a second, softer polymer phase into the plastic. In the
final processed material, this soft, rubbery phase ideally exists as discrete domains
dispersed within the plastic to enable the impact energy absorption, while the con-
tinuous glassy phase dominates the surface hardness and other mechanical proper-
ties.
In some cases, a blend containing the discrete rubber domains may be created
“in-reactor” through chemical process modifications during the manufacture of the
base polymer matrix material. Often it is difficult to properly control the desired
blend morphology, and the extra process steps introduce additional complexity and
cost into the process. Another limitation to the in-situ approach is that a typical man-
ufactured polymer resin may be used in a wide variety of downstream applications,
each with its own unique performance requirements, and therefore the desired ma-
terial modifications may also vary. Improved flexibility in formulating and process-
ing is provided by using an additive approach, in which the characteristics of the
final blend are produced by formulating and adding the desired type and amount of
modifying additives just prior to or during the final melt processing step. In the case
of impact modifiers, emulsion technology provides an ideal method for meeting the
requirements for such an additive system. Emulsion polymerization methods can
produce very high molecular weight, low Tg polymers having ideal elastomeric prop-
erties for impact modification. Particles of highly uniform particle size, in the range
of tens to hundreds of nanometers, may be synthesized. Through the use of standard
crosslinking techniques, particle size is permanently set so that the original emul-
sion particle is preserved during the plastic melt processing step. This ability to pro-
duce and control the optimal blend morphology and final domain size of the rubbery
phase is extremely important in achieving good impact resistance in the resulting
plastic material.
The development of multiple-stage, or “core-shell” emulsion graft copolymers was
an important milestone in impact modifier technology [96, 97]. Using core-shell
technology, the rubber core can be designed to optimize impact performance, while
a higher Tg outer stage eliminates the tackiness normally associated with rubbery
polymers and so allows for easier isolation, storage and handling. The outer stage, or
stages, can also be designed to enhance the processing and dispersion attributes of
the additive, most typically in the case where the shell polymer composition is cho-
sen based on its compatibility with the matrix polymer, which promotes improved
mixing to form the optimal dispersed-phase blend morphology.
In addition to composition, the particle size and distribution of the rubbery modi-
fier must be carefully controlled. It is well known that impact performance is highly
dependent on particle size [98]. Small particles are thought to be effective due to the
larger total number of particles distributed in the matrix, and the resulting shorter
interparticle distances [99–101]. The thin sections or ligaments of matrix between
the particles are more susceptible to induced shear deformation and drawing than a
thicker part or section. In some matrix systems, the energy absorption mechanism
may occur via multiple crazing or cracking, in which case large particles may be fa-
vored due to their ability to initiate and arrest the growth of these localized frac-
tures [102]. Recent work in understanding impact mechanisms has focused on the
possible role of cavitation, or voiding, within the rubber domains during the impact
event, which allows for stress release and increased deformation of the adjacent ma-
trix [103–105]. Larger particles are thought to be more conducive to this cavitation
mechanism. The optimal rubber domain particle size for impact resistance is there-
fore based on a balance of these competitive effects, and varies depending on the na-
ture of the matrix resin system being modified [106, 107].
Impact specifications and test methods vary according to application. Most com-
monly, testing is done using a notched Izod or Charpy pendulum impact test, for ex-
ample, as specified by ASTM D256 or ISO 179 protocols. Specimens are prepared by
cutting a small initial notch into a bar of the plastic material to be tested, and mount-
ed onto a pendulum-type impact tester. The pendulum hammer falls and strikes the
sample to initiate fracture at the notch. The total energy absorbed in the fracture is
measured from the loss in potential energy of the pendulum. Impact energy is nor-
malized and reported in units of energy per area or length of crack.
Another common impact test method involves the use of a dropped weight or dart
to impact a flat surface or sheet of processed plastic material. The dart may be in-
strumented, in which case the actual energy, load and elongation properties of the
material may be measured as the dart punctures the material. A more basic drop test
is the Gardner test, in which the drop height (and therefore potential energy) of the
weight is increased until material failure is observed [108].
14.4.1
Impact Modifiers for PVC
Poly(vinyl chloride) (PVC) is the largest and most important resin for the application
of emulsion-based impact modifiers. In 1999, over 25 million tons (50 billion lb) of
PVC were produced worldwide [109, 110]. Virtually all of the emulsion-made impact
modifiers for PVC applications are of the core-shell variety, with the largest com-
mercial producers being Rohm and Haas, AtoFina, Kaneka and Mitsubishi Rayon.
PVC is a unique polymer in that, while the neat resin is virtually useless, it can be
modified by various additives to provide a tremendous range of properties, ranging
from soft and flexible to rigid and tough. PVC is an inherently tough polymer, but is
characterized as notch sensitive [111]. Notch or crack sensitivity refers to the inabili-
ty of a material to resist fracture in the presence of a notch, crack, flaw or other site of
potential high stress concentration. This feature, along with the potential for embrit-
tlement at sub-ambient use temperatures, lead to most PVC applications requiring
some form impact modification. In a typical impact experiment, as shown in
Figs 14-7 and 14-8, the inclusion of a moderate amount of impact modifier produces
an almost tenfold increase in impact energy absorption vs. the neat resin, and large-
ly negates the negative effects of lower temperatures or sharper notches in the test
specimen.
1200
0.25 mm notch radius
1000
Notched Izod Impact Energy (J/m)
800
23 C.
20 C.
600
400
200
0
0 1 2 3 4 5 6 7
Impact Modifier Level in PVC (phr)
Fig. 14-7 Influence of temperature and core-shell modifier addition on the

impact performance of PVC.
Various mechanisms have been proposed to explain the effectiveness of rubber do-
mains in improving the toughness of plastic resins [106]. It is now generally accept-
ed that the primary source of energy dissipation occurs in the matrix resin itself,
rather than in the rubber domains [98–112]. The primary role of the rubbery
domains is to provide multiple sites of highly localized stress concentrations, which
tend to occur when a load is applied at the interface of materials having different
moduli [101]. In the case of PVC, which is intrinsically ductile, the localized stresses
can exceed the yield stress of the material, and plastic flow or deformation occurs in
preference to crack initiation and/or propagation [101, 113, 114]. In this way, large
amounts of energy are absorbed through an increase in elongation of the material at
moderate load levels (Fig. 14-9).
2500
20 C.
0.25 mm Notch Radius
0.50 mm Notch Radius

2000 1.30 mm Notch Radius
1500
1000
500
0
0 1 2 3 4 5 6 7
Impact Modifier Level (phr)
Fig. 14-8 Notch sensitivity of PVC. At smaller notch radii (sharper notch),
the PVC specimen is embrittled. Core-shell impact modifiers reduce the
notch sensitivity.
Unmodified
Impact
Modified
Yield point PVC Fig. 14-9 Effect of impact
Load modification on the macro-
scopic tensile properties of a
polymer such as PVC. The im-
pact modifier lowers the yield
stress of the polymer, allowing
the polymer to yield and under-
go extensive elongation. The
energy absorbed is calculated
from the area under the stress-
Elongation strain curve.
PVC building products

Rigid, unplasticized PVC is used extensively in the building and construction mar-
kets. Pipe, vinyl siding, and window profiles, all manufactured via profile or sheet ex-
trusion, represent the largest building product markets. Examples of some formula-
tions are shown in Tab. 14-4.
Building products often require a high degree of rigidity, heat distortion resist-
ance, and intrinsic toughness, attributes which are aided by the use of high molecu-
lar weight PVC resins, with K values typically greater than 65. These applications are
generally formulated to be opaque, and white or light pastel in color, so that for the
Tab. 14-4 Examples of PVC formulations for building products (parts per hundred resin).
Siding capstock Window profile Pipe
PVC, K-67 100.0 100.0 100.0

Tin stabilizer 1.2 1.2 0.4
Calcium stearate 1.2 1.5 0.8
Paraffin wax 165 °F 1.0 – 1.2
Polyethylene wax 0.1 – –
Bisamide wax – 1.7 –
Oxidized polyethylene wax – 0.1 0.15
Titanium dioxide 8.0 9.0 8.0
Calcium carbonate 5.0 3.0 5.0
Process aid (K-120 type) 1.0 1.0 0.5
Lubricating proc. aid 0.5 – –
Acrylic impact modifier 5.0 4.0 3.0
purpose of optical properties, additives can generally be designed without considera-

tion to refractive index and particle size.
The key distinguishing feature of impact modifiers used in building products is
weatherability, allowing the final modified PVC parts to retain color and mechanical
properties after extensive exposure to UV radiation. This requirement is well met
through the use of all-acrylic polymer compositions, which contain no residual un-
saturated sites susceptible to UV degradation [115, 116]. Acrylic impact modifiers
have a rubbery core based on low Tg acrylates with moderately long side chains.
Poly(butyl acrylate), with a Tg of approximately –45 °C, is most commonly used com-
mercially, providing good elastomeric properties at reasonable cost. The rubbery
core, which typically makes up 70 to 90 % of the total modifier, is crosslinked
through the addition of small amounts of multifunctional monomers during the free
radical acrylate polymerization, so that the resulting crosslinked core contains less
than 5 % extractable polymer. There are also examples of acrylic modifiers contain-
ing small amounts of non-weatherable, but very low Tg monomers, such as butadi-
ene, which may enhance the rubbery features of the core at the expense of small
tradeoffs in weatherability [117, 118]. Optimal impact performance for all-acrylic
modifiers in PVC building products is attained through the use of particles with di-
ameters in the 80–300 nm range.
A hard stage or shell is polymerized around the rubber core to allow for isolation of
the emulsions into non-compacting, free flowing powders, as well as to provide vari-
ous performance properties. The shell plays a critical role in impact modification by
enabling easier mixing and dispersion of the modifier into the polymer matrix. In
weatherable PVC applications, this is usually achieved through the use of a
poly(methyl methacrylate) based shell composition, which combines a suitably high
Tg with excellent miscibility in PVC [119–121]. The shell polymer, unlike the rubbery
core, is generally not highly crosslinked, so that the shell polymer chains are free to
mix and interact with the surrounding matrix on the molecular level. A modifier
with insufficient amounts of PVC-compatible materials in the shell will result in
poorer dispersion of the modifier (Fig. 14-10), leading to poorer impact (Fig. 14-11).
1.0 mm 1.0 µm
x 50.000 x 50, 000
Fig. 14-10 Modifier shell effects on dispersion shell with poor PVC miscibility, produces large
in PVC. The all-acrylic modifier particles are the agglomerates and there are significant areas of
small white particles in the micrographs, while unmodified matrix. Modifier B has a more mis-
the larger white and black particles are voids cible shell, resulting in more uniform disper-
and inorganic fillers. Modifier A, containing a sion in the PVC resin.
1200
10 % Modifier Modifier A (poor dispersion)
Modifier B (good dispersion)

