1.

POLYMER BASICS
1.1. Introduction
Polymeric materials have been used since early times, even though their exact nature
was unknown. In the 1400s, Christopher Columbus found natives of Haiti playing with
balls made from material obtained from a tree. This was natural rubber, which became
an important product after Charles Goodyear discovered that the addition of sulfur
dramatically improved the properties; however, the use of polymeric materials was still
limited to natural-based materials. The first true synthetic polymers were prepared in the
early 1900s using phenol and formaldehyde to form resins-Baekelands Bakelite. Even
with the development of synthetic polymers, scientists were still unaware of the true
nature of the materials they have prepared. For many years, scientists believed they
were colloids - a substance that is an aggregate of molecules. It was not until the 1920s
that Herman Staudinger showed that polymers were giant molecules or
macromolecules. In 1928, Carothers developed linear polyesters and then polyamides,
now known as nylon. In the 1950s, Ziegler and Nattas work on anionic coordination
reactions catalyzed to the development of polypropylene; high-density, linear
polyethylene; and other stereospecific polymers.

Materials are often classified as metals, ceramics, or polymers. Polymers differ from the
other materials in a variety of ways but generally exhibit lower densities, thermal
conductivities and moduli. A comparative study of the properties of polymers has been
made against metals and ceramics with the findings as shown in the table below:

Table: 1.1.

Materials Specific Thermal Electrical Modulus

gravity Conductivity, Resistivity, (MPa)
-cm
(J-cm/o C cm2
s)
Aluminium 2.7 2.2 2.9 70000
Brass 8.5 1.2 6.2 110000
Metals Copper 8.9 4.0 1.7 110000
Steel (1040) 7.85 0.48 17.1 205000
Alumina(Al2o3) 3.8 0.29 >1014 350000
Concrete 2.4 0.01 - 14000
Ceramics Borosilicate 2.4 0.01 >1017 70000
glass

1
 MgO 3.6 - 105 205000
(2000oC)
High density 0.96 0.0052 1014-1018 350-1250
polyethylene
Plastics Polystyrene 1.05 0.0008 1018 2800
Polymethyl 1.2 0.002 1016 3500
methacrylate
Nylon 1.15 0.0025 1014 2800

The lower densities of polymeric materials offer an advantage in applications where

lighter weight is desired. The addition of thermally and/or electrically conducting fillers
allows the polymer compounder the opportunity to develop materials from insulating to
conducting. As a result, polymers may find application in electromagnetic interference
(EMI) shielding and antistatic protection.

Polymeric materials are used in a vast array of products. In the automotive area, they
are used for interior parts and in under-the-hood applications. Packaging applications
are a large area for thermoplastics, from carbonated beverage bottles to plastic wrap.
Application requirements vary widely, but, luckily, plastic materials can be synthesized
to meet these varied conditions.

1.2. Definitions
What is a "Polymer"?

The word Polymer finds its origin from the Greek "poly" meaning many, and "meros",
parts or units. A polymer is a group of many units. You combine many monomers (one
unit) to create a polymer.

How are polymers formed?

Polymers are formed by the process of polymerization. It is a chemical process in which

an entire molecular structure is generated through repetition of one or more monomer
units.

Degree of Polymerization (D.P.)

The term degree of polymerization gives us the number of monomer units consumed to
form a polymer molecule. Hence it is a measure of the molecular weight of the polymer.

Molecular Weight of polymer = Molecular Weight of each repeating unit X D.P.

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 Simulation of Polymerization Process

= An individual monomer unit

POLYMERIZATION

Polymer

D.P. = 8

Consider each to be an ethylene (CH2=CH2) unit, then the combination of several

thousands of such units would yield a polyethylene --- (--CH2-CH2--) n---- polymer
molecule.

Depolymerization

It is the process of converting a polymer into a monomer or a mixture of monomers.

Unzipping is depolymerization occurring by a sequence of reactions, progressing along

a macromolecule and yielding products, usually monomer molecules, at each reaction
step, from which macromolecules similar to the original can be regenerated.

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 1.3. Classification of Polymers

Polymers

Natural Synthetic Semi-Synthetic

Polymers Polymers Polymers
Eg. : Cellulose, Silk, Polysaccharides etc. Eg. : Cellulose nitrate, Rayon, etc.

Thermal Monomer Type of Type of Type of Type of Application

Behavior sequence Monomer Reaction Process Structure Wise
Polyethylene Molding
Thermoplastic Polypropylene
Extrusion
Thermoset Polystyrene,
Linear Branched Crosslinked Thermoforming, etc.
etc.
Condensation Addition

Bulk Emulsion

Homopolymer Copolymer
Suspension Solution

Polymers are broadly classified based upon their availability to mankind. Thus two
different types of polymers are classified as Natural polymers and Synthetic polymers.
However man has been able to modify the properties of some naturally occurring
polymers by virtue of certain chemical treatments. They have gradually emerged as a
new class of polymers called the semi-synthetic polymers.

a) Natural polymers
b) Synthetic polymers
c) Semi-synthetic polymers

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1.3.1. Natural Polymers
Years ago, before there were plastics and synthetic polymers, in fact, all the way back
to the beginning of the earth, nature was using natural polymers to make life possible.
Natural polymers include the RNA and DNA that are so important in genes and life
processes. In fact, messenger RNA is what makes possible proteins, peptides, and
enzymes. Enzymes help do the chemistry inside living organisms and peptides make up
some of the more interesting structural components of skin, hair, and even the horns of
rhinos. Other natural polymers include polysaccharides (sugar polymers) and
polypeptides like silk, keratin, and hair. Natural rubber is, naturally a natural polymer
also, made from just carbon and hydrogen. Let's look at each of the main families of
natural polymers closely.

The different types of natural polymers include the following:

1) Polysaccharides

1a) DNA and RNA - They contain polymer backbones which are based on sugar units.
This makes them polysaccharides, although in the case of RNA and DNA, there are well
ordered groups attached to the sugar units that give these polymers their unique
capabilities.

1b) Wood and potatoes - Another family of polysaccharides includes starch and
cellulose. Starch is a high molecular weight polysaccharide. Foods like bread, corn, and
potatoes are full of starch. Starch may have as many as 10,000 sugar units all linked
together. Another very important member of the polysaccharide family is cellulose. This
is the main polymer that makes up plants and trees. Wood is primarily cellulose. This
polymer is different than starch. Starch is soluble in hot water and can easily be made
into useful objects. Cellulose, on the other hand, is highly crystalline and almost totally
insoluble in anything. Cotton is a form of cellulose that is used in most of our clothes.

1c) Chitin - Another member of the polysaccharides is chitin. It makes up the shells of
crawfish, shrimp, crabs, lobsters, and other crustaceans. It is hard, insoluble and yet
somehow flexible. Chemically, chitin is poly (N-acetylglucosamine).

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2) Proteins and Polypeptides

2a) Proteins - These were the first examples of polyamides. Both share many common
traits but they are very different in how they are made and in their physical properties.
They are alike in that the both contain amide linkages in the backbone.

2b) Enzymes These are one of the key types of polypeptides and are crucial to life on
earth. Enzymes are the catalysts that do specific jobs. In fact, oftentimes each enzyme
does only one type of job or makes only one kind of molecule. This means that there
have to be lots of different enzymes, all made of different combinations of amino acids
joined in unique ways in polypeptides, to do all the jobs that any living organism needs
done.

2c) Silk - One of the unique polypeptides that we used very early for its superb
properties was silk. Silk is made by tiny caterpillars trying to spin cocoons for their
transformation into moths. The silk is spun into fibers. The structure of silk molecules is
unusual for a polypeptide. It possesses lots of the unsubstituted amino acid, glycine.

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3) Polyisoprene (Natural rubber)

Natural rubber is an elastic hydrocarbon polymer that naturally occurs as a milky

colloidal suspension, or latex, in the sap of some plants. It can also be synthesized. The
scientific name for the rubber tree is Hevea brasiliensis.

1.3.2. Synthetic polymers

These materials do not occur in nature. Hence man has to synthesize them by means of
different chemical reactions called polymerization. The maximum number of polymers
comes under this group. Synthetic polymers can be reclassified based upon their
thermal behavior, monomer sequence, types of monomers, type of reaction, type of
process, nature of application and type of structure.

1.3.2.1. Thermal Behavior

a) Thermoplastics These are polymers having the property of softening or fusing when
heated and of hardening and becoming rigid again when cooled. Thermoplastic
materials can be remelted and cooled time after time without undergoing any
appreciable chemical change. Examples are:

i. Polyethylene (PE)
ii. Polypropylene (PP)
iii. Polystyrene (PS)
iv. Polyethylene terephthalate (PET)

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 Table: 1.3.1. Physical properties of some common Thermoplastics

Thermoplastic Density Tensile Tensile Coefficients Thermal Specific Maximum

2
(g/cm ) Yield Modulus of Conductivity Heat Temperature
Strength (103 Linear (Btu in /h ft2 (Btu/lb Limit
o o
(103 psi) psi) Expansion F) F) o o
( F/ C)
(106 in/in
o
F)

ABS 1.08 7.0 340 60 1.35 0.34 180/80

PVC 1.4 8.0 410 30 1.1 0.25 150/65

PE 0.95 3.2 120 90 3.2 0.55 160/70

PB 0.92 4.2 55 72 1.5 0.45 210/100

PVDF 1.76 7.0 220 70 1.5 0.29 300/150

b) Thermosets These are polymers having the property of becoming permanently

hard and rigid when heated or cured during their processing and thus become infusible
and insoluble.

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 Table: 1.3.2. Physical properties of some Filled Thermosets

Tensile Impact Dielectric Max. use

Density Strength strength strength temperature
Materials
(gm/cm3) Izod (ft
(*1000 psi) lb/in) (V/mil) F C

Phenolic

Wood Flour
filled 1.34-1.45 5-9 0.2-0.6 260-400 300-350 150-177

Mica Filled 1.65-1.92 5.5-7 0.3-0.4 350-400 250-300 120-150

Glass filled 1.69-1.95 5-18 0.3-18 140-400 350-550 177-288

Polyester

Glass filled
SMC 1.7-2.1 8-20 8-22 320-400 300-350 150-177

Glass filled
BMC 1.7-2.3 4-10 15-16 300-420 300-350 150-177

Melamine

Cellulose
filled 1.45-1.52 5-9 0.2-0.4 350-400 250 120

Flock Filled 1.50-1.55 7-9 0.4-0.5 300-330 250 120

Glass Filled 1.8-2.0 5-10 0.6-18 170-300 300-400 150-200

Urea,
Cellulose
Filled 1.47-1.52 5.5-13 0.2-0.4 300-400 170 77

Alkyd

Glass Filled 2.12-2.15 4-9.5 0.6-10 350-450 450 230

Mineral
Filled 1.60-2.30 3-9 0.3-0.5 350-450 300-450 150-230

Epoxy (bis A)

No Filler 1.06-1.40 4-13 0.2-10 400-650 250-500 120-260

Mineral
Filled 1.6-2.0 5-15 0.3-0.4 300-400 300-500 150-260

Glass Filled 1.7-2.0 10-30 - 300-400 300-500 150-260

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Common examples include the following:

i. Bakelite (Phenol-Formaldehyde Resin)

ii. Urea formaldehyde resin
iii. Epoxy resin

1.3.2.2. Monomer Sequence

a) Homopolymers They are composed of only a single type of repeating (chemical)

unit or monomer.

Examples:

i. Polyethylene (PE)

ii. Polypropylene (PP)

iii. Polystyrene (PS)

b) Copolymers They consist more than one type of repeating unit (monomer).

Again, four different types of copolymers are known:

i. Alternate Copolymers

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 The different monomer units place themselves in an alternative sequence
in the polymer chain thereby maintaining a typical order.

ii. Random Copolymers

They are devoid of any definite sequence of arrangement of the monomer

units in their chains.
Examples:
Ethylene Propylene Rubber (EPR, EPDM)

Styrene Butadiene Rubber (SBR)

iii. Block Copolymers

They are characterized by long sequences or blocks of polymer units from

a particular monomer followed by units from other monomers.
Example: Styrene-Butadiene-Styrene triblock copolymer

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 iv. Graft Copolymers

This class of copolymers has polymer branches from one monomer

attached to the main chain (backbone) of polymer from other monomer.
Examples include Acrylonitrile Butadiene Styrene (ABS) resin, Maleic
anhydride grafted polyethylene, etc.

1.3.2.3. Type of Monomers

Based upon the chemical nature of monomers the polymers can be classified
accordingly. Some examples are:

i. Polyolefins like Polyethylene & Polypropylene

ii. Polyamides like Nylon 6, Nylon 11, Nylon 66
iii. Polyesters like Polyethylene terephthalate & Polybutylene terephthalate

1.3.2.4. Type of Reactions

Synthetic polymers are produced by certain chemical reactions called polymerization

reactions. Based upon the nature of these polymerization reactions, they can be
classified as follows:

i. Addition Polymers
e.g. Polyolefins
ii. Condensation polymers
e.g. Polyamides

1.3.2.5. Type of Process

A polymerization reaction can occur by different processes like bulk polymerization,

solution polymerization, suspension polymerization and emulsion polymerization.
Depending upon the type of the polymerization process, polymers can be classified as:

i. Bulk Polymers
ii. Solution Polymers
iii. Suspension /Slurry Polymers
iv. Emulsion Polymers

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1.3.2.6. Type of Structure

The structure of the polymer chain can play a pivotal role in determining its various
physical and mechanical properties like density, strength and toughness, etc. Thus
another way of classifying polymers is by its structure, which can be of the following
types:

i. Linear Polymers

e.g. Polyethylene terephthalate

ii. Branched Polymers

a) Short chain branched

e.g. Linear Low Density Polyethylene

b) Long chain branched
e.g. Low density Polyethylene - having both long as well as short chain
branching.

iii. Crosslinked Polymers

Polymers in which the individual chains are covalently bonded to each other thereby
leading to the formation of a three dimensional network fall under this category.

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Examples of crosslinked polymers are:

a) Vulcanized rubber
b) Bakelite
c) Polyimides

Apart from classification of polymers as linear, branched or crosslinked, they can be

called crystalline, amorphous or liquid crystalline depending upon the pattern of
molecular arrangement of the polymer chains.

Crystalline Polymers

Highly crystalline polymers are rigid, high melting, and less affected by solvent
penetration. Crystallinity makes a polymer strong, but also lowers their impact
resistance. As an example, samples of polyethylene prepared under high pressure
(5000 atm) have high crystallinities (95 - 99%) but are extremely brittle.

Polymer molecules are very large so it might seem that they could not pack together
regularly and form a crystal. It now is known that regular polymers may form lamellar
(plate-like) crystals with a thickness of 10 to 20 nm in which the parallel chains (shown
in different colors in the simulated structure at the right) are perpendicular to the face of
the crystals.

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Amorphous Polymers

Polymer chains with branches or irregular pendant groups cannot pack together
regularly enough to form crystals. These polymers are said to be amorphous. A two-
dimensional schematic of an amorphous polymer is shown below.

Amorphous regions of a polymer are made up of randomly coiled and entangled chains.
They have been compared to a bucket containing a large number of entangled worms -
each one 20-foot long and of 1/4-inch thickness. The worms are so tangled that an
entire worm cannot slide past the others, but small portions of the worms can twist
around within the mass. Amorphous polymers are softer, have lower melting points, and
are penetrated more by solvents than are their crystalline counterparts.

1.3.2.7. Application wise

Polymers, particularly plastics go into applications as finished products which involve

their processing by either molding or extrusion. Thus they are classified as

i. Molding grades
This class includes plastics for blow molding, roto molding, injection molding, etc.
ii. Extrusion grades
Plastics for film application, stretch tapes, pipes, profiles, sheets, etc. fall under
this class.

1.3.3. Semi-Synthetic Polymers

These are naturally occurring polymers that have been modified synthetically to meet
certain requirements pertaining to some special applications. Examples include
Cellulose nitrate, carboxymethyl cellulose, celluloid, halogenated/hydrogenated natural
rubber, etc.

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1.4. Polymer Properties
Types of polymer 'properties' can be broadly divided into several categories based upon
scale. At the nano-micro scale are properties that directly describe the chain itself.
These can be thought of as polymer structure. At an intermediate mesoscopic level are
properties that describe the morphology of the polymer matrix in space. At the
macroscopic level are properties that describe the bulk behavior of the polymer.