960
720
480
240
0
14 16 18 20 22 24
Impact Test Temperature (C.)
Fig. 14-11 Impact performance of the two modifiers compared in

Fig. 14-10. Better compatibility and dispersion of the modifier in the PVC
results in superior impact efficiency.
The shell can further be designed around desired rheological and secondary prop-
erties. Shell molecular weight, degree of grafting, and composition can alter process-
ing and rheology properties such as viscosity, melt strength, die swell and PVC fu-
sion promotion [115, 122, 123]. Final performance properties such as surface gloss,
part shrinkage and thermal stability can also be controlled through the use of appro-
priate design of the outer shell. A well defined core-shell morphology, which can be
obtained through the use of many standard emulsion synthesis techniques, is also
key to achieving optimal performance of the impact modifier. Examples of current
commercially available modifiers are shown in Tab. 14-5.
Tab. 14-5 Commonly used commercial weatherable impact modifiers.
Manufacturer Trade name Product Description
Rohm and Haas Paraloid KM-334 General purpose all-acrylic

KM-355 High efficiency
KM-377 Impact and low gloss
KM-350 Low temperature PVC fusion
Atofina Durastrength D-200 Weatherable with Bd content
D-200L Impact and low gloss
D-300 High efficiency
Kaneka Kane Ace FM-10 General purpose all-acrylic
FM-20 High efficiency
FM-22 Highest efficiency
FM-25 Impact and rheology
Weatherable core-shell impact modifiers are highly efficient, requiring only 4–8
parts in most formulations, and are therefore the most commonly used impact mod-
ifiers for PVC building products. Alternatives to emulsion-based additives include
linear (non-graft) polymers such as ethylene vinyl acetate and chlorinated polyethyl-
ene. The latter polymer is a popular choice for low cost, lower performance applica-
tions, as in some types of PVC pipes. The disadvantage of these non-core shell addi-
tives is the absence of a well-defined, pre-set particle morphology. Optimal morphol-
ogy and impact performance must be achieved through very careful control of the
processing and formulation conditions [124–126].
In Europe, several manufacturers provide pre-toughened PVC resins or con-
centrates. These are an example of in-situ impact modification, where the rubber
polymer is introduced and grafted into the matrix during the PVC polymeriza-
tion [127–129]. These systems provide excellent impact properties without the need
for a separate hard shell or additive step. The corresponding disadvantage to the for-
mulator and processor is the lack of flexibility in adjusting the additive types, levels
and morphology.
PVC Durables and packaging

Core-shell impact modifiers are commonly used in PVC packaging applications,
such as films, sheets and clear bottles, as well as some PVC durable items, including
interior ducts and appliance housings. Unlike PVC building products, which are
commonly manufactured by extrusion, packaging and durable applications are often
made by calendering, injection molding and blow molding. Processing require-
ments, along with final property needs such as flexibility, dictate that somewhat low-
er molecular weight PVC resins are used, typically in the K-50 to K-65 range. Since
lower molecular weight resins have intrinsically lower toughness, it is often neces-
sary to add higher levels of impact modifier. Examples of some formulations are
shown in Tab. 14-6. Note that, in addition to the impact modifier, the combinations
of lubricants in these formulations differ from those associated with building prod-
ucts.
Tab. 14-6 Examples of non-weatherable PVC formulations (parts per hundred resin).
PVC electrical box Bottle Clear film
PVC, K-57-58 100.0 100.0 100.0

Tin stabilizer 2.0 1.5 1.2
Calcium stearate 1.0 – –
Paraffin wax 165 °F – – 0.6
Glycerol monostearate – 0.5 0.6
Montan ester wax – 0.2 0.2
Saturated ester wax – – 0.1
Titanium dioxide 1.5 – –
Calcium carbonate 5.0 – –
Process aid 0.4 1.0 1.0
Lubricating proc. aid 1.2 – 1.0
Bd-based impact modifier – – 20.0
MBS clear impact modifier – 12.0 10.0
Heat distortion additive 30.0 – –
Blue toner – – 0.06
Because weatherability is often not an important requirement, core-shell modi-

fiers in this area are usually based on butadiene rubbers. Polybutadiene is economi-
cal, has an extremely low Tg of approximately –80 °C, and superior elastomeric prop-
erties, leading to higher potential impact performance than all-acrylic compositions.
Core-shell modifiers based on a butadiene homopolymer core result in the highest
impact efficiency, but are useful only in opaque applications. Many packaging appli-
cations require high transparency, which can be achieved through refractive index
matching of the modifier composition with the PVC matrix [130]. Appropriate
amounts of styrene can be incorporated into the core and shell of the modifier to
adjust the modifier refractive index, at the expense of some embrittlement of the
p-Bd rubber and resulting lower impact efficiency. Crosslinking of the Bd or Bd/Sty
core is controlled through process-induced self-crosslinking of Bd, and also through
the use of added multifunctional cross-linkers, such as divinylbenzene.
The role of the shell is analogous to the case of all-acrylic modifiers, although the
molecular structure and composition must be tailored for different processing re-
quirements and secondary properties. Methyl methacrylate and styrene-acrylonitrile
are common compositions that provide good processing and miscibility with the
PVC. In transparent applications, complete breakdown of the modifier powder parti-
cles and complete dispersion back to the emulsion particle size scale are necessary to
avoid haze and optical inhomogeneities cause by gels. Stress whitening is also a
common occurrence in transparent films, and can be minimized by proper design of

the modifier for adhesion and void resistance [131]. Antioxidants and heat stabilizers
are often added to Bd-based modifiers to prevent undue degradation of the modifiers
during the high temperature drying and melt processing operations. In food packag-
ing applications, impact modifiers must also meet specific FDA toxicity and
organoleptic requirements.
Some examples of commercially available Bd-based impact modifiers, and associ-
ated applications, are shown in Tab. 14-7.
Tab. 14-7 Commonly used commercial non-weatherable impact modifiers.
Manufacturer Trade name Product Description
Rohm and Haas Paraloid BTA-730 Clear film and sheet

BTA-833 Clear bottles
BTA-715 Low crease whitening
BTA-753 High efficiency, opaque
BTA-751 High efficiency, opaque, injection molding
Atofina/Mitsubishi, Metablen C-201 Clear film and sheet, bottles
Rayon C-132 Low Crease whitening
C-223 High efficiency opaque
Kaneka Kane Ace B-52 High efficiency opaque
B-51 Low crease whitening
B-22 Clear film and sheet, bottles
14.4.2
Engineering Resins
Engineering resins offer superior performance in various mechanical, thermal and

aesthetic properties, and encompass a wide variety of compositions and applications.
These polymers range from those that are considered inherently tough, such as poly-
carbonate, nylon, and polyethylene terephthalate, to the more brittle polystyrene and
SAN [106]. Although the toughening mechanisms, morphologies and optimal parti-
cle size for impact modification are specific to each type of matrix, the general
approach of adding a second phase of rubbery material is common to most cases. In
contrast to PVC, a much broader range of rubber technologies, both emulsion and
non-emulsion based, is used commercially. The higher processing temperatures of
engineering resins require the addition of significant levels of heat stabilizers and
antioxidants to acrylic or butadiene based emulsion rubbers [132, 133]. Resins other
than PVC are usually compounded as pellets, rather than powders, which lessens
the advantages in powder properties provided by emulsion polymer isolation tech-
niques.
The most widely used emulsion based additives are the all-acrylic or MBS core-
shell polymers. Methacrylate-based shell compositions are generally not highly mis-
cible with the various engineering resin compositions, creating a challenge for prop-
er impact modifier dispersion and adhesion. Common approaches to this problem
include the incorporation of functional polymers in the shell, or a third compatibiliz-

ing polymer, to promote compatibility or chemical reactions between the modifier
shell and resin.
Common examples of toughened engineering resins include polycarbonate and
polyesters. Unlike most other engineering resins, polycarbonate has some miscibili-
ty with PMMA, and traditional core-shell modifiers can significantly enhance the im-
pact performance (Fig. 14-12).
800
Notched Izod Impact Energy (J/m )
640
23 C
480
0C
320
160
0
0 2 4 6 8 10 12
% Acrylic Core-Shell Modifier in Polycarbonate
Fig. 14-12Impact behavior of polycarbonate modified with a core-shell

impact modifier.
PET (polyethylene terephthalate) has poor affinity for traditional shell composi-
tions, but the use of hydroxy-containing compositions can aid in allowing the use of
core-shell type additives for effective toughening [134] (Fig. 14-13).
Transparent PET applications require index refraction matching, imposing anoth-
er constraint on the design of these emulsion additives [134, 135]. In the case of PET,
the additive systems also compete with PETG, available from Eastman Chemical,
which is an inherently tougher resin created by copolymerizing PET and cyclohexa-
nedimethanol [2].
PBT (polybutylene terephthalate) is traditionally toughened using ABS resins,
which may be emulsion-based. Core-shell emulsion polymers, which can be compat-
ibilized with PBT through the use of GMA (glycidyl methacrylate), can be used at lev-
els from 10 to 30 % to efficiently increase impact resistance [2, 136, 137].
PC-PBT blends, offered by General Electric under the trade name Xenoy, are com-
monly used in many automotive applications and can be effectively toughened by
core-shell modifiers. An example of impact modified PC-PBT blend morphology
10
8
Dynatup Drop Dart Energy (J)
6 -10 C
0
0 2 4 6 8 10 12
% Acrylic Core-Shell Modifier in PET (0.94 IV C-PET)
Fig. 14-13 Impact behavior of a PET resin modified with a core-shell
impact modifier.
(Fig. 14-14), clearly shows that the core-shell impact modifier prefers to exclusively
reside in the more compatible PC phase.
ABS (Acrylonitrile-butadiene-styrene) is one of the oldest engineering resins.
Emulsion polymerization can be used to synthesize Bd or Bd-S rubber seeds, fol-
Fig. 14-14 Morpholo-

gy of impact modified
two-phase PC–PBT
blend. The blend con-
tains 40 % PBT, 50 %
PC and 10 % core-shell
modifier. The core-
shell modifier tends to
reside in the polymer
phase it is most com- 20,000 X
patible with, in this
case, PC. 1 µm
lowed by additional polymerization of styrene and acrylonitrile to form an in-situ

impact modified resin. Alternatively, the composition can be blended with addition-
al SAN polymer to produce the desired blend ratios and properties [138]. Core-shell
polymers can be created by minimizing and carefully controlling the SAN polymer-
ization to create the desired morphology. These ABS polymers can be used as addi-
tives to modify SAN and other resin matrices.
Impact modification of nylons is generally achieved through the incorporation of
reactive groups in the rubber [139, 140]. Since these compositions react with the ny-
lon during the melt processing, the conditions and compositions must be carefully
controlled to prevent undesired increases in melt viscosity. While core-shell modi-
fiers have been applied successfully to these systems [141, 142], the most common
commercial approach is the use of olefin-based elastomers grafted with functional
monomers as maleic anhydride.
PMMA, commonly known as Plexiglas®, provides an interesting example of the
application of emulsion synthesis to design multi-layer core-shell impact modi-
fiers [143, 144]. A common three-stage polymer used to impact modify commercial
PMMA resins contains a hard, methacrylate based inner core, surrounded by an
inner, soft acrylate shell, and further encapsulated by a PMMA based outer stage.
The role of the inner hard core is to provide refractive index matching and improved
stiffness retention to the overall matrix. Additional studies have demonstrated the
effectiveness of a large number of alternative multilayer designs in improving the
toughness and balance of properties in impact modified PMMA [145].
Acknowledgment
The authors wish to thank the Rohm and Haas Company for their support.
379
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15
Applications for Dipped Goods
Robert Groves, Andrew Lanham, and Karen Spenceley, Synthoner Ltd, Harlow, UK
15.1
Introduction
The dipping process is, at least in concept, a simple one. The idea of producing a thin
coating by dipping an article into a liquid coating material is well established, being
particularly useful as a method for coating irregularly shaped items, such as car body
parts or toys.
In another guise, the dipping technique can be used to produce flexible, thin-
walled articles from natural or synthetic polymers. The various types of synthetic
polymer used for dipping are discussed in the next section. In the dipping process, a
suitable shape, called in the industry a “mold”, “form” or “former”, is dipped with an
appropriate dwell time into a liquid containing the polymer. The coated former is
then heated to dry and cure the polymer as necessary. Finally, the article is removed
from the former, whose shape it retains. The dipping process therefore provides the
means to make seamless thin-walled items with predetermined, perhaps complex,
shapes.
The thin walled, flexible products normally associated with this process are gloves,
condoms, balloons, catheters and feeder teats and soothers for babies. The polymers
from which they are made often include additives to produce the desired physical
properties. One example of this is the use of curing agents to produce elastomeric
properties, where the final article exhibits the ability to recover its original dimen-
sions after the removal of an applied stress.
This book is concerned with synthetic emulsion polymers, and it has to be said
that at the start of the 21st century their use in the production of dipped goods is rel-
atively limited. The area is dominated by the use of natural rubber for gloves and
condoms. Matching the strength, modulus, tear resistance and dipping characteris-
tics of natural rubber has provided a formidable challenge to the synthetic polymer
chemist.
Balloons and catheters remain the domain of natural rubber, with the very minor
exception of the use of some high modulus synthetic emulsion polymer as a rein-
forcing material for catheters.
384 15 Applications for Dipped Goods
For condoms, no synthetic aqueous emulsion polymer is used. Currently, the al-
ternative to natural rubber is provided by polyurethane dipped from organic solvent.
It is in the area of hand protection that synthetic emulsion polymers have made in-
roads into the dominance of natural rubber. Accurate market figures are difficult to
obtain, but it is believed that currently some 12 % of the estimated 400 000 dry tonne
worldwide market for polymeric gloves (excluding household gloves) is with synthet-
ic emulsion polymers, while about 15 % uses non-aqueous synthetic products.
The protective glove market can be subdivided as follows.
Disposable
Medical Surgical (approx. 12 g per piece)
Examination (approx. 8 g per piece)
Light industrial (approx. 8 g per piece)
Unsupported
Household (approx. 30 g per piece)
Industrial (20 to 100 g per piece)
Fabric-supported (Fabric glove coated with 30–80 g polymer)
Disposable and unsupported gloves consist of a film of a chosen polymer with a

thickness appropriate to the end use. Fabric-supported gloves are made by pulling a
woven fabric “liner” on to a former, and applying a polymer coating to the fabric by
dipping.
Synthetic polymers have found their main use in light industrial, unsupported in-
dustrial and fabric supported gloves. The reasons have been associated with specific
technical benefits, as described in the next section.
15.2
Polymers Used by the Dipping Industry
Although natural rubber dominates the dipping sector, synthetic polymers can offer
significant technical benefits for some applications. The main benefits for synthetics
that have so far emerged are:
– the ability to produce gloves with a much higher degree of resistance to non-polar
organic solvents than is possible with natural rubber;
– to produce skin-contact items that are completely free of proteins, where an alter-
native material to natural rubber is desirable because of potential protein allergy
problems;
– to make gloves which have a lower surface electrical resistance than natural rub-
ber, a useful property in gloves that are used in electronic assembly because of the
reduced risk of damaging sensitive components by static electricity;
– with the correct polymer design, to achieve greater mechanical protection (punc-
ture and abrasion resistance) than is possible with natural rubber.
15.3 Principles of Dipping 385
Several synthetic polymers are used by the glove industry. Clearly, for dipping, the
polymer must be provided in a liquid form. For poly(vinyl chloride) the liquid is a
plastisol, which is a dispersion of the polymer in an organic liquid, most of which is
a plasticizer for the polymer. Heat treatment causes the plastisol to gel and the plas-
ticizer to dissolve in the polymer, giving the final flexible composition. Gloves made
from this composition are commonly termed “vinyl”.
Polyurethane and styrene-butadiene-styrene block copolymers dissolved in organ-
ic solvent have been used to produce gloves and, in the case of polyurethane, also
condoms. However, for the producers of dipped articles, a water-borne polymer sys-
tem is often highly desirable for health, safety and environmental reasons. Some
attempts have been made to convert polymers that have been synthesized in organic
solvent into aqueous emulsions suitable for dipping. So far these attempts have been
largely unsuccessful at the commercial scale, because of the cost involved in the
multistage process and because the relatively large quantity of surfactant added to
achieve emulsification increases the difficulty of controlled gellation during the dip-
ping process.
There are only two commercially important water-borne polymers currently used
by the dipping industry and both are used to manufacture hand-protection articles.
These polymers are:
– Copolymers of butadiene, acrylonitrile and a third monomer that contains a car-
boxylic acid group (usually methacrylic acid). Gloves made from this copolymer
are often termed “nitrile”. The particular advantages of this polymer are resistance
to many solvents and excellent mechanical protection (abrasion and puncture re-
sistance). Nitrile also has a significantly lower surface electrical resistivity than nat-
ural rubber, and therefore finds use in gloves for use in areas where static electric-
ity might be a problem.
– Homopolymers of 2-chloro-1,3-butadiene (“chloroprene”). Gloves made from this
polymer are known as polychloroprene or “Neoprene” (Neoprene is a trademark of
E I DuPont de Nemours and Co). The key attributes of this material are a similar
stress-strain response (“feel”) to natural rubber, resistance to oils and fats and ex-
cellent light and ozone resistance.
Nitrile and polychloroprene latices are made by the industrial process of emulsion
polymerization, in which the polymerization reaction and the formation of an aque-
ous emulsion occur simultaneously. In this process, reaction temperature and con-
trol of the polymer molecular weight are important in order to obtain the desired fi-
nal glove properties. In the case of the nitrile latex, the ratio of the three monomers
can also be used by the polymer chemist as an important tool in tailoring the final
product properties.
15.3
Principles of Dipping
The basic concept of producing a coating or a thin-walled article by the dipping

process is straightforward. A former of the desired shape is dipped into a liquid mix
that contains the material of which the final product is to be made. The process is
arranged so that on withdrawal, a thin deposit of the mix is left on the former. The
process continues by heating the coated former to solidify, dry and cure the deposit-
ed mix. Finally the thin, flexible film is removed from the former to yield the desired
product. Further information on the dipping process has been published by various
authors, including Carl [1], Blackley [2] and Lanham and Eidam [3].
There are several ways in which the deposition of the mix can be controlled, in or-
der to produce the desired wall thickness in the final article. The first is simply by ad-
justing the viscosity and solids content of the liquid, and is applicable to both solu-
tion and dispersion mixes. This process is called simple or straight dipping and is
the method usually employed for making condoms from natural rubber latex.
Straight dipping usually yields thin films. For the manufacture of condoms, the final
film is normally built up by two or more separate dips.
Coagulant dipping is the method most often used to deposit thicker films in a sin-
gle dip, for example to make gloves or balloons. In this process, the mold or former
is first dipped into a coagulant liquid, such as an aqueous solution of calcium nitrate.
After partial drying of the coagulant, the former is dipped into the liquid mix, which
must be provided as a colloidal dispersion. The coagulant causes a localized destabi-
lization and viscosity rise in the dispersion at the surface of the former, thus en-
hancing the amount of mix deposited. The thickness of the deposit can be controlled
by the concentration and drying of the coagulant solution and the colloidal stability
and total solids of the dispersion.
A third method used to control deposition on to the former is to use additives in
the mix that cause destabilization and/or a viscosity increase at elevated temperature.
Deposition of the mix is therefore facilitated if a hot former is used. This method has
been used mainly in the production of thicker items, for example babies’ teats. Heat
sensitizing additives that have been used with natural rubber include polyvinyl-
methyl ether and polypropylene glycol. Obviously, with this system especially, good
control over the temperatures of the dipping mix and former is necessary.
15.4
Dipping Synthetic Polymer Emulsions in Practice
Inevitably, refinements and modifications have to be added to the basic principles to

yield a viable, commercial dipping process. This section describes some of the
methodology used in achieving practical systems. Since at present the only signifi-
cant use of synthetic emulsion polymers is with nitrile and polychloroprene latices
for glove manufacture, the following notes are necessarily directed towards this area.
15.4.1
Former Design
Obviously the main requirement of a former for unsupported glove production, is to

provide the shape of the desired final product. In addition, however, the mix or coag-
ulant must easily wet the former, otherwise an irregular or incomplete deposit re-
sults. The design of the former (Fig. 15-1) should be such that air bubbles are not en-
trained on the former surface as it enters the mix. The design should also minimize
the tendency for the thin film to shrink in the length direction of the former during
drying. The formers should be easy to clean.
Fig. 15-1 Former designs for