1.4.1. Structural Properties

The structural properties of a polymer relate to the physical arrangement of monomers
along the backbone of the chain. Structure has a strong influence on the other
properties of a polymer. For example, a linear chain polymer may be soluble or
insoluble in water depending on whether it is composed of polar monomers (such as
ethylene oxide) or nonpolar monomers (such as styrene). On the other hand, two
samples of natural rubber may exhibit different durability even though their molecules
comprise the same monomers. Polymer scientists have developed terminology to
precisely describe both the nature of the monomers as well as their relative
arrangement:

1.4.1.1. Monomer Identity

The identity of the monomers comprising the polymer is generally the first and most
important attribute of a polymer. Polymer nomenclature is generally based upon the
type of monomers comprising the polymer. Polymers that contain only a single type of
monomer are known as homopolymers, while polymers containing a mixture of
monomers are known as copolymers. Poly (styrene), for example, is composed only of
styrene monomers, and is therefore is classified as a homopolymer. Ethylene-vinyl
acetate, on the other hand, contains more than one variety of monomer and is thus a
copolymer. Some biological polymers are composed of a variety of different but
structurally related monomers, such as polynucleotides composed of nucleotide
subunits.
A polymer molecule containing ionizable subunits is known as a polyelectrolyte. An
ionomer is a subclass of polyelectrolyte with a low fraction of ionizable subunits.

1.4.1.2. Chain Linearity

The simplest form of polymer molecule is a straight chain or linear polymer, composed
of a single main chain. The flexibility of an unbranched chain polymer is characterized
by its persistence length. A branched polymer molecule is composed of a main chain
with one or more substituent side chains or branches. Special types of branched

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polymers include star polymers, comb polymers, and brush polymers. If the polymer
contains a side chain that has a different composition or configuration than the main
chain, the polymer is called a graft or grafted polymer. A cross-link suggests a branch
point from which four or more distinct chains emanate. A polymer molecule with a high
degree of crosslinking is referred to as a polymer network. Sufficiently high crosslink
concentrations may lead to the formation of an 'infinite network', also known as a 'gel', in
which networks of chains are of unlimited extend - there is essentially all chains have
linked into one molecule.

1.4.1.3. Chain Size

Polymer bulk properties may be strongly dependent on the size of the polymer chain.
Like any molecule, a polymer molecule's size may be described in terms of molecular
weight or mass. In polymers, however, the molecular mass may be expressed in terms
of degree of polymerization, essentially the number of monomer units that comprise the
polymer. For synthetic polymers, the molecular weight is expressed statistically to
describe the distribution of molecular weights in the sample. This is because of the fact
that almost all industrial processes produce a distribution of polymer chain sizes.
Examples of such statistics include the number average molecular weight and weight
average molecular weight. The ratio of these two values is the polydispersity index,
commonly used to express the "width" of the molecular weight.
The space occupied by a polymer molecule is generally expressed in terms of radius of
gyration or excluded volume.
The maximum length of a polymer chain is its contour length.

1.4.1.4. Tacticity in polymers with chiral centers

This property describes the relative stereochemistry of chiral centers in neighboring
structural units within a macromolecule. There are three types: isotactic, atactic, and
syndiotactic.
Generally, tacticity applies to addition polymers with one non-hydrogen substitute
attached to the carbon chain for each monomer unit:

H H
| |
-(- C - C -)-
| |
H R
Tacticity has to do with which side of the chain the R group is placed. Fischer
projections can be used to show the three different types of tacticity:

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 Isotactic

It is to be noted that all of the R groups line up on the same side.

Syndiotactic

Here the R groups alternate from side to side.

Atactic

However, here the side to side positioning of R groups is random.

1.4.1.5. Head-Tail Placement

Head-tail placement has to do with which carbon the R group is placed on (rather than
which side the R group is on as in tacticity).

H H
| |
C-C
| |
H R

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The carbon with the R on it can be called the "head", and then to maintain consistency,
the carbon, and the carbon without the R should be called the tail. It has been observed
that polystyrene connection with two benzene groups on adjacent carbons is called a
"head-to-head" placement, so from this it follows that the presence of an R group on a
carbon makes that carbon a "head" carbon.

H H H H
| | | |
C-C-C-C Head to Tail placement
| | | |
H R H R

H H H H
| | | |
C-C-C-C Head to Head placement
| | | |
H R R H

H H H H
| | | |
C-C-C-C Tail-to-Tail placement
| | | |
R H H R

However tail-to-tail placement is the least referred as it is just as legitimate as head-to-

head placement.

1.4.2. Morphological Properties

1.4.2.1 Crystallinity
When applied to polymers, the term crystalline has a somewhat ambiguous usage. In
some cases, the term crystalline finds identical usage to that used in conventional
crystallography. For example, the structure of a crystalline protein or polynucleotide,
such as a sample prepared for x-ray crystallography, may be defined in terms of a
conventional unit cell composed of one or more polymer molecules with cell dimensions
of hundreds of angstroms or more.
A synthetic polymer may be described as crystalline if it contains regions of three-
dimensional ordering on atomic (rather than macromolecular) length scales, usually
arising from intramolecular folding and/or stacking of adjacent chains. Synthetic
polymers may consist of both crystalline and amorphous regions; the degree of

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crystallinity may be expressed in terms of a weight fraction or volume fraction of
crystalline material. Few synthetic polymers are entirely crystalline.

1.4.3. Bulk Properties

The bulk properties of a polymer are those most often of end-use interest. These are
the properties that dictate how the polymer actually behaves on a macroscopic scale.

1.4.3.1. Tensile strength

The tensile strength of a material quantifies how much stress the material will endure
before failing. This is very important in applications that rely upon polymer's physical
strength or durability. For example, a rubber band with a higher tensile strength will hold
a greater weight before snapping. In general tensile strength increases with polymer
chain length.

1.4.3.2. Young's Modulus of elasticity

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Young's Modulus quantifies the elasticity of the polymer. It is defined, for small strains,
as the ratio of rate of change of stress to strain. Like tensile strength this is highly
relevant in polymer applications involving the physical properties of polymers, such as
rubber bands.

1.4.3.3. Shear Modulus

In materials science, shear modulus or modulus of rigidity, denoted by G, or sometimes
S or , is defined as the ratio of shear stress to the shear strain. Shear modulus is
usually measured in GPa (gigapascals) or ksi (thousands of pounds per square inch).

Where F = Tangential force

A = Surface area
x = Transverse displacement
h = Initial length

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1.4.3.4. Compressive Strength & Modulus

The compressive strength of a material is the compressive force per unit area that it
can withstand.

Table: 1.4.1. Typical Compressive Yield Strength and Modulus of Polymers

Polymer Type Compressive Yield Compressive Modulus

Strength (MPa) (GPa)

ABS 65 2.5

ABS + 30% Glass Fiber 120 8

Acetal Copolymer 65 2.5

Acetal Copolymer + 30% 100 7.5

Glass Fiber

Acrylic 110 3

Nylon 6 50 2.3

Polyamide-Imide 130 5

Polycarbonate 70 2.0

Polyethylene, MDPE 20 0.7

Polyethylene 80 1
Terephthalate (PET)

Polyimide 150 2.5

Polyimide + Glass Fiber 220 12

Polypropylene 40 1.5

Polystyrene 70 2.5

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1.4.3.5. Flexural Strength & Modulus

The flexural strength of a material is defined as its ability to resist deformation under
load. For materials that deform significantly but do not break, the load at yield, typically
measured at 5% deformation/strain of the outer surface, is reported as the flexural
strength or flexural yield strength. The test beam is under compressive stress at the
concave surface and tensile stress at the convex surface.

Table: 1.4.2. Typical Flexural Strength and Flexural Modulus of Polymers

Polymer Type Compressive Yield Compressive

Strength (MPa) Modulus (GPa)

ABS 65 2.5

ABS + 30% Glass 120 8

Fiber

Acetal Copolymer 65 2.5

Acetal Copolymer + 100 7.5

30% Glass Fiber

Acrylic 110 3

Nylon 6 50 2.3

Polyamide-Imide 130 5

Polycarbonate 70 2.0

Polyethylene, MDPE 20 0.7

Polyethylene 80 1
Terephthalate (PET)

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 Polyimide 150 2.5

Polyimide + Glass 220 12

Fiber

Polypropylene 40 1.5

Polystyrene 70 2.5

In many applications for reinforced plastics, especially reinforced polyolefins such

as polypropylene and thermoplastic olefins, the product must not only be strong, but
also stiff or rigid to perform as designed. This stiffness is known as the flexural
modulus of the plastic and is expressed in Pascals (Pa) or as pounds per square
inch (psi).
1.4.3.6. Impact Strength

This property determines the ability of the material under consideration to withstand
instant shock loading. There may various impact strength of a plastic material can be
expressed by various terms depending upon the test procedure namely:
a) Izod impact
Specimen is held as a vertical cantilevered beam and is broken by a pendulum.
Impact occurs on the notched side of the specimen.

b) Charpy impact
Specimen is held as a simply supported beam and is impacted on the side opposite
the notch.

c) Tensile Impact
The tensile impact test measures the amount of force needed to break a specimen
under a high speed tensile load introduced through a swinging pendulum. The
thickness and width of the test specimen is recorded. The specimen is then

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 clamped to the crosshead and placed into the pendulum. The pendulum is released
and allowed to strike the anvil breaking the specimen. The tensile impact energy is
recorded and then corrected impact energy is calculated.

d) Falling Weight Impact

For impact resistance testing of plastic film, sheet, and laminated
materials, a specific weight is dropped from a specific height onto a firmly
held sample to determine a 50% failure rate. It gives an idea of the
resistance of the material against failure under multi-axial stress.

1.4.3.7. Stress Relaxation

Stress relaxation describes how polymers relieve stress under constant strain. Polymers
exhibit stress relaxation owing to the fact that they are viscoelastic in nature, i.e. they
have both the properties of an elastic solid material as well as a viscous liquid material.

1.4.3.8. Creep

Creep is the term used to describe the tendency of a solid material to slowly move or
deforms permanently to relieve stresses. It occurs as a result of long term exposure to
levels of stress that are below the yield strength or ultimate strength of the material.
Creep is more severe in materials that are subjected to heat for long periods, and near
the melting point. Creep deformation is "time-dependent" deformation.

1.4.4. Transport Properties

Transport properties such as diffusivity relate to how rapidly molecules move through
the polymer matrix. These are very important in many applications of polymers for films
and membranes.

1.4.5. Thermal Proreties

1.4.5.1. Melting point

The term "melting point" when applied to polymers suggests not a solid-liquid phase
transition but a transition from a crystalline or semi-crystalline phase to a solid
amorphous phase. Though abbreviated as simply "Tm", the property in question is more
properly called the "crystalline melting temperature". Among synthetic polymers,
crystalline melting is only discussed with regards to thermoplastics, as thermosetting
polymers will decompose at high temperatures rather than melt.

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1.4.5.2. Boiling point
The boiling point of a polymer substance is never defined due to the fact that polymers
will decompose before reaching theoretical boiling temperatures.

1.4.5.3. Glass transition temperature (Tg)

A parameter of particular interest in synthetic polymer manufacturing is the glass
transition temperature (Tg), which describes the temperature at which amorphous
polymers undergo a second order phase transition from a rubbery, viscous amorphous
solid to a brittle, glassy amorphous solid. The glass transition temperature may be
engineered by altering the degree of branching or cross-linking in the polymer or by the
addition of plasticizer.

Glass Transition Temperature (Tg) features:

At low temperatures, all amorphous polymers are stiff and glassy, sometimes
called the Vitreous State, especially for inorganic polymers.
On Warming, polymers soften in a characteristic temperature range known as the
glass-rubber transition region.
The glass transition temperature (Tg), is the temperature at which the amorphous
phase of the polymer is converted between rubbery and glassy states.
Tg constitutes the most important mechanical property for all polymers. In fact,
upon synthesis of a new polymer, the glass transition temperature is among the
first properties measured

The following physical properties undergo a drastic change at the glass transition
temperature of any polymer:

a) Hardness
b) Volume
c) Modulus (Youngs module)
d) Percent elongation-to-break

ARDC/CS/Internal 26
 Table : 1.4.3. Glass transition temperatures & melting points of some common
polymers

Polymer Tg (oC) Tm (oC)

Polyethylene -120 137
Polypropylene -18 176
Polystyrene 100 240
Polyethylene terephthalate 69 267
Polymethyl methacrylate 105 160
Polyvinyl chloride 87 212

1.4.5.4. Vicat Softening Point

This is the temperature at which a small, circular, heated, lightly loaded probe
penetrates a specific distance into a thermoplastic test specimen.

1.4.5.5. Heat Distortion Temperature

It is the temperature at which a in. deep test bar, loaded to a specified bending
stress, deflects by 0.010 in. This value is important to the design engineer as a relative
measure of the ability of various materials to perform at elevated temperatures while
supporting loads.
1.4.5.6. Thermal conductivity
It is the rate at which a material conducts heat energy along its length or through its
thickness. This is an important factor, since plastics are often used as an effective heat

ARDC/CS/Internal 27
insulator in heat-generating applications and in structures in which heat dissipation is
important.
1.4.5.7. Flammability
For many plastic applications, the consequences of exposure to an actual flame must
be considered. This is important not only in electrical applications, but also in any
applications where the plastic constitutes a significant percentage of the exposed area
of a defined enclosed space.

1.4.6. Electrical Properties

1.4.6.1. Volume Resistivity

A standard measure of conductivity is the electrical resistance of a material when a
direct current potential is applied to it. Volume resistivity of a polymer specimen is
obtained when the resistance across the volume of the specimen is intended to be
measured and is generally expressed in ohm-cm. Materials with values above 108 ohm-
cm are considered to be insulators, while those between 108 and 101 ohm-cm are
considered to be partial conductors.

1.4.6.2. Surface Resistivity

This property gives an idea of the ability of current to flow over the surface of a material.
Unlike volume resistivity which is a property of the material, surface resistivity is
essentially a measure of the susceptibility of the material to surface contamination,
particularly moisture.

1.4.6.3. Dielectric Strength

When an insulator is subjected to an increasingly high voltage, it eventually breaks
down and allows a current to pass. The voltage reached just before it breaks down per
unit of the sample thickness is known as the dielectric strength of the material measured
in volts/mil.

1.4.6.4. Dielectric Constant (Permittivity)

The ease with which a material can be polarized by imposing an electrical field across it
is measured by a material constant called permittivity. The ratio of the material
permittivity to the permittivity in vacuum is called relative dielectric constant or simply
dielectric constant. This is a dimensionless constant that becomes an important factor
when polymers are used as dielectric materials in high frequency applications.

ARDC/CS/Internal 28
1.4.6.5. Dissipation Factor
When an electrical field is applied across a material, it becomes polarized. Upon
reversal of the potential, the polarization of the material also reverses. This is generally
witnessed with an alternating current and energy is dissipated as heat due to the rapid
change in polarization. The dissipation factor is a measure of that heat dissipation. A
low dissipation factor becomes important when plastics are used as insulators in high-
frequency applications such as radar & microwave equipments.

Table : 1.4.4. Typical values of dielectric constant, dissipation factor and volume
resistivity of various thermoplastics at room temperature
Material Description Dielectric Constant Dissipation Factor Volume Resistivity
(cm-ohm)

Polyacetal 3.7 3.9 0.001 0.007 1014 - 1016

ABS 2.9 3.4 0.006 0.021 1016

Nylon 3.1 8.3 0.006 0.190 1012 - 1016

Polycarbomate 2.9 3.8 0.0006 0.026 1015 - 1017

Polypropylene 2.3 2.9 0.003 0.014 1014 - 1017

1.4.6.6. Arc Resistance

The arc resistance of a material is the time (in seconds) that its surface may be exposed
to an electrical arc before electrical breakdown occurs. A material with a high value of
arc resistance would be advantageous in electrical applications where the possibility of
arcing exists. Examples are switches, circuit breakers, automotive ignition components,
and high-voltage apparatus.

1.5. Polymer Structure/Property Relationships

Polymer bulk properties are strongly dependent upon their structure and mesoscopic
behavior. A number of qualitative relationships between structure and properties are
known.

Chain length
Increasing chain length tends to decrease chain mobility, increase strength and
toughness, and increase the glass transition temperature (Tag). This is a result of the
increase in chain interactions such as Van deer Waals attractions and entanglements
that come with increased chain length. These interactions tend to fix the individual

ARDC/CS/Internal 29
chains more strongly in position and resist deformations and matrix breakup, both at
higher stresses and higher temperatures. Chain length is related to melt viscosity
roughly as 1:103.2, so that a tenfold increase in polymer chain length results in a
viscosity increase of over 1000 times.

Branching
Branching of polymer chains also affect the bulk properties of polymers. Long chain
branches may increase polymer strength, toughness, and Tag due to an increase in the
number of entanglements per chain. Random length and atactic short chains, on the
other hand, may reduce polymer strength due to disruption of organization. Short side
chains may likewise reduce crystalline due to disruption of the crystal structure.
Reduced crystalline may also be associated with increased transparency due to light
scattering by small crystalline regions. A good example of this effect is related to the
range of physical attributes of polyethylene. High density polyethylene (HDPE) has a
very low degree of branching, is quite stiff, and is used in applications such as milk jugs.
Low density polyethylene (LDPE), on the other hand, has significant numbers of short
branches, is quite flexible, and is used in applications such as plastic films. The
branching index of the polymer is a parameter that characterizes the effect of long-chain
branches on the size of a branched macromolecule in solution. Dendrites are a special
case of polymer where every monomer unit is branched. This tends to reduce
intermolecular chain entanglement and crystallization. Alternatively, dendrite polymers
are not perfectly branched, but share similar properties to dendrites due to their high
degree of branching.