(left) thin multi-purpose gloves
(ambidextrous); (center) for
fabric supported gloves (hand
specific) and (right) for indus-
trial unsupported gloves (hand
specific).
Of the many materials tried, unglazed porcelain is favored for formers for unsup-
ported glove manufacture, since it accepts coagulant readily and its micro-roughness
helps to limit length-direction shrinkage of the drying polymer film. For thicker
gloves and thin surgical gloves, specific left and right hand formers are used. For
thin disposable gloves, the same former shape is used for both left and right hands.
The production of fabric supported gloves requires special formers. Since these
gloves are relatively difficult to stretch, the former is often designed with a moveable
joint at the base of the thumb (or even a detachable thumb) to ease the task of re-
moving the final product. Clearly, many of the features required by formers for un-
supported gloves are unnecessary for fabric supported work, where only the fabric
liner should contact the dipping mix.
15.4.2
Mix Design
Although the mix consists mainly of the polymer dispersion, it is usual to use sever-
al additives to achieve the desired performance. A typical mix for producing a glove is
shown in Tab. 15-1 and the various additives are discussed below.
Tab. 15-1 Typical latex-based formulation for dipped gloves.
Ingredient Parts active per hundred dry rubber
Carboxylated nitrile rubber 100

Antioxidant dispersion 0–1.0
Potassium hydroxide solution 0.5
Zinc oxide dispersion 0.5–5.0
Sulfur dispersion 0.5–2.0
Accelerator dispersion 0.5–2.0
Titanium dioxide dispersion 0–0.5
Pigments Trace
Thickeners 0–0.4
Antioxidant is normally included in the latex by the polymer manufacturer, but if

not it can be added to the mix by the compounder.
The alkali (in the example of Tab. 15-1, potassium hydroxide) is normally added to
the latex first, as it tends to stabilize the compound to the addition of the other com-
ponents. The alkali also affects the pick-up on to the former and hence the final poly-
mer film thickness. It is added in dilute form, since concentrations above 5 % can
cause the latex to flocculate. A fugitive alkali, such as aqueous ammonia, can be used
but gives a greater tendency for skin formation on the mix surface. A typical pH for
a dipping mix would be approximately 9.0, but this value will vary according to the
particular grade of latex being used.
Zinc oxide is an interesting ingredient. It is used in fairly large quantities (5–10
parts per hundred of dry polymer) in polychloroprene compounds as a cross-linking
agent, reportedly functioning by acting as a hydrochloric acid acceptor [4]. In nitrile
compounds, zinc oxide is also found to act as a curing agent, having a profound ef-
fect on the physical properties of the final film. In this case it is reasonably certain
that the mechanism is one of interaction of zinc cations with the carboxyl groups
present in the nitrile copolymer [5]. Levels of ZnO used with nitrile polymers are in
the range 0.5–5.0 parts.
The zinc oxide also reduces the colloidal stability of the mix and so influences the
amount deposited on the former during coagulant dipping.
For both polychloroprene and nitrile polymers the zinc oxide, together with the
other accelerators, also activates the sulfur vulcanization. However, for carboxylated
nitrile products, the sulfur curing is thought to be of less significance than the effect
conferred by the interactions between zinc cations and carboxyl groups [3]. Some ac-
celerators that are commonly used to increase the rate of sulfur curing are listed in
Tab. 15-2.
Tab. 15-2 Commonly used accelerators for nitrile and neoprene latices.
Chemical Type Common abbreviation
Benzothiazoles
2-Mercaptobenzothiazole MBT
2,2-Dithiobisbenzothiozole-2-sulfenamide MBTS
Benzothiazolesulfenamides
N-Cyclohexylbenzothiazole-2-sulfenamide CBS
N-t-Butylbenzothiazole-2-sulfenamide TBBS
2-Morpholinothiobenzothiazole MBS
N-Dicyclohexylbenzothiazole-2-sulfenamide
Dithiocarbamates
Tetramethylthiuram monosulfide TMTM
Tetramethylthiuram disulfide TMTD
Zinc diethyldithiocarbamate ZDEC
Amines
Diphenylguanidine DPG
Di-o-tolylguanidine DOTG
The choice of accelerator depends on the curing profile and final properties de-
sired. Care has to be exercised in the use of dithiocarbamates, since these materials
can give rise to discoloration in the presence of trace amounts of copper.
Previously, accelerators such as thiurams, thiazoles and carbamates were used,
but their use has declined because of problems with skin allergies. This issue is dis-
cussed in detail by Estlander et al. [6]. In addition to the problems of contact der-
matitis, it may be necessary to consider the formation of N-nitrosamines by acceler-
ators. Dithiocarbamates and thiuram sulfides have the potential to decompose to
give N-nitrosamine precursors [3]. N-nitrosamines are believed to be carcinogenic,
although conclusive evidence for human carcinogenicity is scant, as discussed re-
cently by Loadman [7].
Titanium dioxide, in the form of an aqueous dispersion, is added as an opacifying
agent. It also enhances the color imparted by the pigment. Titanium dioxide is used,
despite its expense, because its high refractive index gives it a high opacifying effi-
ciency and it can therefore be used in relatively small quantities with minimal im-
pact on the physical properties of the product.
A thickener is often used to control the mix viscosity, which in turn affects pick-up
on to the former. Table 15-3 lists a few of the thickener materials that have been used
in dipping compounds.
Tab. 15-3. Thickeners for dipping compounds.
Chemical type Used in Comments
Polyacrylates Unsupported, Polyacrylates are often supplied as an emulsion,

heavier weight gloves becoming effective on raising their pH.
They usually give a pseudoplastic rheology.
Polyvinyl alcohol Fabric supported gloves Solutions of PvOH can be difficult to prepare.
PvOH usually gives a thixotropic rheology.
Casein Unsupported gloves Expensive. Casein also acts as a colloid stabilizer.
It is susceptible to infection problems.
Other additives are also frequently employed in the dipping mix. Additional sur-
factant may be added to adjust the colloidal stability and thus the thickness or quali-
ty of the dipped film. Materials to discourage foaming in the mix or the formation of
a thin film of wet mix between the fingers of a glove (“webbing”) can also be added.
15.4.3
Coagulant
The usual coagulants employed for glove dipping are calcium salts that are soluble in
water, in particular calcium nitrate and calcium chloride. The advantages of these
materials include their efficiency in coagulating anionic emulsion polymers, their
relatively low cost, low toxicity and low environmental impact. The aqueous coagu-
lant solution is usually held at high temperature (about 60 °C), to accelerate its rate of
drying on the former surface. A surfactant is often added to the coagulant solution to
ensure adequate wetting of the former.
A technique sometimes employed is to dissolve the coagulant in a mixture of wa-
ter and alcohol. The main advantages are an improved drying rate and improved wet-
ting of the former. Because of its faster drying rate, alcoholic coagulant is used at a
lower temperature than the aqueous type, but of course the use of alcohol raises
problems from a health, safety and environmental standpoint.
It is quite common for the coagulant solution also to contain 1 to 5 % of a parting
aid. This is an inert powder, for example talc or calcium carbonate, which reduces
the adhesion between the final dipped film and the former, thus making the removal
of the finished glove easier.
15.4.4
The Dipping Process
Many aspects of the dipping process can be adjusted to suit the particular type of
glove being produced. In the following sections, some process details are given for
each of the three main types of gloves that are made using synthetic latex.
Disposable gloves
These products are often referred to as thin gloves and find use mainly in the health-
care sector, where their primary function is to prevent transfer of infectious agents
between medical workers and patients. A secondary function can be to provide pro-
tection against pharmaceutical preparations. Disposable gloves are also used in in-
dustrial applications, for example electronics, where the purpose of the glove is to
prevent assembly workers contaminating clean items, such as silicon wafers or disk
drive surfaces.
The most usual manufacturing process for disposable gloves is the continuous or
chain process. Here, individual or pairs of formers are attached at intervals to an
endless chain that moves at constant speed, enabling the formers to visit each pro-
cessing station in turn. At stations where dipping occurs, the track bends downwards
then upwards, carrying the formers in and out of the liquid. Entry and exit is there-
fore not vertical. This operation gives high volume output for relatively low cost.
However, the process is rather inflexible and is best suited to large runs of one type
of glove.
A schematic diagram of the process is given in Fig. 15-2 and the various steps are
explained below.
Former Coagulant Latex Bath Beading Leaching

Cleaning Bath
Stripping Drying & Vulcanisation Anti-tack

Fig. 15-2 Bath
Continuous
dipping
process.
The process starts with cleaning of the formers, an essential step without which
poor quality films will result. Cleaning is accomplished by passing the formers
through a bath of mineral acid or alkali containing surfactant, by brush scrubbing,
by ultrasonic treatment or a suitable combination of these methods. Cleaning is fol-
lowed by a thorough rinse with clean water. As required, formers are taken out of the
process for a more extensive cleaning, perhaps with sulfuric or chromic acid.
The next step is to dip the former into the coagulant solution. The solution
strength is typically in the range 10–25 % by weight, the concentration being moni-
tored by specific gravity. The coagulant picked up by the former is dried before the
next step.
At the following station, the coagulant-coated former comes into contact with the
latex and the polymer deposit starts to build up on the former surface, increasing in
thickness with dwell time in the latex bath. In this central step of the process, the for-
mer temperature, speed and smoothness of former entry and exit are important fac-
tors in the production of an even, defect-free film.
On leaving the latex dip tank, the formers are lifted to the horizontal and rotated,
to avoid ungelled latex on the outside of the film flowing to the bottom of the former.
The latex layer continues to consolidate after removal from the latex bath, forming a
firm, gelled coating.
The polymer at the cuff of the glove is then rolled on to itself by the action of me-
chanical rollers or brushes, a process known as “beading”. The tack of the polymer at
this stage of processing is sufficient for the bead to be held in place. The purpose of
the bead is to give the cuff of the thin glove adequate tear-resistance.
Following beading, the glove is leached, a washing process carried out by immers-
ing the glove in warm (40–50 °C), clean water. Long leaching times are preferred
from a technical standpoint, to achieve the maximum removal of water-soluble ma-
terials. However, in practice, leach duration is limited by time, space and cost con-
straints and is normally of the order of 5–10 min. Care must be exercised in the
leaching process, since high leach water temperatures can promote excessive length
direction shrinkage of synthetic latices.
The glove is then dipped into an anti-tack compound, which may be a silicone
emulsion or a slurry of calcium carbonate. The purpose of applying this material is
to reduce the rubber-rubber friction when the glove is ultimately peeled from the for-
mer, thus easing its removal, and to prevent the interior surfaces of the glove stick-
ing together on storage.
The penultimate stage of the process is drying and vulcanization. Sophisticated
cure ovens will allow the curing to be phased, for example to bring the temperature
gradually to around 120 °C to avoid blistering. A slightly cooler temperature may be
programmed for the final oven stage, to make glove removal easier. For the curing of
disposable gloves, approximately 20 min at 120 °C is required. Undercured gloves
tend to have low tensile strength and high elongation, making them difficult to strip.
Incomplete drying can lead to problems of glove surfaces sticking to one another on
storage.
The removal of the glove from the former (“stripping”), is the only fully manual
part of the process, in which teams of three or four workers line each side of the
chain to pull off and briefly check the gloves for holes. Occasionally compressed air
jets are used to assist with the stripping process.
Disposable gloves can be further dried offline, by tumbling in heated ovens. Fol-
lowing tumbling, gloves are usually chlorinated by immersion in an aqueous dilute
chlorine solution (a technique also used for natural rubber disposable gloves). The
chlorine reacts with the surface layer of polymer molecules, giving a marked reduc-
tion in surface tack that makes the gloves easier to don. Finally, the gloves may be
washed, re-dried, QC tested and packed.
Unsupported heavier weight gloves

Thicker walled gloves, capable of being used on multiple occasions, find use in both
industrial and domestic situations. They are often made with a lining of small fibers
(“floc lined”), which improves comfort by absorbing perspiration.
Industrial gloves will probably be destined for use as protective equipment and
will therefore be required to meet specific safety standards. These standards cover ar-
eas such as resistance to chemical penetration, puncture resistance and abrasion re-
sistance. Further information on protective gloves is given in the book edited by
Mellström et al. [6].
Household gloves are normally made from natural rubber and have been regarded
as price-driven commodity items. However, recent concern over protein allergy has
led to the increased use of sophisticated synthetic polymers in this area also.
Heavier weight gloves may be made by the continuous process in a similar man-
ner to that described above, but they are more commonly produced by the batch
process, outlined as follows.
Jigs to which perhaps 20 or 30 formers are fixed are moved sequentially on guide
rails from station to station. Operations such as dipping into a liquid bath are
achieved using hydraulic equipment. Within limits, the time spent at each station
can be independently varied, so more control is possible than with the continuous
process, where the speed of movement round the track is constant.
A schematic diagram of the batch process for thicker unsupported gloves is given
in Fig. 15-3.
Former Coagulant Latex Bath Leaching Flock

Cleaning Bath Bath Adhesive
Stripping Chlorination Drying & Vulcanisation Flocking

Bath Booth
Fig. 15-3
Batch dipping
process.
The various steps in this process are described below and the similarities and dif-
ferences in the production conditions compared to those used for disposable gloves
are highlighted.
The process again begins with the cleaning of formers, using similar methods to
those employed in the thin glove process.
The coagulant solution is of a higher concentration and dip times are much longer
than those used for disposable gloves. The most common coagulant solution is aque-
ous calcium nitrate at 30–40 % by weight. With the batch process, the formers enter
and leave the coagulant at right angles to the solution surface, only moving in the
vertical plane. After withdrawal from the coagulant, the formers are usually inverted
to achieve a more uniform distribution of the solution over the surface.
After drying the coagulant, the former is dipped into the latex bath. As for thin
gloves, the critical factors of entry and exit rate and former temperature have to be
optimized to produce an even polymer film. For thicker gloves, dwell times in the la-
tex bath may be in excess of 2 min and for very heavy gloves a second dip may be em-
ployed. Note that film thickness is not only a function of dwell time in the latex, but
also of the coagulant strength and temperature, the latex mix viscosity and the latex
stabilizing system.
When the polymer film has gelled sufficiently it is leached in warm, clean water.
This stage is essential to remove surfactants and coagulant that would otherwise re-
sult in surface tack on the finished gloves. It is advisable to use as long a leach time
as practicable, and thicker gloves certainly require more time than disposable ones.
Typical leach conditions used for heavier weight gloves are 10 to 15 min with water
temperature in the range 45–70 °C.
If the gloves are to be flock lined, the next step is the application of a flock adhe-
sive, again by dipping. The adhesive should form a good bond with both the glove
polymer and the flock fibers and should not be coagulated by any residual coagulant
that might be on the polymer surface at this stage of the process. To achieve a good
bond, it is common to use an adhesive that is based on the main glove polymer.
The flock normally consists of cotton fibers. The fibers are made airborne by com-
pressed air or electrostatic methods in a booth, into which the gloves are moved.
Flock contacts, and adheres to, the wet adhesive and conditions are adjusted so that
the fibers are wetted by the adhesive, but not immersed in it. The electrostatic
method is useful in this regard, since it can be used to encourage an orientation of
the fibers perpendicular to the glove surface.
The drying and curing of heavy gloves is slower than for disposable gloves. As well
as having more water to evaporate, the drying rate of heavy gloves has to be limited to
prevent escaping water vapor “ballooning” the glove. In addition, industrial gloves
tend to need a higher degree of crosslinking to give chemical resistance. Curing
times of up to 45 min are quite usual.
The chlorination step is similar to that employed with thin gloves. For heavier
gloves, one side may be chlorinated on machine and the other off-line.
Stripping is a manual process and, for thicker gloves especially, it can be a fairly
demanding one, since highly cross-linked polymers can offer significant resistance
to the manipulation required for removal from the former. The best manufacturing
units use both former design and machine layout to ease this process.
After stripping, the gloves may be chlorinated or given a further heat treatment be-
fore being inspected and packed.
Fabric-supported gloves
Fabric-supported or coated fabric gloves are a small but important part of the market.
They are primarily used where a high degree of mechanical protection, combined
with water and chemical resistance, is required. The construction is based on a tex-
tile “liner” which has been coated with a polymeric layer. The liner fabric gives a ben-
efit in user comfort and may be made from cotton, polyester, nylon or even Kevlar.
The liners are formed by cutting and sewing the chosen fabric into the desired
shape, or they are knitted in one piece. While the cut and sewn type predominates
because of its ease of production, the knitted liner is finding increasing popularity
because of the reduced material wastage, lower labor cost and increased comfort.
The dipping of supported gloves is carried out successfully by only a few compa-
nies worldwide and the technology is generally proprietary. As there are many types
of supported glove and production methods vary, no attempt will be made to de-
scribe their manufacture here in any detail. It can be said, however, that the key issue
is to control the application of the polymer coating, so that good coverage and good
adhesion are achieved but without excessive penetration of fabric liner by the mix. In
addition to fabric design, compound low-shear viscosity, compound surface energy
and the depth and duration of dipping are some of the factors that can be used to
achieve a successful over-dip.
The presence of a fabric liner creates some practical problems in the dipping
process. With the correct control of latex compound rheology, straight dipping can,
of course, be used. If a coagulant method is chosen, a significant amount of the co-
agulant may be absorbed into the liner, requiring removal from the finished glove by
thorough washing. The use of a heat-sensitized dipping compound is complicated by
the difficulty of achieving a controlled temperature at the liner surface and the diffi-
culty of controlling the mix viscosity close to the liner in the presence of a hot former.
In general, the coagulant and straight dipping methods are the most favored.
15.5
The Testing of Synthetic Gloves
An increasing number of standards concerned with the performance of gloves are

becoming available. They come from a variety of sources (regulatory bodies), includ-
ing:
International International Standard Organization (ISO)

USA American National Standards Institute (ANSI)
American Society for Testing and Materials (ASTM)
UK British Standards Institution (BSI)
France Association Française de Normalization (NF)
Germany Deutsches Institut für Normung (DIN)
Europe European Standards (EN)
Former USSR State Committee for Standards (GOST)
Note that various professional organizations have also developed standards which
can be useful for glove testing.
15.5.1
Non-safety-critical Gloves
There is a number of standards specifying the general performance of polymeric ma-

terials which might be used in the manufacture of gloves. For example, both the
ASTM and BSI have issued methods for testing the physical properties of rubbers
and the effects on rubbers of accelerated aging.
The ASTM has issued a standard for household or beautician’s gloves, which sets
out specifications aimed at assisting in the achievement of performance consistency.
Tests specified include tensile strength and elongation (before and after aging),
physical dimensions and freedom from holes. This standard refers to general meth-
ods for testing elastomeric materials, such as those mentioned in the preceding para-
graph.
Gloves that are used in electronic assembly are designed primarily to protect the
product under manufacture, rather than protect the worker. Some standards relating
to glove material cleanliness and to the testing of static electrical properties of mate-
rials are available and used in this area.
15.5.2
Safety-critical Gloves
The hand is perhaps exposed to more hazards than any other part of the body. These
hazards include physical damage, chemical contact and contact with biological
agents. Clearly, one means of minimizing the risk of these hazards actually causing
harm, is to select an appropriate glove.
There are many standards that specify tests and performance for protective gloves.
The general tests relating to the physical properties of glove materials, referred to
above, may be used. The European Union has detailed a number of requirements for
protective glove manufacturers in the Personal Protective Equipment Directive
89/686/EEC. Gloves meeting these requirements carry the CE mark, which allows
them to be marketed throughout all European Community countries.
There are individual standards for assessing protection from mechanical, chemi-
cal, biological and radioactive hazards, as well as protection from heat and cold. Par-
ticular standards dealing with surgical and examination gloves exist, some of which
are material specific, and for gloves designed to give protection against electrical
hazards.
Some of the standards that have found use in the protective glove area are listed in
Tabs. 15-4, 15-5 and 15-6.
Tab. 15-4 North American standard test methods.
ASTM D120 E1 Standard Specification for Rubber Insulating Gloves