Chemical cross-linking
Cross linking tends to increase Tag and increase strength and toughness. Cross linking
consists of the formation of chemical bonds between chains. Among other applications,
this process is used to strengthen rubbers in a process known as vulcanization, which is
based on cross linking by sulfur. Car tires, for example, are highly cross linked in order
to reduce the leaking of air out of the tire and to toughen their durability. Eraser rubber,
on the other hand, is not cross linked to allow flaking of the rubber and prevent damage
to the paper.

Degree of crystalline
Increasing degree of crystalline tends to make a polymer more rigid. It can also lead to
greater brittleness. Polymers with degree of crystalline approaching zero or one will
tend to be transparent, while polymers with intermediate degrees of crystalline will tend
to be opaque due to light scattering by crystalline / glassy regions.

ARDC/CS/Internal 30
 2.0 Polymerization Reactions
There are two fundamental polymerization mechanisms. Classically, they have been
differentiated as addition polymerization & condensation polymerization.

2.1 Addition Polymerization

Addition polymerization, also called polyaddition or chain growth polymerization, is a
polymerization technique where unsaturated monomer molecules add on to a growing
polymer chain one at a time.

The formation of a polymer by addition polymerization is an example of a chain reaction.

Once a chain reaction gets started, it is able to keep itself going. The three steps of this
reaction to focus on are:

How the reaction gets started (INITIATION)

How the reaction keeps going (PROPAGATION)
How the reaction stops (TERMINATION)

In addition polymerization new monomer adds on the growing polymer chain via the
reactive active centre which can be a

Free radical in free radical addition polymerization

Carbocation in cationic addition polymerization

Carboanion in anionic addition polymerization

Organometallic complex in coordination polymerization

Common addition polymers are:

Most synthetic rubbers, polyvinyl acetate, polypropylene, polystyrene (Styrofoam), poly

methyl methacrylate (Perspex), polytetrafluoroethylene (Teflon), polyvinyl chloride
(PVC), polyacrylonitrile (orlon, a synthetic textile), saran (cling wrap), carbowax,
neoprene etc.

ARDC/CS/Internal 31
2.1.1. Free Radical Polymerization
One of the most common and useful reactions for making polymers is free radical
polymerization. It is used to make polymers from vinyl monomers, that is, from small
molecules containing carbon-carbon double bonds. A free radical is simply a molecule
with an unpaired electron. The tendency of this free radical to gain an additional
electron in order to form a pair makes it highly reactive so that it breaks the bond on
another molecule by stealing an electron, leaving that molecule with an unpaired
election (which is another free radical). Free radicals are often created by the division of
a molecule (known as an initiator) into two fragments along a single bond. Polymers
made by free radical polymerization include polystyrene, (poly methyl methacrylate),
poly (vinyl acetate) and branched polyethylene.

This process is often used to make polyolefins: addition polymers of olefins (what are
now known as alkenes).

During the formation of a polymer chain of subsequent kinetic events take place:

1. Radical formation
2. Initiation
3. Propagation
4. Termination

Free Radical Formation: The formation of free radicals can take place in a number of
ways. Radicals can be produced by photo-initiation, radiation (gamma-radiation or
electron beam), and electrochemical reaction or by thermal initiation. They are
commonly generated by breaking chemical bonds in such a way that the two electrons
involved in the bond end up on the two separate fragments of the original molecule.
This is called 'homolytic cleavage. The stability of a radical refers to the molecule's
tendency to react with other compounds. An unstable radical will readily combine with
many different molecules. However a stable radical will not easily interact with other
chemical substances. The stability of free radicals can vary widely depending on the
properties of the molecule.

The following diagram shows the formation of a radical from its initiator benzoyl
peroxide & 2, 2-azo-bis- isobutyrylnitrile (AIBN).

ARDC/CS/Internal 32
Initiation: The first step in producing polymers by free radical polymerization is
initiation. This step begins when an initiator decomposes into free radicals in the
presence of monomers. The instability of carbon-carbon double bonds in the monomer
makes them susceptible to reaction with the unpaired electrons in the radical. In this
reaction, the active center of the radical "grabs" one of the electrons from the double
bond of the monomer, leaving an unpaired electron to appear as a new active center at
the end of the chain. Addition can occur at either end of the monomer. This is the
addition of the first monomer unit to the initially formed free radical.

ARDC/CS/Internal 33
The whole process including the breakdown of the initiator molecule to form radicals
followed by the radicals reaction with a monomer molecules is called the initiation step
of the polymerization.

Propagation: This is the process for the growth of the chains. In the propagation stage,
the process of electron transfer and consequent motion of the active center down the
chain proceeds.

The radical derived from the initiator will grab another electron from the nearest
convenient source - if a carbon-carbon double bond is present, this will result in the
formation of a new single bond and the regeneration of the radical centre.

This process, the adding of more & more monomer molecules to the growing chains is
called the propagation.

Termination: Termination is the third and final step of a chain-growth polymerization.

Termination occurs when a radical reacts in a way that prevents further propagation.
The most common method of termination is by coupling where two radical species react
with each other forming a single molecule.

ARDC/CS/Internal 34
Another, less common method of termination is chain disproportionation where two
radicals meet, but instead of coupling, they exchange a proton, which gives two
terminated chains, one saturated and the other with a terminal double bond.

ARDC/CS/Internal 35
2.1.2. Cationic Polymerization
Cationic polymerization is the one of the three major types of chain polymerization
involving positively charged or electrophilic active centers at the growing chain end.
Both alkenes & heterocyclic monomers can be polymerized catatonically.

Cationic polymerization is not only important commercial processes, but in some cases
are attractive laboratory techniques for preparing well-defined polymers & copolymers.
Polyacetal, poly (tetramethylene glycol), poly (e-caprolactam), polyaziridine,
polysiloxanes as well as butyl rubber, poly (N-vinyl carbazol), polyindenes &
poly(vinylether)s are synthesized commercially by cationic polymerization.

The mechanism of cationic polymerization is a kind of repetitive alkylation reaction.

Electron donating groups are needed as the R groups because these can stabilize the
propagating species by resonance. Examples:

ARDC/CS/Internal 36
Propagation is usually very fast. Therefore, cationic vinyl polymerizations must often be
run at low temperatures. Unfortunately, cooling large reactors is difficult and expensive.
Also, the reaction can be inhibited by water if present in more than trace amounts; so
careful drying of ingredients is necessary (another expense).

Examples of Commercial Cationic Polymers

ARDC/CS/Internal 37
Drawback of cationic polymerization:

The biggest drawback of cationic polymerization is its high reactivity & instability
of the growing carbonations leading to uncontrollable polymerization
characterized by incomplete initiation, important chain transfer & irreversible
termination reaction.
Cationic polymerization is less efficient than free-radical polymerization due
to the caustic nature of cation-producing reagents. An example of a cation-
initiated polymerization is the reaction of ethene with sulfuric acid.

The reaction continues and gives

Which finally reacts with HSO4 to create the polymer

Cationic vinyl polymerization is plagued by numerous side reactions, most of

which lead to chain transfer. It is difficult to achieve high MW because each
initiator can give rise to many separate chains because of chain transfer. These
side reactions can be minimized but not eliminated by running the reaction at low
temperature.

2.1.3. Anionic Polymerization

An anionic addition polymerization is an addition polymerization initiated by a strong
base and anion, such as an alkali, amide, or an organometallic compound, such as n-
butyl lithium. A nucleophilic carbanion is formed containing an unshared pair of
electrons.

ARDC/CS/Internal 38
The mechanism of anionic polymerization is a kind of repetitive conjugate addition
reaction

Electrons withdrawing groups (ester, cyano) or groups with double bonds (phenyl, vinyl)
are needed as the R groups because these can stabilize the propagating species by
resonance. Examples:

Anionic addition polymerization is not confined to vinyl compounds. It equally occurs

when 1, 2 - epoxyethane (commonly known as ethylene oxide) reacts with a small
amount of a base, such as sodium methoxide. It turns, through polymerization, into a
polyether of high molecular weight.

ARDC/CS/Internal 39
Formation of polyether from a methoxide & 1, 2 epoxy ethane

The beauty of anionic polymerization lies in the lack of termination reactions when
carried out under the appropriate conditions (living polymerization). This means that the
propagating species remains unchanged at the chain end when the monomer is
consumed, so subsequent chemical reactions can be carried out.

2.1.4. Co-ordination Polymerization

Polymerization carried out in the presence of a coordination catalyst is called co-
ordination polymerization where each polymerization step involves the complications of
the monomer before its enchainment at the active site of the catalyst.

Coordination polymerization is a form of addition polymerization in where monomer

adds to a growing macromolecule through an organometallic active center. The
development of this polymerization technique started in the 1950s with heterogeneous
Ziegler- Natta catalysts based on titanium tetrachloride and an aluminum co-catalyst
such as methylaluminoxane. They usually involve complexes formed between a
transition metal & the electrons of the monomer. Coordination type polymers are also
streoregular and can be isotactic or syndiotactic instead of just atactic. This tacticity
introduces crystallinity in otherwise amorphous polymers. From these differences in
polymerization type the distinction originates between low-density polyethylene (LDPE),
high-density polyethylene (HDPE) and even ultra high molecular weight polyethylene
(UHMWPE). These types of polymerization usually lead to linear & stereo-regular
chains & often use so called Ziegler Natta Catalysts, various metal oxides, or more
recently metallocene catalyst.

The first step in the polymerization process is the formation of a monomer-catalyst

complex between the oranometallic compounds & the monomer:

ARDC/CS/Internal 40
Here Mt represents transition metals such as Ti, Mo, Cr, V, Ni or Rh. In the formation of
this monomer-catalyst complex, a coordination bond is involved between a carbon atom
of the monomer & the metal of the catalyst. The coordinated metal-carbon formed in
the monomer catalyst complex acts as the active centre from where propagation starts.
The incoming monomer is incorporated at the active centre of the metal carbon bond,
from where the chain growth starts.

ARDC/CS/Internal 41
Life cycles of catalysts for olefin coordination polymerization:

1. Early generation Ziegler- Natta catalysts for ethylene & propylene polymerization
2. Philips catalyst for ethylene polymerization
3. Forth generation Ziegler-Natta catalyst for ethylene polymerization
4. Forth generation Ziegler-Natta catalyst for propylene polymerization
5. Metallocene based catalyst for olefin polymerization leading to polymers of
various stereoregularity.

The best-known Ziegler- Natta catalysts are those derived from TiCl4 or TiCl3 and an
aluminium alkyl. The catalyst system appears to function by formation of coordination
complex between the catalyst, growing chain & the incoming monomer. Hence the
process is referred to as coordination addition polymerization & the catalyst as
coordination catalyst.

The catalyst complex of the TiCl3/AlR3 system essentially acts as template for the
successive orientation & isotactic placement of the incoming monomer units. Though a
number of structures have been proposed for the active species, they fall into either of
two general categories: monometallic & bimetallic.

Structure (I), represent a bimetallic species, is the coordination complex that arises from
the interaction of the original catalyst components (titanium & aluminium compounds)

ARDC/CS/Internal 42
with exchange of R & Cl group. Structure (II) represent a monometallic species
constitutes an active titanium site at the surface of a TiCl3 crystal. Besides the four
chloride ligands that the central Ti atom shares with its neighbouring Ti atoms, it has an
alkyl ligand a vacant orbital. Chain propagation by the bimetallic mechanism occurs at
metal centers of the bridge complex. With the chain growth taking place always from the
metal end, the incoming monomer is oriented, for stearic reason, with the =CH2 group
pointing the lattice & the CH3 group to one side, with the result that the process leads to
the formation of an isotactic polymer.

It is generally accepted that the d-orbital in the transition element are the main source of
catalytic activity & that it is the Ti-alkyl bond that acts as the polymerization centre
where chain growth occurs. For -TiCl3 catalyst the active centre is formed by the
interaction of aluminium alkyl with an octahedral vacancy around Ti. To elaborate the
five coordinated Ti3+ on the surface has a vacant d-orbital, which facilitates
chemisorption of the aluminium alkyl & this is followed by alkylation of the Ti3+ ion by an
exchange mechanism to form the active centre TiRCl4. The vacant site at the active

ARDC/CS/Internal 43
centre can accommodate the incoming monomer unit, which forms a complex with
the titanium at the vacant d-orbital & is then inserted into the Ti-alkyl bond. After the
monomer is inserted into the Ti-alkyl bond, the polymer chain migrates back to the initial
state, while the vacant site migrates to its original position to accept another monomer
molecule. This migration is necessary, as otherwise an alternating position would be
offered to the monomer leading to the formation of a syndiotactic polymer instead of an
isotactic polymer.

ARDC/CS/Internal 44
Ziegler-Natta polymerization is a great way to make polymers from hydrocarbon
monomers like ethylene and propylene. But it doesn't work of for some other kinds of
monomers. For example, we can't make poly (vinyl chloride) by Ziegler-Natta
polymerization. When the catalyst and co catalyst come together to form the initiating
complex, radicals are produced during intermediate steps of the reaction. These can
initiate free radical polymerization of the vinyl chloride monomer. Acrylates are out, too,
because Ziegler-Natta catalysts often initiate anionic vinyl polymerization in those
monomers.

For a long time, Ziegler-Natta polymerization was the most useful and versatile reaction
for producing polymers of a specific desired tacticity. But recently a new type of
polymerization, also using metal complexes as initiators, has been developed, called
metallocene catalysis polymerization.

The fourth generation of polymerization catalysts, based on metallocene compounds, is

now evolving towards industrial success. Kaminsky and Sinn suspected that the water
and AlEt3 reacted to form methyl aluminoxane (MAO), and they subsequently
discovered that MAO-activated homogeneous metallocene catalysts were capable of
polymerizing propene and higher olefins. This seminal discovery by Kaminsky and Sinn
started the search for single-site catalysts.

This catalyst system boosted the activity of metallocene-based catalyst & produced
uniform polyethylene with the narrow molar mass distribution typical of single site
catalyst. This metallocene catalyst system provides a unique opportunity for new tailor
made polymers increased the range of co-monomers that could be used. An interesting
peculiarity of metallocene system is that the difference in the reactivities of ethane,
propene & higher - olefins is markedly less compared to the conventional Ziegler-Natta
catalyst. This opens many possibilities for the synthesis of copolymers.

2.2. Condensation Polymerization

Condensation polymerization, a form of step-growth polymerization, is a process by
which two molecules join together, with the loss of a small molecule which is often
water. The type of end product resulting from a condensation polymerization is
dependent on the number of functional end groups of the monomer, which can react.
Monomers with only one reactive group terminate a growing chain, and thus give end
products with a lower molecular weight. Linear polymers are created using monomers
with two reactive end groups and monomers with more than two end groups give three
dimensional polymers which are crosslinked.

ARDC/CS/Internal 45
Cross-linking often involves joining monomers with an -OH (hydroxyl) group and a freely
ionized -H on either end (such as a hydrogen from the -NH2 in nylon or proteins).
Normally, two or more different monomers are used in the reaction. The bonds between
the hydroxyl group, the hydrogen atom and their respective atoms break forming water
from the hydroxyl and hydrogen, and the polymer.
Polyester is created through ester linkages between monomers, which involve the
functional groups carboxyl and hydroxyl (an organic acid and an alcohol monomer).
Nylon is another common condensation polymer. It can be manufactured by reacting di-
amines with carboxyl derivatives. In this example the derivative is a di-carboxylic acid,
but di-acyl chlorides are also used. Another approach used is the reaction of di-
functional monomers, with one amine and one carboxylic acid group on the same
molecule:
The carboxylic acids and amines link to form peptide bonds, also known as amide
groups. Proteins are condensation polymers made from amino acid monomers.
Carbohydrates are also condensation polymers made from sugar monomers such as
glucose and galactose.
Condensation polymerization is occasionally used to form simple hydrocarbons. This
method, however, is expensive and inefficient, so the addition polymer of ethene
(polyethylene) is generally used.
Condensation polymers, unlike addition polymers may be biodegradable.
The most commonly known condensation polymers are proteins, fabrics such as nylon,
silk, or polyester.

The Mechanism of Condensation Polymerization

The monomers that are joined by condensation polymerization have two functional
groups. A carboxylic acid and an amine can form an amide linkage, and a carboxylic
acid and an alcohol can form an ester linkage. Since each monomer has two reactive
sites, they can form long-chain polymers by making many amide or ester links. Let's
look at two examples of common polymers made from the monomers.

Example 1.
A carboxylic acid monomer and an amine monomer can join in an amide linkage.

As before, a water molecule is removed, and an amide linkage is formed. An acid group
remains on one end of the chain, which can react with another amine monomer.

ARDC/CS/Internal 46
Similarly, an amine group remains on the other end of the chain, which can react with
another acid monomer.

Thus, monomers can continue to join by amide linkages to form a long chain. Because
of the type of bond that links the monomers, this polymer is called a polyamide. The
polymer made from these two six-carbon monomers is known as nylon-6, 6. (Nylon
products include hosiery, parachutes, and ropes.)

Example 2:
A carboxylic acid monomer and an alcohol monomer can join in an ester linkage.

ARDC/CS/Internal 47
 3.0 Polymerization Processes
Polymerization is the process of bonding repeating single units (monomers) into long
chains polymers. It is a very common chemical process, which involves numerous
different variables. The functionality of a polymer is related to its physical structure and
shape, so being able to create different families of size distribution can create different
functional products.

Different process parameters can affect the physical structure of the polymer, so being
able to precisely control the critical parameters of paramount importance.

Polymerization is a very common chemical process, used to create a wide range of

products in a variety of ways.

The technologies that have been developed for the production of polyolefins, olefin
homopolymer & copolymers are:

Bulk Polymerization (monomer is solvent for polymer)

Solution polymerization (Solvent present)
Suspension Polymerization (Particles of polymer with catalyst suspended in a
hydrocarbon liquid)

Emulsion Polymerization (Immiscible monomer in water plus surfactant)

Fluidized bed polymerization (Gas phase, catalyst/polymer particles fluidized in
the monomer gas )

Classification of some of the polymers on the basis of their polymerization process:

Bulk Solution Suspension Emulsion

Polymerization Polymerization
Polymerization Polymerization

Polyamide Polyethylene (LDPE) Polysulphides Poly vinyl acetate

Polycarbonate Poly (methyl Poly (methyl Styrene butadiene

methacrylate) methacrylate) copolymer

Poly (ethylene Polyethylene (HDPE) Poly (vinyl chloride)

terepthlates)

Polyethylene Polypropylene
(LDPE)

Poly (methyl Polystyrene

methacrylate)

ARDC/CS/Internal 48
The fundamental differences in the various olefin polymerization processes reflect the
different approaches that have been devised to remove the substantial heat of
polymerization.

3.1. Bulk Polymerization:

Bulk polymerization is the process of conversion of monomer into polymer without any
use of solvent other than catalyst & is thus the simplest in terms of formulation. It is
used for most step growth polymers & many types of chain growth polymers. It is
carried out in the liquid monomer at definite pressure & temperature. Here
polymerization is started through heating, ultraviolet radiation or the addition of initiator
(e.g. Peroxides, azo compounds & others). After a shot period of heating, the reaction
mixture continues to heat by itself & it becomes necessary to remove heat of reaction
because as the conversion increases viscosity increases & it becomes really very
difficult to remove such an extent heat with agitation. With increasing temperature bulk
polymerization can take turbulence & even explosive in presence of large amount of
monomers.

There could be two possibilities if the resulting polymer is soluble in a monomer the
viscosity of the medium increases gradually in the course of polymerization & the net
result is a monolithic block of polymer .The other is, if the polymer is insoluble in a
monomer the polymer obtained is in the form of powder or a porous body. The latter
process is more preferred.

Polymers made by free radical polymerization are typically mixtures of macromolecules

with different molecular structural characteristics (e.g. copolymer composition, short &
long chain branching frequencies). Since the molecular features of the produced
polymers are directly related to their end use properties, control of the polymer chain
microstructure during polymerization is of profound importance.

The major advantages are:

It is one of the simplest methods of polymerization.

This process does not require any other kind of additivation apart from monomer
& the catalyst.
The polymers produced are almost in the purest form.

But apart from advantages, there are disadvantages:

ARDC/CS/Internal 49
 Since polymerization process takes place at very high temperature & high
pressure, as a result of which major processing parameters heat transfer &
viscosity are difficult to achieve.
Polymerization temperature & rate of reaction can only be controlled by vigorous
agitation.
Due to vigorous agitation control over degree of polymerization & growth of
polymer chain also becomes difficult resulting in poor control over molecular
weight & density.
Bulk polymerization result in a very low conversion of ~ 30%. The conversion
doesnt increase with longer reaction time.

Because of these disadvantages, it is used in few cases, which are produced in large
scale.

This process is used to produce low-density polyethylene, polyvinylchloride &

polystyrene, poly (methyl methacrylate).

High pressure LDPE has certain properties, which are difficult to obtain by low-pressure
technologies. Typical features for LDPE are long branching of the polymer chains & a
wide variation in molecular weight distribution, which may be reasonably narrow,
medium or broad as well as symmetrical or asymmetrical. The molecular structure is
usually tailored according to the specific application.

LDPE has been commercially produced in high-pressure reactors for more than four
decades. The polymerization of branched polyethylene was discovered by ICI in 1933,
when chemical reactions under very high pressure were studied. Development of
commercial free-radical-initiated, high pressure PE process technology by the end of
1930s was the foundation of the polyolefin industry. Two-reactor technology i.e. tubular
& autoclave are employed in the high-pressure polymerization of ethylene.

LDPE: Free radical Extreme operating condition (150 -3000C & 2500-3000 atm)

High pressure reactor technology

ARDC/CS/Internal 50
Polymerization Condition:

Temperature: 250 C

Pressure: 1200-1500 bar

(a) Autoclave: Large capacities- small residence time.

ARDC/CS/Internal 51
 High degree of back mixing.

Thick wall- inefficient heat removal.

Low conversion (15- 30%).

Steps involved in Polymerization

A tubular LLDPE reactor is a long heat exchanger.

Free radical polymerization uses peroxide initiators or oxygen to promote
polymerization reactions
Ethylene is circulated through a compressor a hyper compressor accomplishes
the main pressurization of the feed stream.
Initiators are introduced at various points along the length of the tube- Zone
temperature are accurately controlled.
No back mixing takes place in the tubular system, residence time is limited/short.
The exothermic heat of reaction is removed via- water jacket on the outside walls
of the tube.
Upon existing the reactor the material passes through medium pressure & low-
pressure separators (separates ethylene from PE), PE moves to the extruder.

Product properties may be controlled, e.g. by the pressure, temperature profile

across the reactor & addition of chain transfer.

ARDC/CS/Internal 52
Polymerization Condition:

Temperature: 150-300 C

Pressure: 1300-3400 bar

(b) Tubular: Large capacities- small residence time.

Low degree of back mixing.

Better heat removal.

High conversion (25-40%).

Steps Involved in polymerization

Free radical type polymerization uses peroxide initiators typically.

System utilizes a stirred cylindrical vessel.
Ethylene feed gas & peroxide are introduced to a compressor & then pumped
with peroxide initiator into the stirred autoclave reactor.

ARDC/CS/Internal 53
 Proprietary designs baffle or partition the reactor into discreet zones enabling
control of molecular species & amount of long chain branching of polymer in
these zones.
Back mixing does take place in the autoclave reactor.
Walls of the autoclave unit are thick to accommodate high pressure- heat of
reaction is removed by the introduction of fresh feed.
Upon exiting the reactor the material passes through medium pressure & low-
pressure separators (separate ethylene from LDPE polymer).
Polymer enters the pelletization process to be pelletised.

All the new world scale LDPE plants are tubular process technology. This technology is
widely licensed by a number of companies, including Sabic Euro Petrochemicals
/Stamicarbon, Basell (Lupotech T), ExxonMobil, EniChem & Atofina. Autoclave
technology is available from Equistar, Enichem, Exxon Mobil & Simon-Carves (ICI
process.

3.2. Solution Polymerization

A polymerization process in which the monomers and the initiators are dissolved in a
non-monomeric liquid solvent at the beginning of the polymerization reaction is
characterized by solution polymerization. The liquid is usually also a solvent for the
resulting polymer or copolymer. Solvents must be carefully chosen, however, so that
they do not undergo chain-transfer reactions with the polymer. Because it can be
difficult to remove solvent from the finished viscous polymer, the solvent acts as the
heat exchange medium while stirring. Here also arise two possibilities of polymer
formation one if both the monomer & polymer are soluble in the solvent resulting in
the polymerization of polymer solution called a lacquer, which has a direct application in
the field of coating. And the other is, if conversion up to 95% can be achieved with
narrow molecular weight distribution having good flow properties.

These polymerization process posses a number of advantages:

The main advantages of this process (in which monomer, polymer & solvent
coexist) are that the solvent can absorb a great part of the heat of reaction.
Consequently polymer structure, molecular weight & molecular weight
distribution can be controlled resulting in a good product homogeneity & uniform
quality.
The benefits of this type of polymerization, over the conventional bulk
polymerization, are that it reduces the viscosity of the reaction not allowing auto-
acceleration at high monomer concentrations.

ARDC/CS/Internal 54
 If the temperatures required to melt the monomer are too high, or if bulk
polymerization would be so exothermic as to be hazardous, one may wish to use
solution polymerization process.
Change penalties i.e no production loss during the grade change.
This process produces polymer resin of narrow MWD (i.e. injection molding
grades).

Disadvantages:

Reaction temperature is limited by the boiling point of the solvent used, which in
turn restricts the rate of reaction that may be achieved
The solubility of a polymer decreases with increasing molecular weight and it is
necessary to select a good solvent to dissolve the polymer. To select a good
solvent, one has to compare the solubility parameter of the polymer to the
solubility parameters of the available solvents
It is difficult to free the solvent, which means that there is almost always chain
transfer to the solvent & hence a restriction on the molar mass of the product

The application of solution process is confined to the manufacture of copolymers for

use in surface coatings.

A systematic diagram of low-pressure solution polymerization is shown below:

ARDC/CS/Internal 55
 1. Stirred Autoclave Reactor
2. Separator
3. Separator
4. Pelletiser
5. Compressor

Steps Involved in Polymerization:

1. All raw ingredients including ethylene feed, hydrogen, etc are dissolved into a
solvent resulting in a solution composed of the raw ingredient required.
2. Catalyst s required in the reactor.
3. Solution is introduced into one or more stirred autoclave reactors-temperature,
residence time & mixing are controlled.
4. Polymer solution exits the reactors solvent is flashed off in a separator & returns
to distillation.
5. Polymer passes through a low-pressure separator into an extruder.
6. A devolatization extruder is used in some cases to remove residual hydrocarbons
while stripping vessels (post extrusion) may also be used in some processes to
accomplish this task.

Three main types of solution processes have been developed by DOW (Dowlex), DSM
(Compact, now owned by Sabic Euro Petrochemicals) & Dupont (Sclaritech, now owned
by Nova Chemicals). The strength of a solution process are short product transition
times, ability to produce polyethylene of very low density (e.g. VLDPE, PE elastomers &
elastomer) and the ability incorporate higher alpha olefins co-monomers such as 1-
octene. LLDPE & other low-density polyethylene with higher alpha olefins show good
strength, toughness & sealing properties.

3.3 Suspension / Slurry polymerization

This technique is very similar to solution polymerization except that the monomer is
suspended rather dissolved in an inert liquid, often water.

It is a batch process, which is widely, practiced industrially in which the dispersion

medium is usually water & the monomer or the mixture of monomer is dispersed as a
droplets in the size ranging from .4mm to .8mm by mechanical agitation. The
polymerization mechanism is similar to that of bulk polymerization because there are
large numbers of micro droplets undergoing bulk polymerization. A catalyst is dissolved

ARDC/CS/Internal 56
in monomer, which is dispersed in water. A dispersing agent is incorporated to stabilize
the suspension. For any nonpolar monomer this process offers a method of eliminating
many of the problems, which are encountered in bulk & solution polymerization, heat
removal in the former case & solvent reactivity & solvent removal in the latter.

Advantages:

Easy heat removal.

The polymer is obtained in a convenient, easy handled & often directly useful
form.
The impurity levels are lower than the emulsion polymerization.
Suspension polymerizations are generally easier to control & there is little, if any
loss in clarity or electrical insulation properties. Varying the dispersing systems &
the rate of stirring may control particle shape, size & size distribution.

Disadvantages:

For the polymers (synthetic elastomer) that are very soluble in their monomer,
stirring has to be extremely vigorous otherwise the partially reacted droplets
undergo agglomeration. For tacky polymers (such as synthetic elastomer) are
very prone to undergo agglomeration, so that suspension polymerization cannot
be used for the polymers.
The monomer recovery is very difficult.

Despite these disadvantages the suspension technique is used industrially, poly (vinyl
chloride) being produced by this method. In this process vinyl chloride monomer is
suspended in demineralised water to which gelatin has been added as suspending
agent & caproyl peroxide added as initiator. Polymerization takes place under an
atmosphere of nitrogen at 50 C, taking 12 hours to reach 85-90 % completion, at which
point reaction is stopped. Pure PVC is obtained from the suspension by centrifugation.

The primary product in the slurry units is HDPE with MDPE as a secondary product.
Chevron Philips, BP Solvay, Basell, Borealis & Sumitomo Mitsui have their own slurry
technology. Currently, long jacketed loop reactors & continuous stirred tank reactors
are mostly used for slurry polymerization.

ARDC/CS/Internal 57
A systematic loop reactors used for ethylene polymerization by solution polymerization
is shown below:

Steps Involved in Polymerization:

1. The reactor is a circulation loop, water-jacketed to remove the heat.

2. A hydrocarbon carrier circulates the reactive ingredients around the loop reactor.
3. The reaction of ethylene, co-monomer, hydrogen, etc results in polymer particles
forming, suspended on the carrier.
4. Polymer settles out & is removed from the reactor into a flash vessel that
separates granular polymer from residual hydrocarbon
5. Polymer granules exit the flash vessel into a purge vessel where hydrocarbons
are removed.
6. Additives are incorporated granular material is extruded & pelletised.

ARDC/CS/Internal 58
3.4. Emulsion polymerization
Emulsion polymerization is a complex heterogeneous polymerization that at present is
most widely used & important route to synthetic polymer colloid. This process is also
carried out in a water medium. An emulsifier either anionic or cationic soap, is added to
break the monomer into very small particles. The initiator is in solution in the water.
After polymerization, the polymer can be precipitated, washed & dried or the mixture
can be used directly. The major difference suspension with that of emulsion
polymerization is that in the latter case the monomer droplets are approximately 0.1 to
1mm in size & the particles in the former are 10-7 to 10-6 mm in size & second the
catalyst is dissolved in the aqueous phase in the latter but is incorporated directly into
the droplets in the former.

Emulsion polymerization is a type of radical polymerization that usually starts with an

emulsion incorporating water, monomer, and surfactant. The most common type of
emulsion polymerization is an oil-in-water emulsion, in which droplets of monomer (the
oil) are emulsified (with surfactant) in a continuous phase of water. Water-soluble
polymers, such as certain polyvinyl alcohols or hydroxyethyl celluloses, can also be
used to act as emulsifiers/stabilizers. Polymerization takes place in the latex particles
that form spontaneously in the first few minutes of the process. These latex particles are
typically 100 nm in size, and comprise many individual polymer chains. The particles
are stopped from coagulating with each other because each particle is surrounded by
the surfactant ('soap'); the charge on the surfactant repels other particles
electrostatically. When water-soluble polymers are used as stabilizers instead of soap,
the repulsion between particles arises because these water-soluble polymers form a
'hairy layer' around a particle that repels other particles, because pushing particles
together would involve compressing these chains.

Emulsion polymerization is used to manufacture several commercially important

polymers. A dispersion resulting from emulsion polymerization is often called a latex
(especially if derived from a synthetic rubber) or an emulsion (even though "emulsion"
strictly speaking refers to a dispersion of a liquid in water). These emulsions find
applications in adhesive, paints, paper coating and textile coatings. They are finding
increasing acceptance and are preferred over solvent-based products in these
applications as a result of their eco-friendly characteristics due to the absence of VOCs
(Volatile Organic Compounds) in them.

Advantages of emulsion polymerization include:

High molecular weight polymers can be made at fast polymerization rates. By

contrast, in bulk and solution free radical polymerization, there is a tradeoff
between molecular weight and polymerization rate.

ARDC/CS/Internal 59
 The continuous water phase is an excellent conductor of heat and allows the
heat to be removed from the system, allowing many reaction methods to
increase their rate.
Since polymer molecules are contained within the particles, viscosity remains
close to that of water and is not dependent on molecular weight.
The final product can be used as is and does not generally need to be altered or
processed.
The very small particles formed resist agglomeration thus allowing the
preparation of tacky polymers.
Inverse phase (water in oil) emulsion is possible.
The polymer is obtained in a convenient, easily handled, & often directly useful
form.

Disadvantages of emulsion polymerization include:

Surfactants and other polymerization adjuvants remain in the polymer or are

difficult to remove.
For dry (isolated) polymers, water removal is an energy-intensive process.
Emulsion polymerizations are usually designed to operate at high conversion of
monomer to polymer. This can result in significant chain transfer to polymer.
A somewhat less pure polymer than from bulk polymerization, since there are
bound remanants of suspending agents adsorbed on the particle surface.
It cannot be used to make condensation polymers or for ionic or Ziegler-Natta
polymerization (anything which react with water).
Low yield per reactor volume.