ASTM D412 Standard Test Methods for Vulcanized Rubber – tension
ASTM D573 Standard Test Method for Rubber – deterioration in an air oven
ASTM D624 Standard Test Method for Tear Strength of Conventional Vulcanized Rubber
and Thermoplastic Elastomers
ASTM D991 Standard Test Method for Rubber Property – volume resistivity
of electrically conductive and antistatic products
ASTM D1418 Standard Practice for Rubber and Rubber Latices – nomenclature
ASTM D3577 Standard Specification for Rubber Surgical Gloves
ASTM D3578 Standard Specification for Rubber Examination Gloves
ASTM D4679 Standard Specification for Rubber Household or Beautician Gloves
ASTM D5151 Standard Test Method for Detection of Holes in Medical Gloves
ASTM D5250 Standard Specification for Polyvinyl Chloride Gloves for Medical Application
ASTM D5712 Standard Test Method for Analysis of Protein in Natural Rubber
and its Products
ASTM D6319 Standard Specification for Nitrile Examination Gloves for Medical Application
ASTM E595 Standard Test Method for Total Mass Loss from Outgassing in a Vacuum
Environment
Tab. 15-5 European standard test methods.
BS/EN 368 Protective Clothing for Use against Liquid Chemicals – penetration
of liquids
BS/EN 369 Protective Clothing for Use against Liquid Chemicals – permeation
of liquids
BS/EN 374-1 Protective Gloves against Chemicals and Microorganisms –
terminology and performance requirements
determination of resistance to penetration
determination of resistance to permeation by chemicals
BS/EN 388 Protective Gloves against Mechanical Risk
BS/EN 407 Protective Gloves against Thermal Risks (heat and/or fire)
BS/EN 420 General Requirements for Gloves
BS/EN 421 Protective Gloves against Ionizing Radiation and Radioactive
Contamination
BS/EN 455-1 Medical Gloves for Single Use – specification for freedom from holes
BS/EN 455-2 Medical Gloves for Single Use – specification for physical properties
BS/EN 464 Protective Clothing – Protection against Liquid Chemicals – gas leak test
BS/EN 511 Protective Gloves Against Cold
BS 903 :A2 Physical Testing of Rubber – determination of tensile stress–strain properties
BS 903: A9 Methods of Testing Vulcanized Rubber – determination of abrasion resistance
BS 903: C1 Methods of Testing Vulcanized Rubber – determination of surface resistivity
BS 2782: Part 2 Methods of Testing Plastics – electrical properties
BS 2782:
Method 231A Methods of Testing Plastics – determination of surface resistivity
BS 7506:1 Measurement in Electrostatics – guide to basic electrostatics
Tab. 15-6 Professional standard test methods
UK Dept of Health Specification for non-sterile NR latex examination gloves

M.D.D. TSS/D/300.010
Institute of Environmental Gloves and finger cots used in clean rooms and
Sciences and Technology (USA) other controlled environments
IES-RP-CC005.2
These lists are not intended to be exhaustive, but are included to give the reader
some idea of the breadth of standards available. Clearly, as new technologies evolve,
standards will be updated and others newly issued.
References
1 J. C. Carl, Neoprene Latex – Principles 5 L. Ibarra, M. Alzorriz, Polym. Int. 1999,

of Compounding and Processing, 48, 580.
E. I. Dupont De Nemours, Wilmington, 6 T Estlander, R Jolanki, L Kanerva, in:
Delaware, USA, 1962. Protective Gloves for Occupational Use,
2 D. C. Blackley, Polymer Latices Science G. A. Mellström, J. E. Wahlberg,
and Technology, 2nd edn, Vol. 3, Chap- H. I. Maibach (eds), CRC Press,
man and Hall, London, UK, 1997. Boca Raton, Florida, USA, 1994.
3 A. Lanham, N. Eidam, in: Wäßrige Poly- 7 M. J. R. Loadman, Proc. Int. Rubber
merdispersionen, D. Distler (ed.), Wiley- Conf., Manchester, UK, 1996.
VCH, Weinheim, Germany, 1999.
4 D. M. Bratby, in: Polymer Latices and their
Applications, K. O. Calvert (ed.), Applied
Science, London, UK, 1982.
Index
a – cationic 315
abrasion cohesion test Esso (ACTE) 323 – cured 318
abrasion resistance 115, 332 – ductility 317
accelerators 389 – elastic recovery 317
acorn structure 5 – latex modified 318
acrylates 90 – medium-setting 313
acrylic adhesive 220 – modification 301
acrylic dispersions 6, 12, 90, 108, 130 f., 142, – penetration 317
154, 193 ff., 217, 273 f., 285, 291, 358 – properties 309
acrylic esters 90, 94 – rapid-setting 313
additives 78, 132, 240, 332 f., 355 – slow-setting 313
adhesion 191 ff., 299, 330, 332, 338 f., 339 – softening point 317
adhesion level 210 – specification 304
adhesion-elongation 238 – tests 317
adhesive raw materials 192 – torsion recovery 317
adhesives 191 ff., 334 automotive coating 163 ff., 176 f., 183
agglomeration number 28 – appearance 169
aggregates 332 – basecoat 167
aging resistance 299 – clearcoat 167
American Standards (ANSI) 335 – crosslinking 183
analytical ultracentrifuge 51 – electrocoat 167
antifoam agents 6, 114, 136, 202 – emulsion polymers 176
antifreeze agents 235 – formulation 168
anti-sag 334 – function of ingredients 168
apparel leather 284, 293 – function 167
applications tests 97 f., 114 f., 142 ff., 147 f., – layer 167
151, 156 f., 159 f., 168 ff., 210 ff., 221 f., – main ingredients 168
228 ff., 232, 237 f., 240, 246 f., 249, 261, – microgels 177
275 ff., 296 ff., 304 ff., 321, 335 ff., 368, – miniemulsions 177
395 ff. – performance 169
aqueous 1 – primer 167
aqueous flexo news ink 121 – standard tests 169
aqueous ink 104 automotive leather 284, 294
aqueous phase analysis 57 average degree of polymerization 195
asphalt binder 304
asphalt composition 310 b
asphalt consumption 301 back-coating of carpets 259, 262
asphalt emulsion 302, 303, 313 ff. bally flexometer 297
– anionic 315 barrier coatings 7
– application 314 basecoat 173 ff., 287, 344
400 Index
bending beam rheometer 306, 308 chain transfer agent 32, 178, 198
bimodal 5 characterization 41 ff.
binder 78, 84 ff., 127, 253, 291, 332 chelating agent 34
– natural 90 f. chemical bonding 273
– paints 127 chemical reacting adhesives 192
– sole binder 90 chemical resistance 116
– styrene-acrylate 96 f. china clay 86
– styrene-butadiene 95, 97 chip seal 316, 321
– synthetic 90 f. – application test 321
binding strength 87, 92 ff. coagulant dipping 386
biocides 6, 135, 203 coagulants 390
biodegradability 6 coagulation 3
blistering 93 ff. coagulum 37
block resistance 116 coagulum grit 42
board 92 coating 205
branching 18 coating color 81, 85, ff.
brightness 84, 86, 93 – co-binder thickeners 87
butadiene 9, 90, 94 f. – pigments 86
butadiene-styrene copolymers 11, 90, 256 ff., – sheet-fed offset 86
273 f., 285, 291, 303 ff. coating layers 166
butadiene-acrylonitrite copolymers 385 ff. coating of carpets 261
butyl acrylate 90 coating support materials 205
coating weight of adhesives 207
c co-binder 84, 87 ff.
calcium carbonate 86 f. coefficient of friction 116
calender 85 f. colloid mill 313
capillary hydrodynamic fractionation 53 color 65
capillary water absorption 345 concrete 242, 346 ff.
carboxylated styrene/butadiene (XSB) – maintenance 347
dispersions 6, 90, 256 ff., 273 f. – rehabilitation 349
carboxylic acid 26 – repair 347 f.
carboxymethylcellulose 88, 90 construction adhesives 224
carpet 253 construction industries 191
carpet backcoating 259 contaminants 36
carpet backing 253 conversion 22
carpet backing binders 253, 256, 258 conversion process 363
– carboxylated styrene-butadiene 256 – melt rheology 363
– cold SB (styrene-butadiene) 256 conversion-time curve 23
– high solids styrene-butadiene latex core-shell modifiers 373
(HSL) 256 core-shell structure 4 f.
– hot SB (styrene-butadiene) 256 core-shell impact modifier 376
– natural latex 256 core-shell particle 71
carpet laminating 259, 263 f. corona discharge 118
– adhesive scrim coat 263 corona-pretreated film 218
– pre-coat 263 corrosion inhibitor 114
– unitary backing 264 CPVP 126
carpet production 255 cracking 336
carpet terminology 260 crinkle resistance 116
cement 333 critical micelle concentration
cementitious topcoats 345 (CMC) 19, 27
centrifugation 51 critical PVC 126
ceramic tile adhesives 238 ff., 332 ff. critical surface tension 65
chain entanglement 21 cross-linking 4, 9, 21, 33, 70, 113, 167, 183 f.,
chain transfer 18 220
Index 401
cup and plate inks 120 electric double layer 26