The first successful theory to explain the distinct features of emulsion polymerization
was largely developed by Smith and Ewart, and Hawkins1 in the 1940s, based on their
studies of polystyrene.
The following steps2 summarize the Smith-Ewart-Harkins theory for the mechanism of
free-radical emulsion polymerization:
A monomer is dispersed or emulsified in a solution of surfactant and water
forming relatively large droplets of monomer in water.
Excess surfactant creates micelles in the water.
Small amounts of monomer diffuse through the water to the micelle.

ARDC/CS/Internal 60
 A water-soluble initiator is introduced into the water phase where it reacts with
monomer in the micelles. (This characteristic differs from suspension
polymerization where an oil-soluble initiator dissolves in the monomer, followed
by polymer formation in the monomer droplets themselves.) The total surface
area of the micelles is much greater than the total surface area of the fewer,
larger monomer droplets; therefore the initiator typically reacts in the micelle and
not the monomer droplet.
Monomer in the micelle quickly polymerizes and the growing chain terminates. At
this point the monomer-swollen micelle has turned into a polymer particle. When
both monomer droplets and polymer particles are present in the system. More
monomer from the droplets diffuses to the growing particle, where more initiators
will eventually react.
Eventually the free monomer droplets disappear and all remaining monomer is
located in the particles. Depending on the particular product and monomer,
additional monomer and initiator may be continuously and slowly added to
maintain their levels in the system as the particles grow.
The final product is a dispersion of polymer particles in water. It can also be
known as polymer colloid, latex, or commonly and inaccurately as emulsion.
High molecular weights are developed in emulsion polymerization because the
concentration of growing chains within each polymer particle is very low.

Emulsion polymerizations have been used in batch, semi-batch, and continuous

processes. The choice depends on the properties desired in the final polymer or
dispersion and on the economics of the product

Polymers commercially produced by emulsion polymerization are synthetic rubber

(SBR, Polybutadiene, polychloroprene, Nitrile rubber etc), plastics (PVC, PS, PMMA,
ABS, Polyvinylidene fluoride)

ARDC/CS/Internal 61
3.5. Gas Phase Fluidized Bed Polymerization
Gas phase polymerization is the newest technology introduced for the manufacture of
polyolefins. It was developed for the production of polyethylene with the third
generation Ziegler Natta catalyst in the late 1960s. A gas fluidized bed reactor is widely
used in polymer industry for production of polyethylene due to the ability of operation at
lower pressure & temperature, no need of solvent using better solid mixing & heat
removal. In a gas phase reactor the polymerization takes place in a fluidized bed of
polymer particles. Inert gas or gas mixture is used for fluidization. The gas flow is
circulated through the polymer bed & a heat exchanger in order to remove the
polymerization heat.

The development of the gas phase technology represents a major advance for the
commercial production of polyolefins. A gas phase process avoids the problem of the
high cost remaining in the high mileage slurry & solution processes (associated with
recycling of diluents or solvent and drying of the polymer)

The first commercial gas phase HDPE plant using a fluidized bed reactor was
constructed by Union carbide in 1968 other gas phase polymerization processes using
different types of reactors have also been developed by BASF, Naphthachimie &
Amoco.

The gas phase polymerization of ethylene is typically carried out at 85-100 C under a
pressure of 20-25 atm. The ethylene monomer circulates, thus removing the heat of
polymerization & fluidizing the catalyst bed. In order to keep the temperature of the
process at values below 100 C, gas conversion is maintained at 2-3 per pass. In the
production of polypropylene by the gas-phase process usually the polymerization
temperature is lower & ranges from above 50 to 85 C& the pressure ranges from 15 to
40 atm.

ARDC/CS/Internal 62
Steps Involved in Polymerization:

1. Feed gases such as ethylene, butene or hexene, hydrogen etc are introduced to
the fluidized bed in the base of the gas phase reactor.
2. Catalyst is introduced to the reactor.
3. The exothermic heat of reactions controlled by the fresh feed gas circulation.
4. High reaction throughput rates & low conversion rates per pass typically
achieved- fed gases recycle through the reactor entering the base & exiting at
the top.
5. Granular PE product is produced in the reactor & intermittently discharged out of
the reactor into a purge bin, hydrocarbons are removed, granular materials
conveyed to pelletisation followed by pellet conveying to finishing area.

Although an innovative technology, the process for high-density polyethylene did not
offer clear economic advantages over the established slurry process. In the case of
linear low-density polyethylene, the fluidized bed process is competitive with the
solution & high-pressure processes, with lower capital & operative costs. In the case
of polypropylene industry uses two different methods for carrying out propylene

ARDC/CS/Internal 63
 polymerization depending on the chosen method of heat removal. Use is made of
fluidized bed, as in the case of polyethylene manufacture, & of mechanically agitated
dry powder beds with evaporative cooling in vertical & horizontal autoclaves;
propylene is recycled by removal as condensed vapour & reintroduction into the
monomer feed. This has the effect of removing the majority of the heat of
polymerization.

In all these & other polymerization techniques, the ultimate properties of the
polymer such as molecular weight, molecular weight distribution, molecular structure
& chemical homogeneity are very much dependent on factors such as effective
removal of heat of polymerization, provision of proper residence time & effective
mixing to ensure uniform temperature profile & reactant distribution throughout the
system.

ARDC/CS/Internal 64
 Comparison between the Different Polymerization Processes
Bulk
Polymerization
Homogenous system
Viscosity of the medium
increases very rapidly &
at high conversion proper
mass transfer becomes
difficult
Exothermic dissipation
difficult, may lead to auto
acceleration
Require longer duration
for high conversion
Suitable for producing
medium to high molecular
weight products.
Most widely used in
industrial processes
involving free radical
polycondensation &
polyaddition
polymerization.
Products is minimum
contaminated, easy to
isolate & can be directly
used for molding products
ARDC/CS/Internal
Solution Polymerization
Homogenous system
Viscosity of medium
increases slowly but not
difficult to maintain proper
mass transfer even at
high conversion
Exothermic dissipation
easy.
Require longer duration
for high conversion
Suitable for producing low
molecular weight
products.
Suitable for free-radical,
cationic, anionic & co-
ordination polymerization
Isolation becomes
difficult, products
contaminated with solvent
& solvent related
impurities.
Suspension Polymerization
Heterogeneous system
Viscosity of the medium does
not increases appreciably
Exothermic dissipation easy.
Require longer duration for
high conversion
Suitable for producing
medium to high molecular
weight products.
Suitable for free radical &
polycondensation
polymerization.
Isolation is easy as the
product is obtained as
powder/beads & can be used
for direct molding purposes.
65
Emulsion
Polymerization
Heterogeneous system
Viscosity of the medium
increases throughout the
polymerization.
Exothermic dissipation
the best.
High conversion achieved
in shorter duration
Suitable for producing
very molecular weight
products.
Suitable for free radical &
polycondensation
polymerization.
Emulsion can be directly
used for paints,
adhesives & so on. Solid
products can be isolated
by breaking the emulsion.
Product contaminated
with emulsifier, stabilizer
& so on.
 Comparison of Different Polyethylene Processes

Process Type Bulk Gas Phase Slurry(Suspension) Solution Process

Polymerization Fluidized Bed Process

Temperature (oC) 150 - 300 75 - 100 75 - 100 130 - 270

Pressure (Kg/cm2) > 1000 20 - 30 7 - 20 50 - 200

Residence Time <1 300 120 2

(min)

% Conversion per 17 - 20 5 97 95
Pass

Solvent/Diluent None None n-Hexane Cyclohexane

Comonomers

a) Type Propylene Propylene Propylene 1-Octene

1-Butene 1-Butene 1-Butene 1-Butene

4-Methylpent-1-ene

b) % Max
8 - 10 9 - 10 8 - 10 8 - 10

Catalyst Ziegler Type Chromate-Titanate- Supported Zeigler- Zeigler type

Silicate on Natta Vanadium
Silica/Alumina Compounds

Polymer Recovery Molten polymer Intermediate Solvent Stripping Solvent Stripping

Discharged Discharge With Steam From Molten
Followed By Drying Polymer

Density 0.918 0.940 0.915 0.965 0.928 0.960 0.918 0.965

Melt Index 0.7 - 120 <0.01 - 200 <0.01 - 70 0.33 - 120

(gm/10 min)

ARDC/CS/Internal 66
4.0 Polyolefin Manufacturing Technologies

4.1. Polyethylene Technologies

Global demand for polyethylene (PE) has grown quickly since its early days. The
primary reasons for this sustained growth are:

a) PE is a well-established plastic resin with a broad application range. Its use has
grown faster than overall economic growth worldwide.
b) PE continues to have the potential to replace traditional materials like glass,
wood, paper and metal. Today, the family of polyethylene resins represents the
largest single group of plastic materials produced and consumed in the world.

Not all organizations have the capabilities or want to invest in acquiring the capabilities
to develop process technologies. Instead, licensing third party technology enables many
organizations to utilize state-of-the-art process know-how to fulfill their resin needs or to

ARDC/CS/Internal 67
enter a particular market, without having to invest heavily in developing proprietary
process technologies.

Typically, a company desiring to produce polyethylene would acquire a license for a

particular process technology, and perhaps catalyst technologies as well, from a
process licensor. Currently, there are over 25 licensors offering technologies to produce
linear polyethylenes. There are many factors associated with picking an appropriate
technology license including, but not limited to, (1) capability of the process to produce
the desired resin grades, (2) breadth of the process technology, (3) ability to produce
specialty grades, (4) catalyst options, and (5) most importantly, cost.

Some of the world-renowned polyethylene manufacturing technologies have been

discussed below:

Polyethylene - low density (LDPE) Production and

Manufacturing Process

High pressure LDPE production was first started in the 1950s and, while this technology
has been overshadowed in recent years by its LLDPE rival, processors still appreciate
LDPE's good optical and processing qualities.

Two basic processes are available for the production of low density polyethylene:
stirred autoclave or tubular routes. The tubular reactor has been gaining preference
over the autoclave route due to its higher ethylene conversion rates. The reaction is
carried out using a free radical initiator consisting of one or two peroxides with or
without oxygen. The processes can generally be used to make copolymers with polar
comonomers, such as EVA polymer.

4.1.1. High Pressure Process Technology from

ExxonMobil
Process mechanism:

In this process, the polymerization reaction is a free-radical polymerization, with organic

peroxides providing the source of the free radicals. As per the usual free radical process
kinetics, the three important steps of polymerization include initiation, propagation and

ARDC/CS/Internal 68
termination. Another free radical step, which has an immense importance as far as
polymerization of LDPE is concerned, is the chain transfer reactions. In this step the
active free radical sites at the ends of growing chains jump to another site on the same
polymer molecule, another polymer molecule, or a solvent, monomer, or a modifier.
Chain transfer affects the size, structure, and end groups of the polymers. The chain
transfer agents are those that can donate hydrogen atoms during the reaction.

Parameters controlling the reaction mechanism:

Peroxide type and concentration, as well as reactor temperature, control the initiation
rate. The propagation rate increases with pressure and temperature. The rate of chain
termination is controlled by free radical concentration and by the amount of chain
transfer agent present in the reaction mixture.

Critical factors during polymerization:

The efficient removal of the high heat of polymerization (~ 22 kcal/mol)

produced during the chain propagation steps
Type and amount of the peroxide initiator
Proper maintenance of reaction pressure and temperature
Amount of chain transfer agent in the reaction mixture

Properties of the manufactured LDPE resin:

Physical properties: Average molecular weight, molecular weight distribution, number of

short chain branches, and number of long chain branches control physical properties of
LDPE.
Morphological properties: The degree of crystallinity (and hence the density) is
controlled by the number of short branches (2 to 4 C atoms per branch). Short-chain
branches are formed as the result of intramolecular chain transfer or back-biting
reaction. A temperature decrease or a pressure increase decreases this branch
formation. Intermolecular chain transfer between a completed polymer molecule and a
growing polymer radical or between two growing polymer radicals forms long-chain
branches.

Rheological properties: These properties of the molten polymer are controlled by

molecular weight, the molecular weight distribution, and the number of long- chain
branches.

ARDC/CS/Internal 69
In the high-pressure LDPE process, the molecular weight of the individual polymer
chains is not uniform. The breadth of this molecular weight distribution depends on the
reactor process (tubular or autoclave) and can be further influenced by the reaction
conditions.

Process Overview
The overall processes for the tubular reactor and the autoclave reactor systems are
very similar except for the design of the reactor system itself. The two reactor
technologies have the capabilities of producing different products for different end-use
markets.

The main steps occurring during the process include the following:

1) Polymerization-grade ethylene is supplied to the battery limit and is boosted to

300 bar by the primary compressor and then divided into two separate streams.
2) One stream is fed to the secondary compressor suction, whereas the other is
added to ethylene-polymer mixture downstream of the reactor pressure control
valve.
3) In the secondary compressor combination of the gas from high pressure recycle
system and ethylene from the primary compressor takes place. Injection of chain
transfer agents and/or comonomers also occur in this section followed by
boosting of the pressure upto the reactor operating pressure (2500 to 3100 bar
for tubular reactor and 1200 to 2000 bar for autoclave reactor.
4) The ethylene mixture then flows to the reactor system (either autoclave or
tubular), where mixtures of organic peroxides diluted in liquid hydrocarbon
solvent are injected to initiate the exothermic polymerization reaction.
5) The reactor mixture (polyethylene and unreacted ethylene) is finally
decompressed to 300 bar pressure through the reactor pressure control valve.

ARDC/CS/Internal 70
Tubular Reactor Features

The tubular reactor is essentially a plug flow reactor. Multiple peroxide injection points
are used along the length of the reactor to maximize conversion of ethylene to LDPE
and optimize product properties.

Autoclave Reactor Features

The autoclave reactor is a continuous-stirred-tank reactor (CSTR) with an agitator to

promote good mixing. The multiple zones in the reactor allow for manipulation of the
temperature profile for tailoring of product properties.

ARDC/CS/Internal 71
Since the autoclave is an adiabatic CSTR, addition of the cooler, fresh feeds of ethylene
balances the heat of polymerization.

Product capability/Grade Slate

With ExxonMobil high-pressure autoclave technology, the grade-slate capability is:

Homopolymer LDPE ranging from 0.910 to 0.935 g/cm3 density

EVA copolymers up to 40 wt % vinyl acetate content
Specialty copolymers of ethylene methyl acrylate, ethylene acrylic acid, and
ethylene n-butyl acrylate
Extrusion-coating grades
High-clarity grades for film applications

With ExxonMobil high-pressure tubular technology, the grade-slate capability is:

ARDC/CS/Internal 72
 Homopolymer LDPE ranging from 0.915 to 0.935 g/cm3 density
EVA copolymers up to greater than 30 wt % vinyl acetate content
Very-high-clarity grades for specialty film applications

4.1.2. Lupotech T Technology from Basell

Process overview
The Lupotech T process is the leading high pressure tubular reactor process for the
production of low density polyethylene (LDPE) and Ethylene Vinyl acetate copolymers
(EVA). Worldwide over 50 licenses for this technology with a total capacity of over six
million tones per year have been granted with single line capacities of up to 400kt/a.
Products from the Lupotech T process cover the whole range of melt flows and
densities, and can be used for all LDPE applications including the wide range of EVA
grades.

High pressure tubular reactors are offered in two generally different forms, shown in the
figures. In a TS reactor the total ethylene flow from the hyper-compressor is preheated
to 150-180C and fed to the inlet of the first reaction zone. Reaction is initiated by
injection of organic peroxides. As the reaction mixture cools after the first reaction peak,
additional peroxide initiator is added to start a second reaction zone. There can be
further peroxide injection points giving a total of three to five reaction zones.
In a TM reactor (multiple cold gas injection) the compressed ethylene is split into
several streams and fed into the reactor at a number of positions. 40 to 70% of the total
ethylene is preheated to 150-180C before addition of peroxide that, together with the
oxygen, sets off the first reaction zone. The other 30-60% of the ethylene is cooled and
further split into more or less equal quantities that are injected at different locations
along the reactor. Together with addition of initiator this results in the desired number of
reaction zones.

ARDC/CS/Internal 73
ARDC/CS/Internal 74
Products and Applications
LDPE

Plant design tailored to the product portfolio requirements including specified

additive systems.
EVA grades, with up to 28% comonomer, especially suited for low temperature,
stress cracking resistance, flexible and transparent applications.

Film

Wide range of film applications include shrink and heavy-duty packing films, films
for laminates, carrier bags, composite and crack films, deep freeze bags and
agricultural films. Injection molding & blow molding
Enhanced technical properties include flowability, rigidity and stress cracking
resistance
Full range of grades includes specialty products for high purity pharmaceutical
applications and good organoleptic properties.