curtain coater 289 f. electrical tapes 208
electrocoat 170 ff.
d electrokinetics 56
decorative coatings 123 ff., 137, 139 electrolytes 33
defoamer 6, 114, 136, 202 electrophoretic mobility 56
degradation time 360 elongation at break 6, 63
delaminating 336 elpo 170
delamination resistance 221 embrittlement 299
density 43 emission measurement 230
diafiltration 58 – chamber method 230
dialysis 58 emulsified asphalts 302
differential scanning calorimetry 60 emulsifier coverage 55
dilatancy 45 emulsifiers 9
dipped gloves 388 emulsion polymerization 3, 16, 17, 20, 330,
dipped goods 383 356
dipping 384 ff. – at atmospheric pressure 16
– forms 386 – at high pressures 16
– mix design 388 – mechanism 17
– polymers 384 emulsion 1
– practical aspects 386 emulsion polymers 15
– principles 385 – synthesis 15
– process 383, 390 ff. emulsion vehicle 109
direct print corrugated inks 119 engineering resins 375
disc centrifuge 53 environmental impact 325
dispersing aids 133, 235 equipment 39
dispersion 1 ethene 8, 10
dissolution 66 ethylene/vinyl acetate copolymers 6, 90,
double-sided adhesive tapes 209 330 ff.
Dougherty-Krieger equation 47 extenders 132
dry adhesion 299 extensibility 361
dry mix mortars 333, 352 exterior decorative coating 146 ff.
dry mortar technology 332 – application tests 148
– pre-mixed 332 – exterior exposure testing 148
– pre-packed 332 – formulations 147
– redispersible powders 332 – performance tests 147
drying test 116 – standard application tests 147
dwell time 212 exterior insulation and finish systems
dynamic light scattering 49 (E.I.F.S.) 332
dynamic mechanical analysis 63 f. exterior insulation systems 341
dynamic shear rheometry (DSR) 306 exterior thermal insulation compounds
(E.T.I.C.S.) 332
e
E.I.F. systems 342 f
e-coat 170 fastness 299
eco-efficiency analysis 323 fatigue cracking 306
efflux time 44 Fikentscher’s K-value 195, 360
elastic modulus 62 fillers 86, 202
elastic recovery 237 film formation 128 f.
elasticity 6 – coalescing agent 129
elastomeric roof coatings 247 – latex 128
elastomeric wall coating 149 f. film forming emulsion polymer 117
– application tests 151 film morphology 70
– formulation 150 film whitening 67
402 Index
finish systems 341 glossy film lamination 219

finishing 287 glove dipping 391, 393
finishing coats 287 – batch process 393
flexibility 332, 336, 338 – continuous process 391
– mortar 338 gloves 384, 391 ff.
flexible 217, 330, 336 – dipping 391
– packaging 217 – disposable 391
flexing endurance 297 – fabric supported 394
flexographic 103 – polymeric 391
– ink formulation 107 – protective 396
– printing press 105 – testing 395
flexural strength 332 – unsupported 392
flocculation techniques 57 gradient polymer elution chromato-
flock lining 394 graphy 69
floor-covering adhesives 224 grain impregnation 287
flow behavior 44 gravure 103
flow curve 44 – ink 106
flow, Newtonian 45 – ink formulation 107
flow, pseudoplastic 45 – printing press 106
foam backing 257 – roll 206
foam impregnation 274 Green Label certification 227
foaming 6 – of adhesives 227
foaming behavior 48 green strength development 230
fogging test 300
foil duct tapes 208 h
folding carton inks 118 heat distortion temperature (HDT) 356
food packaging 7 heat resistance 116
form 386 heat sensitivity 33
– dipping 386 Helio test 100
form cleaning 391 high float emulsions 314
– dipping 391 hot light aging 300
formulation 86 f., 107, 117 ff., 141, 147 ff., hot mix asphalt 302 f.
150, 152 f., 156 f., 168, 171, 199 ff., 203 f., hydration 337
219, 224, 227 f., 233, 236, 239, 243, 245, 249, hydrodynamic particle diameter 50
263 f., 274, 388 hydrophobicity 332
free radical 18
free-radical polymerization 25 i
freeze-thaw 116, 245, 336 impact behavior 376
– stability 48 impact modification 370
functional monomers 26 impact modifiers 11, 367, 373, 375
furniture automotive 222 – non-weatherable 375
furniture leathers 295 – weatherable core shell 373
fusion promotion 359 impact performance 369, 372
impact resistance 367
g impurities 35 f.
gas chromatography 56 induction period 21
gas permeation 68 industrial maintenance coatings 155 ff.
gel effect 21 – application tests 156, 158
gel fraction 67 – formulation 157
gel permeation chromatography 69 – performance tests 156
glass transition temperature 1, 6, 60, 94, – salt spray testing 158
128, 154, 195, 288, 338, 357 inisurf 9
gloss 65, 93, 99, 112 initiation 18
gloss enamel 142 initiator 9, 31, 178
Index 403
– half-life 31 – structure 283

– thermal decomposition 32 leather articles 292
– thermally dissociating 31 leather finishing 285 f., 296
initiator systems 30 – test methods 296
– half-life 30 leather industry 283
– peroxides 30 leather production 284
– persulfate 30 letterpress 103
ink 93 life-cycle analysis 324
– absorption 93 light-fastness 300
– additives 113 light transmission 49
– color strength 114 liquid soaps 7
– composition 106 loaded wheel test (LWT) 322
– for films 117 loss modulus 63
– jet papers 81 low film forming temperature 112
– splitting 97 ff. low temperature cracking 306
in-line injection 311 lubrication 364
interior decorative coating 139 ff.
– adhesion test 144
– application tests 142 m
– block resistance 145 manufactures 12
– formulation 140 f. manufacturing processes 34
– freeze-thaw stability 142 – batch 34
– heat age stabilitiy 142 – continuous 34
– interior flat coatings 140 – plug-flow continuous reactor 34
– performance test 145 – semi-batch 35
– print resistance test 145 Maron plot 55
– scrub test 144 masking tapes 209
– stability heat age test 142 mastic products 231
– stain resistance test 144 mechanical characterization 62
– wall coatings enamels 140 mechanical stability 48
interior enamels 140 medical diagnosis 7
internal surface area 3 melt homogeneity 359
interparticle crosslinking 67, 70 melt rheology 363
intrinsic viscosity 69 melt strength 361
isolation technology 356 f. melt viscosity 362
membrane filtration techniques 58
j membranes 350 f.
joint filling compositions 233 – waterproof 350 f.
metallic effect 186
k metallic flog (MF) index 182
kaolin clay 86, 87 micellar nucleation 20
micelles 19
l microgels 70, 177
laboratory reactors 15 microorganisms 6, 203
laminating adhesives 217 f., 222 – protection against 203
laser light scattering 49 microscopic characterization 68
latex 3 microsurfacing 316, 321
– definition 3 – application test 321
– paints 125 – pavement 320
lawn and garden bag inks 118 Mie scattering 4
layers 166 milk carton ink 120
– automotive coatings 166 milk carton wet rub 116
leather 283, 291 mineral topcoats 344
– binder 291 miniemulsions 177
404 Index
minimum film formation temperature optical characterization 65

(MFFT) 59, 128 organic pigments 107
model system 17 original equipment manufacturers
modified fretting 323 (OEM) 164
modifier shell effects 372 – coatings 164
modulus of elasticity 336
moisture vapor transmission 247 p
molecular weight 69, 127, 357 P&I test 99
monomer 23 f., 94 packaging tapes 208
monomers 23, 25 f. paint formulations 125
– butadiene 24 paints 127
– concentration 21 – binder 127
– diene 24 paper coating 76, 79, 81, 84
– fox equation 23 – coating colors 84
– functional 26 – coating techniques 84
– major 23 paper gloss 84
– polymer design 25 paper industry 75 f.
– polymer properties 23 paper machine 78
– vinyl monomer 24 paper products 120
mortar 239, 241 ff., 348 ff. – inks 120
mottling 93, 99 paper properties 78
multiple wall bags 121 paperboard coatings 75
– inks 121 particle morphology 70
particle size 48, 94 f.
n particle size distribution 52, 94, 331
natural adhesives 192 – dispersion/redispersion 331
natural rubber latex 11, 303 particle surface 54
needlepunched carpet 255 patch mortar 346
neoprene latex 303 paving 303, 313
newspapers 121 peel resistance 229
– inks 121 – measurement 229
non-weatherable impact modifiers 375 peel strength 196, 210 ff.
non-weatherable PVC formulations 374 peel value 197
non-woven manufacturing systems 270 performance grading 304 f.
non-wovens 267 ff. permanent deformation 306
– application tests 275 permanent paper label 203
– applications 268 permeability 7
– binders 273 permeation 66
– standard test methods 276 pH 43
notch sensitivity 370 photon correlation spectroscopy 49
pick strength 93
o – see binding strength
OEM coatings 164 pigments 82 ff., 109, 132, 202
offset printing 82, 85, 93 ff. – coat 288
– rotogravure printing 93 – dispersion 108
– sheet-fed 85 f. – dispersion stability 104
– web offset printing 93 – extender 132
offset test 99 – surface treatment 109
oligomeric radicals 20 – volume content of paints (PVC) 125 f.
opacifying aids 134 plastic materials 355
– hollow sphere particles 134 – modification 355
– TiO2 134 plasticizer 201, 286
opacity 82, 86, 93 – migration 286
open time 113, 230 plastics production 10
Index 405
plywood on lumber shear test 232 pre-mixed 332