Pipe Coating

Corrosion protection properties with a well-balanced property profile for long term
durability, excellent processing, high mechanical strength and chemical resistance

Wire & Cable

Broad applications including power cables, insulation for coaxial cables and
telephone cable cores and sheathing materialInsulation for 1kV overhead cables and
conductive compounds
Very high resistance to environmental stress cracking

ARDC/CS/Internal 75
Linear Low Density and High density Polyethylene
Production Technology
4.1.3. Spherilene Technology from Basell
Basells Spherilene technology is an advanced gas phase process platform for the
production of polyethylene. The process can be used to produce the entire range of
linear polyethylene grades using a single catalyst system with true swing capability. The
product range includes linear low density polyethylene (LLDPE), medium density
polyethylene (MDPE) and high density polyethylene (HDPE). Premium bimodal grades
for demanding applications such as pressure pipes and high strength film are the
highlights of the Spherilene process.

ARDC/CS/Internal 76
Process Parameters Features

Basell (Spherilene) Multiple Uni & Bi Modal Products

Reactor Tailoring MWD possible
Wide Range of Products from VLDPE to
Low Pressure: 20 25 bar HDPE
Temp.: 85 116C Low Cost of Operation
Catalyst: Ziegler Natta Very Steady Process
Comonomers: C4, C6 Easiest to Swing

Process Advantages:

a) Versatility

Continuous operation, swing capability between LLDPE and HDPE using a single
family of Avant Z Ziegler catalysts
Spherilene S configuration with a single fluidized bed gas phase reactor provides
a low investment and operating cost option for production of a focused range of
polymers with monomodal molecular weight distributions
Spherilene C configuration with two fluidised bed gas phase reactors in cascade
provides the broadest range of ethylene polymers, including premium bimodal grades

b) Reducing Resource Intensity

High yield catalysts with excellent morphology control

Absence of solvents in the process
Complete recovery and recycling of all process streams
Absence of undesired by-products

c) Reliability

Operability rate of about 97%

Full hydrocarbon gas composition ensures efficient heat transfer preventing
lump formation
Use of state-of-the-art, Avant Z morphology controlled catalysts eliminates fines,
fouling and sheeting

ARDC/CS/Internal 77
d) Quality

Complete low pressure PE product portfolio with a density range from 0.915
to 0.962 g/cm3
Excellent process stability
Superior quality with minimum property variation
High first pass prime with low off-spec production

Products and Applications

Typical customer applications include:
LLDPE

General purpose film and bags

Agricultural film
Stretch film for Industrial applications
Bimodal specialty film

MDPE

Rotomolding for tanks and containers

Textile
Geomembranes and general purpose film
Wire & Cable

HDPE

Injection molding
Raffia, fiber and filament
Blow molding
Bimodal Film
PE80 and PE100 pipe

ARDC/CS/Internal 78
4.1.4. Hostalen Technology from Basell
Process overview:

Basells Hostalen PE process is a state-of-the-art slurry cascade technology that has

been designed to produce products with bimodal molecular weight distribution.The
mechanical properties of bimodal grades, such as stiffness and stress crack resistance,
have been significantly improved compared to unimodal resins. With total worldwide
licensed capacity of over six million metric tonnes per year, the process delivers
materials beyond the ordinary.

The latest enhancement to Basells Hostalen technology is the Hostalen Advanced

Cascade Process (ACP). It extends product performance by enabling the production of
premium multimodal HDPE products. Tailored HDPE resins for use in a variety of local
markets are now accessible with one catalyst chemistry by adjusting the process
conditions in a fast and flexible manner.

ARDC/CS/Internal 79
 Process Parameters Features

Pressure:~ 5-10bar, Multimodal HDPE with good combination

Temp. : 75-85C of Process & Performance
Solvent: Hexane Product Strengths HMHDPE Pipe, Blow
Catalyst: Ziegler Natta Molding
Co-monomers: C4, C6

Process advantages

a) Safety and Loss Prevention

Polymerization at low pressure and low temperature

Over 30 million metric tones of HDPE produced worldwide

b) Reduced Resource Intensity

No undesired by-products
Reduced resource consumption and lower emissions through closed-loop
hexane system during polymerization

c) Production costs

Conversion rate up to 99.5% for ethylene

Butene recovery and hexane recycle leads to minor losses on co-monomer and
diluent

d) Design Flexibility

Single-line capacities from 40 to 400 kTA/a

e) Process Versatility

Broad range of HDPE resins for all HDPE applications

Can be tailored to meet customer needs due to its flow rate ratio (FRR)

f) Product Quality

Excellent HDPE quality and product consistency due to process stability

g) Economical

ARDC/CS/Internal 80
 Cash cost advantages over other processes for bimodal HDPE production
Outstanding HDPE resins can be sold at higher business margins
Monomer purification unit not required if monomer is delivered from a state of-
the-art cracker

Products and Applications

Typical customer applications include:

Bimodal pipe products

Bimodal film products
Medium molecular film applications
Blow molding products
Tapes and monofilaments
Injection molded products

ARDC/CS/Internal 81
4.1.4. Sclairtech LLDPE/HDPE Swing Technology
from Nova Chemicals
Process overview:

Sclairtech technology offers polyethylene producers a unique and flexible way to grow
with their emerging market needs. The versatile solution process technology allows
resin manufacturers to participate in all market segments by economically producing, on
a single line, LLDPE and HDPE grades across a very wide range of melt indices, by
utilizing butene or octene comonomer. Resins can also be designed with a molecular
weight distribution from narrow to broad, according to the needs of the processor and
the application. The unique tailoring capability of the technology provides the ability to
produce high performance resins to meet the customer needs in diverse market
segments.

Process Parameters Features

Pressure:~ 27bar, Temp. : 160 200C

Uniform Co-monomer distribution
Solvent: Cyclohexane Low Xylene solubles
Catalyst: V - Ti catalyst (ST), Single Site Excellent Film Opticals
catalyst (AST)
Co-monomers: C4 and C8 Pdt. Strength Film & Raffia
Weak in RM, BM, IM, HM-HDPE
High Cost of Operation

ARDC/CS/Internal 82

Sclairtech Process Flowchart

Sclairtech Technology offers many advantages including the following:

The flexibility of the process allows grade transitions to be made in a

quick, efficient and economic manner. This unique ability allows producers
to make several grade changes in a day while minimizing off-spec
production and inventory build-up
The versatility of the process allows producers to participate in all major
market segments. The ability to economically make LLDPE through HDPE
with narrow or broad
MWD on a single line allows producers to select the best product mix for
their market at any given time
The process offers low operating costs along with the ability to make high
performance premium products
The unique ability of the process to produce gel free resins

Product Capability:

VLDPE Specialties
LLDPE Film
Extrusion Coating
Wire and Cable Jacketing
Rotomolding
Injection Molding
Pipe/Pipe coating
MMWHDPE Film
Blow Molding
Nonwovens

ARDC/CS/Internal 83
4.1.5. Mitsui CX Process
Process Overview:

It is a bimodal slurry phase process to produce high quality HMW-HDPE for Ultra-thin
film, Small & Large blow molding and Gas/Water pipes.
A Mitsui plant generally consists of the following sections:
Catalyst/Co-catalyst handling & metering

Polymerization unit consisting of two reactors

Polymer separation & drying

Extrusion & Pelletization

Product homogenization

Product storage & bagging

ARDC/CS/Internal 84
 The presence of two CSTR in a Mitsui line creates two possible routes of
polymerization:
a) Parallel Polymerization Route where the two reactors are connected in parallel
with respect to each other as shown below:

Reactor - 1 Second
Flash Centrifuge For Drying /Extrusion
Drum
Reactor - 2

Under parallel polymerization route again there are two different modes of operation:

Parallel A mode Parallel B mode

Operating Conditions are same in both Operating Conditions are different in

reactors both reactors
MFR/Density same in both reactors MFR/Density different in both reactors
Used for Narrow MWD Used for Medium MWD

b) Series Polymerization Route where the two reactors are connected in series with
respect to each other as shown below:

Reactor-1 First Flash Reactor-1

(High MFR) Drum (Low MFR)

Second Flash
For Drying / Centrifuge
Drum
Extrusion

In the series mode the following are observed:

ARDC/CS/Internal 85
 Operating Conditions are different in both reactors
MFR/Density different in both reactors
Used for Broad MWD

Process Parameters Features

Mitsui CX Twin CSTR Easy Tailoring of MWD by altering operation modes

Pdt. Strength HM Film, HM Pipe, HD Blow
Pressure:~ 8bar
Temp. : 75-85C
Solvent: Hexane
Catalyst: Ziegler Natta
(PZ-RZ/HS)

Co-monomers: C4, C6

Product Capabilities

The CX Process can provide resins t6o suit a wide variety of applications by simply
changing the operating conditions of the reactor system without a catalyst change. CX
products cover all important applications of CX products as mentioned below:

Ultrathin film
Heavy-duty bags
Bleach and detergent bottles
Automobile fuel tanks
Large Industrial containers
Telecom cable insulation
Gas pipes
High Pressure water pipes
Beer crates & vegetable containers
Rope & nets
Tape

ARDC/CS/Internal 86
4.1.6. Slurry-Loop-Reactor Technology from Chevron
Phillips
Process Overview:

At the heart of the process is the slurry-loop reactor. It contains a low-boiling

hydrocarbon (isobutane), which is a poor solvent for PE. It is used as a diluent for
suspending the catalyst, dissolving the monomer (ethylene gas) and comonomer (1-
hexene), and transferring the exothermic heat of the polymerization reactor to the
cooling surfaces of the reactor. This loop reactor is operated liquid-full at about 40
kg/cm2 pressure.

Since the PE particles do not reach temperatures high enough to go into solution, they
form discrete white particles the size of sand that form a slurry in the liquid isobutane.
The separation of the polymer particles from the slurry is done by allowing a slipstream
of reactor slurry to leave the process and drop from 40 kg/cm2 pressure to almost
atmospheric pressure. This pressure drop vaporizes the isobutane diluent, whereas the
remaining polymer particles drop by gravity into a fluidized bed of polymer particles,
where most of the remaining hydrocarbons are removed by a countercurrent flow of
nitrogen.

After drying the polymer particles are pneumatically conveyed to the extruder,
additivated with small amount of special chemicals and pelletized.

Phillips Slurry-Loop Reactor

ARDC/CS/Internal 87
Process Parameters Features

Unimodal Product
Ease of Operation - Loop Structure Ideal for
Pressure:~ 39bar, Temp. : 100 150C Removal of Heat
Solvent: Isobutane Product Strengths HDPE Pipe & HDPE Blow
(Marlex Grades)
Catalyst: Chromium oxide based catalyst
Single Reactor Process Tailoring of MWD
Co-monomers: C4,C6 difficult

Advantages of Slurry-Loop-Reactor Technology:

Benchmark advantages available in Chevron Phillips Chemical technology today

include costsavings, world-scale single reactor designs and proprietary catalysts.
Technical advantages of this process include the following:

Efficient Monomer Use

Efficient Heat Removal
Uniform Reactor Contents
Reliability
Quick Product Transitions
High-Activity catalyst Capability
Constructability
Loop Not Limited in Capacity

ARDC/CS/Internal 88
4.1.7. Borstar Loop-Gas Technology from Borealis

Process Overview:

It combines a loop reactor using supercritical propane as the polymerization medium,

placed in series with a gas-phase reactor where the second stage of the reaction takes
place.

The process starts when catalyst is fed into the loop reactor. With Borstar, no further
addition of catalyst is required for the gas-phase reactor.

The loop reactor can be run in a stable manner due to the use of supercritical propane
as the polymerization medium. The special conditions also significantly reduce reactor
fouling. This key advantage comes from reduced polymer solubility above the critical
point.

Borstar Process Flowchart

ARDC/CS/Internal 89
Process Parameters Features

Bimodal Product
Pressure: ~ 65,20bar, Temp. : 80C Tailored MWD possible
Solvent : Propane Pdt. Strengths Broad MWD Frac. MFI
LLDPE Film, HDPE BM
Catalyst: Ziegler Natta
Weakness High Haze in LLDPE Film
Co-monomers: C4

With Isobutane, as used in other processes, Polymer solubility is higher. This increases
the risk of reactor fouling and limits the density range that can be achieved.

Separate control of the two reactors is at the very heart of Borstar benefits. The resin's
modality is easily controlled, whether unimodal or bimodal.

For bimodal polymers, low molecular weights are formed in the loop, while high
molecular weights are formed in the gas-phase reactor. And the same high production
rates are possible with unimodal resins.

It's also possible to manipulate the comonomer content between the two reactors for
bimodal polymers. Increasing this content in the gas phase reactor - where the high
molecular weight fraction is produced - provides softness, higher impact resistance and
improved sealability.

Advantages of Borstar Loop-Gas Technology:

a) Borstar yields a number of special property and structural benefits. These include
high environmental stress-cracking resistance (ESCR), low shrinkage and long-term
creep/burst resistance.

b) The Borstar process offers simultaneous improvements in conversion economics and

in key environmental aspects, such as source reduction and recyclability.

Borstar PE Products
Film
Pipe
Extrusion coating
Injection Molding
Wire and cables
Blow Molding

ARDC/CS/Internal 90
 4.1.8. Unipol PE Gas Phase Process

Process overview
The process requires high degree of purity of the raw materials and polymer grade
ethylene. Raw material purification steps involve the use of molecular sieves, guard
beds, etc.

The reaction system can be subdivided into several sections: reaction loop, catalyst
feeding, and product discharge and separation.

Unipol PE Process Flowchart

Process Parameters Features

Single Reactor Process

Unimodal Product
Pressure : (20 25) bar Strengths
Temperature: (85 116) C BP: LL-Rotomolding & HD-IM
Unipol: Film, Hi MI LLDPE
Catalyst: Ziegler Natta, Chromium
Weak in BM,HM-HDPE
Comonomer: C4, C6
Low Operation Costs
Single Reactor Tailoring MWD difficult

ARDC/CS/Internal 91
4.2. Polypropylene Technologies

The first commercial production of polypropylene was in the 1950s following the
discovery of Ziegler-Natta catalysts. Since then, the process technology for PP
manufacture has kept pace with catalyst advances and the development of new product
applications and markets. In particular, the relationship between process and catalyst
technology was clearly symbiotic and that of a partnership. Advances in one technology
had always exerted a strong push-pull effect on the other to improve its performance.
The progress in process technology has resulted in process simplification, investment
cost and manufacturing cost reductions, improvement in plant constructability,
operability, and broader process capabilities to produce a wider product mix.

The PP industry is exciting and will continue to grow globally at a rate attractive to
making new investments. This is at par with the growing global demand of PP resin as
shown in the graph below:

Obviously the industry is highly competitive and the resin customers have high
expectations. To favorably compete and to satisfy customers, PP producers must have

ARDC/CS/Internal 92
access to world-scale technology when new investment is being considered. The
criteria for world-scale technology are the following:

1) Simple and efficient process

2) Attractive economics for resin manufacture: low plant investment and
operating cost
3) Efficient and high performance with fourth-generation catalysts
4) Capability for a wide range of products, with the ability to allow easy product
transitions in manufacturing
5) Environmentally clean and safe operations
6) Capability of plant design for high single-line capacity
7) Commitment of technology provider to continuous improvements and
innovations
Meeting the above criteria, various world-class PP manufacturing technologies have
emerged out of which some are discussed below:

4.2.1. Spheripol Technology from Basell

Basell`s Spheripol process is the result of many years of continued commitment in
polypropylene technology development. This technology offers licensees an elegant
and economical method to produce a wide range of premium quality polypropylene
products.

Today, more companies use Spheripol technology than the technologies of the three
closest competitors combined. More than 20 million tonnes of Spheripol process
capacity have been licensed worldwide. The capabilities of the Spheripol process have
been further enhanced using the latest-generation catalyst technology, which has the
ability to produce new families of reactor-based products with improved properties.

Process Overview:

The Spheripol process is a modular technology. In its most widely adopted configuration
the polymerization section involves the following main units:

Catalyst feeding

Polymerization

- Bulk polymerization (homopolymer/random copolymer and terpolymer)

ARDC/CS/Internal 93
- Gas-phase polymerization (heterophasic impact and specialty copolymer) - option
(gas-phase copolymer unit can be added at a later stage without affecting initial plant
configuration or involving significant implementation costs)

Finishing

The catalyst system used in this process is Ziegler Natta type. It is composed of three
basic parts: (1) a solid catalyst, generally TiCl4 supported on MgCl2; (2) stereoregulating
agents, an internal and external Lewis base; and (3) an aluminium alkyl.

ARDC/CS/Internal 94
 Spheripol Process

Process Advantages

a) Safety, loss prevention and reliability

Nearly seven million operating hours without a major incident

Average overall operability rate is about 98%

b) Reducing resource intensity

Spheripol technology has the leading position in low resource

consumption and emissions from the process
No solvents used in process
Recovery and recycling of non-reacted monomers
Absence of undesired by-products from the reaction

c) Versatility

A Spheripol process plant offers, on a single polymerization line, a very

wide range of homopolymers, random copolymers and terpolymers, as
well as heterophasic impact and specialty impact copolymers covering
all PP application markets.

ARDC/CS/Internal 95
 d) Quality

Minimum property variation due to excellent process stability and

consistency in Basell's catalysts performance

e) Design flexibility

Proven, single line capacities, from 40 to 550 kTA/a are available for
homopolymer, random copolymer or heterophasic impact copolymer
production
Tailored design for chemical or polymer grade monomer feedstock

f) Modular installation

50% average expansion of the initial capacity of existing plants that are
in operation for more than 10 years
Expansion achievable through minor adjustments
Extension of product range by introducing Metallocene PP technology
as an add-on technology
Flexible modular design has very low impact on investment costs

g) Low capital and operating costs

Capital costs are competitive with currently available PP processes

Lowest operating costs and high transition efficiency

Products and Applications

Random copolymers can be produced with excellent optical properties and seal
initiation temperatures in compliance with the U.S. Food and Drug Administration (FDA)
regulations for food contact.

Heterophasic copolymers with outstanding low-temperature behavior, high-impact

strength and enhanced stiffness can be obtained in a wide range of melt viscosities.

Typical customer applications using polypropylene manufactured from the Spheripol

process include:

Fibers and filaments

Oriented and cast film
Injection-molded products

ARDC/CS/Internal 96
 Thermoformed containers
Blow-molded bottles and parts

4.3.2. Spherizone technology from Basell

Basell`s new, breakthrough Spherizone multi-zone circulating reactor process provides
an economical and efficient method of manufacturing an growing range of high quality
polypropylene and novel, propylene-based polyolefinic resins.

With its ability to drive products to new extremes in properties and performance, the
technology continues to emerge as the new benchmark for polypropylene production.
Spherizone technology-based resins have the potential to enlarge the market for
polypropylene into entirely new application areas.

Spherizone technology was commercialized in 2002, when Basells Spheripol process

plant in Brindisi, Italy was upgraded through the installation of the Spherizone multi-
zone circulating reactor. Since 2004 about three million tonnes of polypropylene
capacity have been licensed based on Spherizone process technology.

Process Overview:

Because the Spherizone process is a modular technology, it typically includes the

following sections:

Catalyst feeding and activation

Polymerization

- Polymerization in MZCR-multi zone circulating reactor (homopolymer and random

copolymer)

- Gas-phase polymerization in a fluidized bed reactor (heterophasic impact and

specialty copolymer) is an option (gas phase copolymer unit can be added at a later
stage without affecting initial plant configuration or involving significant implementation
costs)

Finishing

ARDC/CS/Internal 97
The catalyst system used in this process is Ziegler Natta type. It is composed of three
basic parts: (1) a solid catalyst, generally TiCl4 supported on MgCl2; (2) stereoregulating
agents, an internal and external Lewis base; and (3) an aluminium alkyl.

Process Advantages:

a) Safety, loss prevention and reliability

Basells process technologies have a safety record among the best in the
industry
Structurally identical to the Spheripol process, Spherizone has shown high
reliability

ARDC/CS/Internal 98
b) Reducing resource intensity

Reduction of both: resource consumption and emissions

Recovery and recycling of non-reacted monomers
No undesired by-products from the reaction
Low energy consumption

c) Versatility

Wide range of high quality PP products possible

Novel resins with expanded properties and performance achievable
Modular approach in Spherizone process enables production of impact
copolymers

d) Quality

High product quality, allowing bimodality (MFR, composition)

Minimum property variation due to process stability and Basells catalyst
performance consistency

e) Design flexibility

Single line capacities up to 450 kTA/a can be provided

Homopolymer, random copolymer or heterophasic impact copolymer production
designs possible
Can utilize polymer grade propylene or chemical grade propylene

f) Modular installation

Flexible modular design, allowing low cost addition of a fluidized bed gas-phase
reactor for heterophasic impact copolymers

g) Low capital and operating costs

Capital costs are competitive with any PP technology currently available

Operating costs are typically lower

ARDC/CS/Internal 99
Products and applications
Typical customers manufacturing processes and end uses include:

Film extrusion
MuItifilaments
Nonwovens (meltblown and spunbonded)
Injection molding
Blow molding
Profile extrusion

ARDC/CS/Internal 100
4.3.3. Chisso Gas Phase PP Process

Press Overview:

Chisso Gas Phase PP Process Flowchart

Chisso Gas Phase Polypropylene Process features the use of a horizontal agitated
reactor and the high performance JPP Catalyst. This process provides high
performance and wide-ranging products with competitive investment and operation
costs. The right of license was given to Japan Polypropylene Corporation (JPP),
which is a PP joint venture between Chisso and Mitubishi Chemical Corporation.

ARDC/CS/Internal 101
 Comparison between CSTR and Chisso Horizontal Reactor

The Chisso Horizontal Reactor

Special features:

Plug Flow Movement

Heat Removal by Evaporative Cooling
Mild Mechanical Agitation

Rapid Grade Transition

Maximized Catalyst Activity
High Productivity
Uniform & Stable Temperature Control

ARDC/CS/Internal 102
 Importance of Plug Flow Characteristics for Impact Copolymer

Plug Flow Concept

Catalyst & Polymerization Technology

JPP Advanced Catalyst Technology

Catalyst Particle Size Distribution of JPPs Catalyst

High Activity
High & Tailored Stereo-Regularity
Excellent Morphology, Less Fines

ARDC/CS/Internal 103
 Integration of Catalyst, Polymerization & Manufacturing Technologies of JPP bring
Superior Product

Comparison of Stiffness and Impact Balance of Impact Copolymer

ARDC/CS/Internal 104
Product Attributes

Homopolymers

Injection molding
Blow molding
Thermoforming
Sheet
Tape (raffia)
Fiber
Cast and BOPP films
Profile extrusion

Random copolymers

Thin-walled injection molding

Low-heat-seal and high transparency films
Blow molding
Medical
Packaging parts

Impact Copolymers

Automotive parts
Appliances
House wares
Rigid packaging
Injection molding Thermoforming

ARDC/CS/Internal 105
4.3.4. Unipol PP Technology from Dow
Process Overview:

The UNIPOL PP process for polypropylene is a comprehensive technology and

services package with established worldwide success. It combines product and catalyst
know-how with leading gas-phase process technology and technology transfer
expertise. Licensed by Union Carbide since 1985, UNIPOL PP technology is now
available through Dow. Dow's commitment to the UNIPOL PP process is evidenced
by a significantly increased R&D effort directed at process technology improvements, a
continuing flow of advanced catalysts, and advantaged products to meet the needs of
market segments world-wide.

Compared to other processes, UNIPOL PP is a simple and elegant system, consisting

of either one or two gas-phase fluidized-bed reactors. To produce homopolymers and
random copolymers, a single reactor is used. For impact copolymers, a second-stage
reactor adds the key elastomeric component to the growing polymer chains. The
thoroughly back-mixed nature of the reactors leads to exceptional product consistency.

ARDC/CS/Internal 106
Catalyst system available from Dow is high-activity Ziegler-Natta-based catalysts
supported on MgCl2. An aluminium-alkyl is used as a co-catalyst. Internal and external
donors are used to vary isotacticity and molecular weight distribution.

Comprehensive PP Technology Offerings

The UNIPOL PP Process offers a broad and competitive product capability, including
homopolymer, random copolymers using ethylene or butene, and impact copolymers.
The advanced technology of the UNIPOL PP process is easy to operate, highly reliable,
and provides high product consistency.

Products and Features

Homopolymers

Commercial melt flow range of ~ 0.5 - 40 dg/min

BOPP film grades including market leading capability to process at over 400
m/min
Leading cast film grades
Tubular water quenched grades to meet regional market needs
Premium spun bond fiber grades
Controlled rheology molding grades for low warpage
Low taste and odor

Random Copolymers

Commercial melt flow range of ~ 0.1 - 100 dg/min

Superior heat seal performance from high ethylene content and special
CEFOR butene copolymers
New high clarity grades for double bubble process shrink film
New premium grades for spun bond fiber
High clarity molding grades
Unique high ethylene heat seal grade with excellent metallization

Impact Copolymers

Commercial melt flow range of ~ 0.1 - 100 dg/min

New IMPPAX grades providing high impact/ stiffness balance
High melt flow and high impact resistance
Rubber content up to 35%
Automotive, appliance, toy, thin wall, and general purpose molding applications

ARDC/CS/Internal 107
 5.0. Polyolefin Processing & End-Use Products
A large part of polymer processing technology can be summed up in the statement: get
the shape then set the shape. The general techniques, which are followed for shaping
polymers, include:

I. Deformation of polymer melt - Examples of processing technologies based upon

this technique are extrusion, injection molding, calendaring, etc. In tonnage terms
this is the most important processing class.
II. Deformation of a polymer in the rubber state - Vacuum forming, pressure forming
& warm forging techniques are based on this principle.
III. Deformation of a polymer solution either by spreading or by extrusion as used in
making cast film & certain synthetic fibers & filaments.
IV. Deformation of a suspension- a very popular technique for rubber latex & other
lattices & with PVC paste.
V. Deformation of low molecular weight polymer or polymer precursor such as in the
casting of acrylic sheets & preparation of glass reinforced laminates.
VI. Machining operations

The term polymer includes elastomers, plastics & fibers. Here different plastic
processing techniques & plastic end use products would be discussed.

Out of the six polymer processing techniques, the first one, which involves the
deformation of polymer melts, is the most widely used technique in plastic industry.
The reason for this may be as follows:

a) Easier processability of polymer melts in terms of mixing with additives & the final
shaping operation.
b) Simplicity in designing the melt processing equipments as compared to the other
techniques.
c) Lower energy consumption during polymer melts processing.
Deformation of a polymer melt can be done conveniently through extrusion, various
molding operations & sometimes a combination of both the technologies.

5.1. Extrusion Process

Extrusion process consists of forcing a polymer in liquid form (usually molten) under
pressure through a die to produce a continuous section or profile. This may then

ARDC/CS/Internal 108
 be sized, drawn down, corrugated, etc., to modify & control the shape & dimension
of the section & in some cases the properties (mechanical, optical, etc.). The
process of extrusion is carried out in equipment called extruder.

5.1.1. Equipment Design:

5.1.2. Extruder Screw Design:

The screw is the most important component of the extruder. There are five possible
zones in a thermoplastic screw. Since terminology is not standardized in the industry,
different names may refer to these zones. Different types of polymer will have differing
screw designs, some not incorporating all of the possible zones.

a) Feed zone - Also called solids conveying zone. This zone feeds the resin into
the extruder.
b) Melt zone - Also called the transition zone. The resin is melted in this section.

ARDC/CS/Internal 109
 c) Pressurizing zone - Also called metering or melt conveying. This zone gives
the plastic uniform pressure and flow characteristics.
d) Devolatization zone - In this zone, the melt is unpressurized, allowing trapped
gases to escape and be vented out.
e) Mixing zone -There are two types of mixing zone. They either distribute small
particles evenly, or break large particles into small ones, which can then be
mixed.

5.1.3. Process Overview:

In the extrusion of plastics, raw thermoplastic material in the form of small beads (often
called resin in the industry) is gravity fed from a top mounted hopper into the barrel of
the extruder. Additives such as colorants and UV inhibitors (in either liquid or pellet
form) are often used and can be mixed into the resin prior to arriving at the hopper.

The material enters through the feed throat (an opening near the rear of the barrel) and
comes into contact with the screw. The rotating screw (normally turning at up to 120
rpm) forces the plastic beads forward into the barrel, which is heated to the desired,
melt temperature of the molten plastic (usually around 200 C/400 F). In most
processes, a heating profile is set for the barrel in which three or more independently
controlled heaters gradually increase the temperature of the barrel from the rear (where
the plastic enters) to the front. This allows the plastic beads to melt gradually as they
are pushed through the barrel and lowers the risk of overheating which may cause
degradation in the polymer. Extra heat is contributed by the intense pressure and
friction-taking place inside the barrel. In fact, if an extrusion line is running a certain
material fast enough, the heaters can be shut off and the melt temperature maintained
by pressure and friction alone inside the barrel. In most extruders, cooling fans are
present to keep the temperature below a set value if too much heat is generated.

At the front of the barrel, the molten plastic leaves the screw and travels through a
screen pack to remove any contaminants in the melt. The screens are reinforced by a
breaker plate (a thick metal puck with many holes drilled through it) since the pressure
at this point can exceed 5000 psi (34 MPa). The screen pack/breaker plate assembly
also serves to create backpressure in the barrel. Backpressure is required for uniform
melting and proper mixing of the polymer. This breaker plate also does the function of
converting "rotational memory" of the molten plastic into "longitudinal memory"

After passing through the breaker plate, the molten plastic enters the die. The die is
what gives the final product its profile and must be designed so that the molten plastic
evenly flows from a cylindrical profile, to the product's profile shape. Uneven flow at this
stage would produce a product with unwanted stresses at certain points in the profile.

ARDC/CS/Internal 110
These stresses can cause warping upon cooling. Almost any shape imaginable can be
created so long as it is a continuous profile.

The product must now be cooled and this is usually achieved by pulling the extrudate
through a water bath. Plastics are very good thermal insulators and are therefore
difficult to cool quickly. Compared with steel, plastic conducts its heat away 2000 times
more slowly. In a tube or pipe extrusion line, a sealed water bath is acted upon by a
carefully controlled vacuum to keep the newly formed and still molten tube or pipe from
collapsing. For products such as plastic sheeting, the cooling is achieved by pulling
through a set of cooling rolls.

5.1.4. Basic Advantages of Extrusion Process:

1. Complex extruded shapes close to the finished product profile can be produced in
one operation, which enables very significant savings to be made on raw material
usage. The material yield loss due to machining or finishing operations can be greatly
reduced or totally eliminated by using a near net extruded section. The higher value
materials give greater savings using the extrusion route.

2. The extrusion process is well suited to short production runs. The tooling costs are
low and the production change over down time between different sections is very short.
Therefore either long or short production runs are both practical and economical using
the extrusion process.

3. The tooling charges for a set of extrusion dies are very modest when compared to the
set up costs for rolling, casting and forging. Extrusion production lead times can be
relatively short. Overall production times and costs can be significantly reduced,
compared to other methods of manufacture by reducing or even eliminating machining
and finishing operations

5.1.5. Products from extrusion Process

A. Films

Film

Blown Film Cast Film Biaxially Oriented film

1. Blown Film
One of the most common methods of film manufacture is Blown Film (also referred to as
the Tubular Film) Extrusion. The process involves extrusion of a plastic through a

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circular die, followed by "bubble-like" expansion. The principal advantages of
manufacturing film by this process include the ability to:
Produce tubing (both flat and gussetted) in a single operation
Regulation of film width and thickness by control of the volume of air in the
bubble, the output of the extruder and the speed of the haul-off.
Eliminate end effects such as edge bead trim and non uniform temperature that
can result from flat die film extrusion.
Capability of biaxial orientation (allowing uniformity of mechanical properties)
Blown Film Extrusion can be used for the manufacture of co-extruded, multi-layer films
for high barrier applications such as food packaging.

Polyethylenes (HDPE, LDPE and LLDPE) are the most common resins in use, but a
wide variety of other materials can be used as blends with these resins or as single
layers in a multi-layer film structure. These include PP, PA, EVOH. In some cases,
these materials do not gel together, so a multi-layer film would delaminate. To
overcome this, small layers of special adhesive resins are used in between. These are
known as tie layers.

Blown film can be used either in tube form (e.g. for plastic bags and sacks) or the tube
can be slit to form a sheet.

Typical applications of blown films:

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Industrial Packaging

Consumer Packaging
These include the packaging film for frozen products, shrink film for transport
packaging, food wrap film, packaging bags, or form, fill and seal packaging film and
carry bags.

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Laminating film

Polyolefin films are used for laminating aluminium or paper used for packaging
condensed milk or coffee.

Barrier film
These films, made of raw materials such as polyamides and EVOH acting as an aroma
or oxygen barrier, are used for packaging food, e.g. cold meats and cheese.

Agricultural film

Films such as greenhouse film, crop forcing film, silage film, and silage stretch films are
used in agricultural applications.

2. Cast Film

The cast film process involves the extrusion of polymers melted through a slot or flat
dies to form a thin, molten sheet or film. This film is "pinned" to the surface of a chill roll

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(typically water-cooled and chrome-plated) by a blast of air from an air knife or vacuum
box. The film quenches immediately and then has its edges slit prior to winding.

Because of the fast quench capabilities, a cast film generally has much better optics
than a blown film and can be produced at higher line speeds. However, it has the
disadvantage of higher scrap due to edge-trim, and very little film orientation in the
cross-direction.

Cast films are used in a variety of markets and applications, including stretch/cling films,
personal care films, bakery films, and high clarity films.