polyacrylate dispersions 194, 291 pre-packed 332
– leather-finishing 291 pre-print corrugated inks 119
polyacrylates 11 pressure sensitive adhesives 193, 205, 207,
polybutadiene dispersions 291 210
polychloroprene adhesives 225 – test methods 210
poly-coated board 120 pressurized aging vessel (PAV) 304
polyken probe tack 214 primer 172 f.
polymer characterization 68 – composition 173
polymer colloids 1 – formulations 152 f.
polymer compositions 129 – polymers used 172
– binder 129 – requirements 172
– styrene-butadiene copolymers 129 – surfacer 172
polymer corporation 131 primer coating 151 ff.
– acrylic copolymers 131 – application tests 153
– specialty monomers 131 – marker stain resistance 153
polymer design 25 – stain blocking 153
polymer dispersion 2 f., 10 ff., 41, 273 print bonding 274
– characterization 41 printability 93
– chemical bonding 273 printability tests 99
– commercial importance 10 printing 103
– definition 3 printing inks 103, 115
– manufactures 12 – tests 115
– names 2 printing processes 92, 103
– properties 3 probe tack method 214
– suppliers 13 process aids 355
– synthesis 15 process conditions 37
polymer films 58 – branching 37
polymer isolation technology 357 – crosslinking 37
polymer modified cement concrete – monomer/polymer concentration 37
(PCC) 349 – number of particles 38
polymer strength 6 – temperature 38
polymer/cement ratio 337 processing aids 359 ff.
– flexibility 337 – effect 366
polymeric impact modifiers 355 – for PVC 359
polymeric modifiers 358 – for resins 366
– classification 358 – types 364
– processing aids 358 product resistance 116
polymeric gloves 397 propagation 18
– standard test 397 propagation rate 21
polymerizable surfactants 30 propene 9 f.
polymer-modified asphalt 309 protective coatings 123, 154
polymer-modified mortars 241 protective colloid 6, 9
polyolefins 10 protective films 209
polystyrene 10 protective gloves 384
polystyrene dispersions 7 pulp 77 ff.
polyurethane adhesives 223 pulp suspension 79
polyurethane dispersions 7, 170, 172, 175, pump-in 311
179 ff., 191, 217 f., 222 f., 285, 288, 292 PVC durables 373
polyurethanes 110 PVC formulations 371
polyvinyl acetate 90 – for building products 371
polyvinyl alcohol 88 ff., 332
polyvinyl chloride 10
porosity 93
406 Index
q – types 235
quasielastic light scattering 49 seed polymer 39
quick-stick 213 seeded emulsion polymerization 20
seeded processes 29
r selected conversion processes 364
raspberry structure 4, 5 self-adhesive articles 210
rate of polymerization 19, 21 – labels 194, 205
raw hide production 285 – products 199
raw materials 8 – tapes 207
reactive monomers 9 self-leveling underlayments (SLU) 345
recycling 10 serum separation techniques 57
redispersible powders 329, 332, 339 shear strength 198, 210, 216, 229
– adhesion 339 – measurement 216
– building materials 329 shear thinning 45
– building/construction industry 329 shear value 197
– dry mix mortar technology 329 shoe upper leather 292
– premixed 329 shotcrete process 350
– pre-packed 329 silane-based coupling 235
repair mortar 241, 346, 350 size press 79
residual volatiles 56 sizing agent 78, 80
residue characterization 319 – low molecular weight 80
resin 104 – polymeric 80
– support 110 slot-die coating 207
resinated pigments 109 SLU 345, 347
resistance to flow 237 – abrasion resistance 347
re-solubility 112 – surface 347
reverse gravure 205 slurry seal 316
re-wetting 116 soap titration 55
rheology control agent 181 solids content 42
roll coating 289 f. solubility parameters 67
rolling ball 215 solution polymers 113
roof coating 248 solution vehicles 112
rosin fumarate ester 110 solvent based ink 103
rosin fumarates 104 soy protein 90 f.
rotating thin film oven test (RTFOT) 304 spray drying 330, 357
rotogravure printing 82 f., 86, 94, 99 – emulsion polymerization 330
rubber milk 3 spray-dry process 331
rub-fastness 298 spray dyeing 287
rub test – metal corrugator 116 spray machine 289
rutting 306 spraying 289
stability 47
s starch 79 ff., 88, 90 f.
safety 40 static light scattering 51
– capacity limitation 40 steady shear viscosity profile 182
– design pressure 40 steam cracker products 8
– relief devices 40 storage modulus 63
sand 333 storage stability 48
saturation 274 stress-strain measurements 62
scale-up criteria 15 styrene 10, 90, 94
scrim coat 262 styrene-butadiene dispersions 6, 90, 129,
sealant 233 f., 236 f. 204, 217, 256 ff., 273 f.
– production 237 styrene-butadiene rubber (SBR) latex 227,
– slurries 351 256 ff., 303 ff.
– tensile stress values 236 sub-floor mastics 231
Index 407
superpave binder specification 305 transparency 6, 65

superpave performance grade 304 tufted carpet 254 ff.
surface-active materials 27
surface print inks 118 u
surface sizing 76, 79 ff. unitary coating 264
surface tension 43
surface tension of films 117 v
surface treatment 108, 314 vario gravure 206
– of pigments 109 vinyl acetate copolymers 6, 11, 90, 130, 141,
surfactant 27 ff., 114 273 f., 330 ff.
– physical properties 27 vinyl chloride 10
– structural influences on properties 28 vinylidene chloride 7
surfmer 9 viscosity 5 f., 45, 96, 182
swelling 66 – dilatant 6
synthetic additives 78 – pseudoplastic 5
synthetic adhesives 192 – shear rate 5
– thixotropic 5
t viscosity, Zahn efflux cup 117
tack 6, 195, 210, 213 volatile organic compounds (VOC) 165, 258
tackifying resins 200
tack measurement method 214 w
tanning 283 wall coatings 139
tensile strength 63 wall mastics 231
termination 18 water based ink 103
test methods 97 f., 114 f., 142 ff., 147 f., 151, water impermeability 332
156 f., 159 f., 168 ff., 210 ff., 221 f., 228 ff., water loss of green concrete 248
232, 237 f., 240, 246 f., 249, 261, 275 ff., water resistance 117
296 ff., 304 ff., 335 ff., 368, 395 ff. water uptake 67
thermoset coatings 183 water-borne binders 176
thick bed mortar technique 334 – aqueous polyurethane dispersions 179
thickeners 7, 84 ff., 133, 235, 390 – for automotive coating 179, 181
– anionic 235 – rheology control agents (RCA) 181
– dipping compounds 390 – secondary acrylic dispersions 179
thickening 201 water-borne coatings 163
thin bed mortar technique 334 – applicaton properties 185
thixotropy 45 water-borne emulsion polymers 124
tile adhesives 240 waterproofing membranes 244, 250, 350
– test methods 240 waterproofing sealing 351
tile grouts 332, 334, 340 f. waterproofing system 350
– ANSI Standards 341 water-soluble binders 185
– EN Standards 341 – properties 185
titanium dioxide 84, 86, 132 f., 147, 160, water-soluble oligomers 4
202 wax emulsions 113
top coats 288, 341, 344 weatherability 374
torque rheometry 360 weatherable impact modifiers 373
toughness 63, 367 web consolidation 272
towel and tissue ink 122 – chemical bonding 272
traffic marking paints 158 ff. – mechanical bonding 272
– application tests 159 f. – thermal bonding 272
– dry-through time 159 web formation 271
– formulation 160 – dry-laid 271
– no-pick-up test 160 – spun-laid 271
– retro-reflectance 160 – wet-laid 271
transmission electron microscopy 70 wet adhesion 299
408 Index
wet finishing 286 y

wet pick strength 94 ff. yellowing 94, 299
wet track abrasion test (WTAT) 322 Young’s modulus 62
wetting 65
wetting agents 201 z
wetting aids 136 zeta potential 56
white-point temperature 60 Zosel tack measurement 215
workability 332
work of fracture 63
woven carpet 254 f.

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Polymer Dispersions and Their Industrial Applications.

Edited by Dieter Urban and Koichi Takamura

edited by Dieter Urban and

Editors This book was carefully produced. Never-

Library of Congress Card No.:

British Library Cataloguing-in-Publication Data

Die Deutsche Bibliothek – CIP Cataloguing-

© 2002 Wiley-VCH Verlag GmbH,

Printed in the Federal Republic of Germany

2 Synthesis of Polymer Dispersions 15

3 Characterization of Aqueous Polymer Dispersions 41

3.3 Polymer Films 58

4 Applications in the Paper Industry 75

5 Applications for Printing Inks 103

5.7.1 Multiple Wall Bags 121

6 Applications for Decorative and Protective Coatings 123

6.9 Traffic Marking Paints 158

7 Applications for Automotive Coatings 163

8 Applications in the Adhesives and Construction Industries 191

8.4.7 Elastomeric Roof Coatings 247

9 Applications in the Carpet Industry 253

10 Non-wovens Application 267

11 Applications in the Leather Industry 283

11.6 Production of Selected Leather Articles 292

12 Applications for Asphalt Modification 301

13 Applications of Redispersible Powders 329

14 Applications for Modification of Plastic Materials 355

15 Applications for Dipped Goods 383

Charlotte, North Carolina, USA Dieter Urban

Fig. 4-7 Effect of coated paper on offset printing.

Fig. 4-8 Effect of coated paper on rotogravure printing.

Fig. 12-15 Photo-

Dieter Urban and Dieter Distler

Swedish, Turkish) and emulsions (Arabic, Chinese, English, Indonesian, Italian,

The aggregate state of a polymer dispersion is thermodynamically unstable. The very

Fig. 1-2 What is a polymer dispersion?

Fig. 1-4 Electron photomicro-

Polymer dispersions with a high amount of acrylic/methacrylic acid convert to

Fig. 1-6 Steam cracker products.

Propene cannot be polymerized by means of free radicals. It is, however, a feed-

Million Metric tons

Other 14% Polymer Dispersions (dry) 4%

Fig. 1-8 Production by polymer class [21].

state of aggregation of the dispersions is consequently often more important than

Fig. 1-9 Aqueous polymer dispersions by product class.

Company Product lines Applications Trade names

Fig. 1-10 Major suppliers of aqueous poly- dispersions, PU polyurethane dispersions,

Fig. 2-1 Typical laboratory

Fig. 2-2 Laboratory equipment

Ingredient Quantity Influence

Water 100–150 Solids content; viscosity

1 Parts per hundred parts of monomer

ization, the monomer is dispersed in droplet form in a continuous medium that is

Fig. 2-3 Emulsion polymerization [7].

Within an individual particle, assuming an active radical is present, the rate of

1.6 Fig. 2-4 Typifying the

Fig. 2-6 Conversion- 100

Tab. 2-2 Some major monomers used in emulsion polymerization.

Monomer Structure Normal Tg of homo-

1,3-Butadiene CH2=CH–CH=CH2 –4.4 –85

Fig. 2-7 Possible *

Tab. 2-3 Some aspects of polymer design through composition.