2. Biaxially Oriented Film

Biaxially oriented film is the film, which is stretched in both the machine & the
transverse direction, producing molecular chain orientation in two directions.

Two process variants are used:

Ribbon extrusion, melt cooling and simultaneous tenter (stenter) drawing in

two directions
Tubular extrusion, rapid melt cooling followed by IR heating and then biaxial
blowing and drawing the PP below its melting point

The most common manufacturing BOPP film is produced by the tubular process, in
which a tubular bubble is inflated or a tentor frame process, in which a thick extruded
sheet is heated to the softening point & is mechanically stretched by 300-400%.
Stretching in the tentor frame produced is usually 4.5:1 in the machine direction & 8:1
in the transverse direction.

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 BOPP tenter line production

A. Extruder
B. Melt pump
C. Chill roll
D. Stretching in machine direction
E. Stretching in cross direction
F. To winding euipment
In the double bubble process, a cast tube is blown into a large bubble with
simultaneous stretching in both directions to produce a balance film. This processs is
used to make heat-shrink films as well as standard BOPP films.
Biaxially oriented films are used in food packaging & are replacing cellophane in
application such as snack & tobacco packaging due to favorable properties & low cost.
Oriented films are used as heat shrinkable films in shrink-wrap application.

Tubular Quenched film

A tubular film process in which the bubble is quenched with water so as to improve the
clarity of films made from crystalline, thermoplastic materials such as polypropylene.

The tubular water quench process combines the airblown process with chill roll or
conventional water bath and includes drawing a bubble of molten film to a desired
diameter.
Among the different techniques commercially available is shell Tubular Quench (TQ)
process, which involves downward extrusion from an annular die followed by rapid
cooling on water-covered converging boards. At the same time the tubular molten film is
inflated with air in the normal way to give it the required layflat width and thickness.

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Another process known is the Dow-Taga process. In this process, the blown film goes
Through a hollow ring where it is coated with a film of water, which flows from the ring
and on to the film before it, is collapsed. The water film that runs down the converging
boards shock cools the film and causes rapid crystallites formation and hence the
formation of small spherulites with a consequent increase in clarity.

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 Among the advantages of the water-cooled tubular process mentioned above are
(1) Low cost,
(2) Ease of conversion into bags and
(3) Flexibility of operation.
These factors have been largely responsible for the large-scale penetration of low-
density PP films into packaging markets. Techniques of water-cooling tubular PP film,
however, have opened up ways of producing clear films, with greater toughness and at
no greater cost than cast PP (CPP) films.

Application: General purpose packaging films such as for garments bags, food
packaging, and other transparent packaging bags.

Pipes
Polyethylene pipes account for a large number of applications and are slowly but
steadily replacing PVC pipes from their application domains. The common applications
of polyethylene pipes include pressure pipes, sprinkler irrigation, gas pipes, drip lateral
pipes and PLB ducts.

Sprinkler Irrigation
Gas Pipes
Pressure pipes
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 Drip Laterals
PLB Ducts

The pipe extrusion process involves forcing the polymer melt through a circular die. The
general steps of pipe extrusion can be summarized as below:

Polymer granules are fed into the hopper & conveyed by a rotating screw through a
long cylindrical barrel.

This is then subjected simultaneously to high temperature and pressure, forcing the
melt through the die at a predetermined rate.

The extrudate from the die is sized, cooled and the formed pipe is pulled to the winder
or a cut off device with the aid of haul off device.

The Pipe Extrusion Process A Schematic

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 Profiles
To manufacture plastic pipe, industry uses a process known as Profile Extrusion.
This process is used to manufacture plastic products with a continuous cross-
section such as; drinking straws, decorative molding, window trimming and a wide
variety of other products polymer melt into the hollow mold cavity under high
pressure.

The plastic is fed in pellet form into the machines hopper (this machine is known as
an Extruder), the material is conveyed continuously forward by a rotating screw
inside a heated barrel being softened by both friction and heat. The softened plastic
is then forced out through a die and directly into cool water where the product
solidifies. From here it is conveyed onwards into the take-off rollers, which actually
do the pulling of the softened plastic from the die.

The die is a metal plate placed at the end of the extruder with a section cut out of its
interior, this cutout, and the speed of the take-off rollers, determines the cross-
section of the product being manufactured. A simple way to understand this
concept is to consider squeezing a toothpaste tube, the product comes out in a
solid rod because of the opening at the end of the tube, if that opening had a
different cross-section than the product produced would take on that new cross-
section.

Typical Materials for Plastic Profiles: HDPE (High Density Polyethylene), LDPE (Low
Density Polyethylene), LLDPE (Linear Low Density Polyethylene), PETG, Flexible PVC,
Butyrate, Polypropylene Polystyrene ABS

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Advantages

Equipment widely available in all geographical areas. Short lead times.

Relatively low tooling costs
Inexpensive process
Product combinations possible
Design freedom

Disadvantages

Design possibilities severely limited because of linear nature of process.

Sheet Extrusion
Sheet extrusion is a technique for making flat plastic sheets from a variety of resins. The
thinner gauges are thermoformed into packaging applications such as drink cups, deli
containers, produce trays, baby wipe containers and margarine tubs. Another market
segment uses thick sheet for industrial and recreational applications like truck bed
liners, pallets, playground equipment and boats. The third primary use for extruded
sheet is in geomembranes, where flat sheet is welded into large containment systems
for mining applications and municipal waste disposal.

Thermoplastic sheet production is a significant sector of plastics processing.

Thermoplastic sheets are flat, plastic materials with a gauge of at least 250 microns and
which include both flexible and rigid materials, as well as solid, foamed, and hollow
materials.

Solid sheet extrusion units consist of at least one extruder and one sheet extrusion die.
They are followed by the polishing stack, in general comprising 3 calenders, calibrating
and cooling the sheet with their surfaces or calender nips. Behind this the roller
conveyor and the draw-off rolls for air cooling are located. The sheet is finally cut and
stored.

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Materials: Polystyrene continues to be the most common polymer for use in sheet
extrusion. It is the dominant material for thermoformed packaging and competes with
ABS and PP in technical markets. End use applications include tubs and pots for yogurt,
margarine, and desserts. Thermoformed packaging is also used in many other
applications in the food industry.

Applications

Within the building and construction industries, sheet extrusion is used for a variety of
applications. One of the main uses of extruded PS sheet is for thermal insulation
materials for walls, roofs, and under floors.

In the automotive industry, sheet is currently used to produce interior trim, panels, and
dashboards. Foamed polyolefin sheet, both cross-linked and non-cross-linked, is also
used in automotive applications.

There are a number of other applications where thermoformed sheet plays a significant
role. These include the manufacturing of luggage, refrigerator liners, and shower units

Wires & Cables Coating:

Coating wire & cable with a polymer is accomplished via a crosshead extrusion
process. The wire or cable to be coated is pulled at constant rate through a crosshead
die, where molten plastic covers it. A crosshead extrusion operation has the extruder
set at right angles to the wire reel & the rest of the down stream equipment. Wires enter
the die at a 90 angle to the extruder, with the polymer entering the side of the die &
exiting at a 90 angle from the extruder.

The figure shows a block diagram of a crosshead extrusion operation with typical
equipment in the line
Unwind station or other wire or cable source to feed the line
Pretensioning station to set the tension through out the process
Preheat station to prepare the wire for coating
Crosshead die
Cooling trough to solidify the polymeric coating

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 Test station to assure the wire is properly coated
Puller to provide constant tension through the process
Winder to collect the product

Typical polymers used in wire coating application are Polyethylene, PVC, Polyamide,
Polybutylene terepthlate, Thermoplastic elastomers, ethylene propylene, and
fluropolymers.
These polymers are chosen because of their electrical properties, flexibility, & durability.
Cross linked polyethylene is used in wire coating operation.

Stretch tapes:

Slit film tapes made of polyolefin's such as polypropylene (PP), high density
polyethylene (HDPE) and linear low density polyethylene (LLDPE) and other similar
polymeric materials ate well known and have several applications. The major area of
application includes woven sacks, large industrial sacks and packaging fabrics, geo-
textiles, ropes and twines and miscellaneous industrial woven fabrics.

Slit film tapes can be produced from extruded cast flat or tubular (blown) film. . The
majority of slit film tapes are made from cast films. In this method desired orientation in
slit film tape is accomplished through a series of rollers with increasing speeds and
increasing temperature. After the slit film tapes have been stretched in the machine
direction, they may be reheated on a set of heated rollers and cooled on a set of cooled
rollers to reduce residual shrinkage.

The molten polyolefin is extruded through a suitable extrusion die to form sheet of
required thickness that is suitably cooled by a device like water- quench or chilled
roll(s). Then the substantially amorphous sheet is transported under tension to a
suitable slitting device to be slit into film tapes. The slit film tapes are mono-axially
oriented by drawing in a longitudinal direction, under heated conditions, to arrive at slit

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film tapes which can be defined in terms of an orientation ratio, sometimes also referred
to as the draw or stretch ratio. The unstretched slit film tapes are heated by means of
hot air oven to a temperature just below softening temperature during the drawing or
stretching process & then winding the slit film tapes; characterized in that before the
stretching step, it has a stage of pre-stretching made by passing the slit film tapes
through one set of heated holding rollers turning at a given speed and one set of cooled
pre-stretch rollers turning faster than the heated holding rollers, wherein at least one of
the rollers of the set of holding rollers is heated and at least one of the rollers of the set
of pre-stretch rollers is cooled.

The process diagram is shown below:

The stretch tapes manufacturing process involves the following steps

Extruded flat film Slit to flat tapes Stretched hot oven/bed Wound In
Bobbins Woven in circular /Flat looms Coated / Stitched / Printed for
bags

Applications :

Fertilizer bags, tarpaulins, woven fabric etc

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 Monofilaments
Monofilament fabrics are constructed from monofilament yarns, recognized by most
people for their use in fishing or weed-wacker line. Monofilament yarn size range, in
nominal diameter, from0.001 (25 microns) up to 0.040 (1,000 microns) and very
consistent in diameter, with the exception of polypropylene which is difficult, to spin
(extrude) without diameter variation.
However the manufacturing process is similar to that of stretch tapes except with a
difference of die type & the processing parameters. The die, which is used in the
monofilament, is a circular die with large number of holes of specified dimension.

The process diagram is shown below:

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 Yarn from the die

Application areas: Mosquito Nets, Fishing Nets, Ropes

5.2. Molding Process

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5.2 Plastic Molding Process
Molding is the process of rendering shape to materials by the allowing the plastic melt
to flow, mostly under pressure, into a solid and confined framework called mold.

5.2.1 Injection Molding

One of the most common methods of shaping plastic resins is a process called injection
molding. Injection molding is a manufacturing technique for making parts from both
thermoplastic and thermosetting plastic materials in production. In injection molding,
plastic granules are heated and "injected" under pressure into metal molds, where the
molten plastic hardens into a designated shape. The mold then opens and the newly
formed part is removed and inspected, ready for shipment or secondary manufacturing
operations. Injection molding is an extremely versatile and popular form of molding.

It is a fast process and is used to produce large numbers of identical items from high
precision engineering components to disposable consumer goods.

Equipments design

The injection system consists of a hopper, a reciprocating screw and barrel assembly,
and an injection nozzle the plasticizing screw, a barrel, band heaters to heat the barrel,

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a stationary platen, and a movable platen. This system confines and transports the
plastic as it progresses through the feeding, compressing, degassing, melting, injection,
and packing stages

The process of injection molding can be reduced to four simple individual steps:
Plasticizing, Injection, Chilling, and Ejection. Each of those steps is distinct from the
others and correct control of each is essential to the success of the total process.

Plasticizing - describes the conversion of the polymer material from its normal
hard granular form at room temperatures, to the liquid consistency necessary for
injection at its correct melt temperature.
Injection - is the stage during which this melt is introduced into a mold to
completely fill a cavity or cavities.
Chilling - is the action of removing heat from the melt to convert it from a liquid
consistency back to its original rigid state. As the material cools, it also shrinks.
Ejection - is the removal of the cooled, molded part from the mold cavity and from
any cores or inserts.

Process Parameters

1. Temperature: Typical temperature profiles are based on gradually increasing

temperature during the compression phase with cooling at the nozzle.
2. Injection speed: A slow to moderate injection speed should be used if injection
speed is too fast. The frictional heat can cause surface imperfections. Injection
speed causes inner friction that helps together with barrel temperature to keep
the material as melt.
3. Mold temperature: A mold temperature between 10C to 40C is used. When
using temperatures below 10C care must be taken to ensure cavities will
consistently fill and no condensation appears on the mold face.
4. Mold cooling: The purpose of mold cooling is to control the rate at which heat is
removed from the molding. If there is no cooling on the mold then initially the
mold will be cool and will heat up due to the heat transfer from the molded parts.
This effect can result in varying shrinkage rates.

Advantages

Produce discreet parts having complex & variable cross section

Make parts with wide range of surface textures

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 Highly repeatable process
Almost all thermoplastic & some thermoset can be used
Highly automated, little post-molding finishing required
Direct route from raw material to finished parts.

Disadvantages

High initial equipment investment

High startup and running costs possible
Lacking in automated feedback & control system

Products from Injection molding

House Hold Items: Containers, Bins, Buckets, Toys & Novelties

Crates: Soft Drink Bottle Crates, Multipurpose Crates ,Milk Crates

Large Crates: Jumbo Crates for Agriculture, Industrial & Retail sectors

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 Caps & Closures

5.2.2 Blow Molding

Blow molding is a manufacturing process by which hollow plastic parts are formed.

It is best suited for basically hollow parts (such as plastic bottles) with uniform wall
thicknesses, where the outside shape is a major consideration.

This process usually uses commodity materials such as:

Polypropylene PP
Polyethylene PE
Polyethylene - Terephthalate PET
Polyvinyl chloride PVC
HDPE

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Equipments design:

The Basic Process

1. A thermoplastic resin is heated to a molten state

2. It is then extruded through a die head to form a hollow tube called a
parison.
3. The parison is dropped between two mold halves, which close around it.
4. The parison is inflated.
5. The plastic solidifies as it is cooled inside the mold.
6. The mold opens and the finished component is removed.

There are basically three types of blow molding used in the production of plastic bottles,
jugs and jars. These three types are:

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 1. Extrusion blow molding

In extrusion blow molding the parison is formed by forcing molten plastic through
an annular orifice in a die that is part of the die head assembly. The orifice is
formed by the space between the mandrel and the die. Extrusion may be directly
from an extruder, or for large parts for which more material is needed than the
extruder can continuously provide an accumulator is used.

The parison is extruded and drops to between the mold halves and when the
mold closes the parison is sealed. Air injected into the parison inflates it to the
shape of the mold cavity. After cooling and solidification the mold is opened and
the part removed.

Process steps

Step 1. Parison Extrusion. Parison dented by arrow

Step 2. Mold Halves close onto parison.

When the parison has reached a sufficient length a hollow mould is
closed around it. The mould mates closely at its bottom edge thus
forming a seal. The parison is cut at the top by a knife prior to the
mould being moved sideways to a second position where air is blown
into the parison to inflate it to the shape of the mould.

Step 3. Parison inflated against inflated internal mold walls.

The parison is cut at the top by a knife prior to the mould being moved
sideways to a second position where air is blown into the parison to
inflate it to the shape of the mould.

Step 4. Mold halves open, Blow molding part ready for ejection
After a cooling period the mould is opened and the final article is
ejected. To speed production several identical moulds may be fed in
cycle by the same extruder unit.

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Advantages of Extrusion Blow Molding:

Low initial mold tooling costs.

Flexibility of tooling. Molds can accommodate interchangeable neck finishes and
body sections.
Flexibility in production: Neck inner diameters (I.D.) can be easily controlled to
varying requirements. Bottle weights are adjustable.
Container sizes can range from less than 1 oz. to 55 gallons and up. (Custom
Bottle's equipment is most efficient producing containers up to 1 liter in capacity.)
Container shape is not restricted by blow-up ratios. Bottles can be long and flat
or have handles.
Wide selection of machine sizes: Molds can be geared to volume requirement

2. Injection blow molding

Injection blow molding is a two-stage process since the parison is produced in a

separate operation. In the first process molten plastic is injected into a heated preform
mold around a hollow mandrel blow tube or core rod. This is similar to insert injection
molding. The workpiece for the second, blow molding, and process is the preform-
mandrel assembly. The preformed parison is placed in a larger mold cavity for blow
molding. Between the preform production and blow blow molding processes a heated
preform may be held in a temperature conditioning stage or a cooled preform re-heated.
After blow molding the part is stripped from the core rod at an ejection station.

Process Steps

Step 1. Injection
The injection blow molding machine is based on an
extruder barrel and screw assembly which melts the
polymer. The molten polymer is fed into a manifold
where it is injected through nozzles into a hollow,
heated preform mould. The preform mould forms the
external shape and is clamped around a mandrel (the
core rod), which forms the internal shape of the
preform. The preform consists of a fully formed
bottle/jar neck with a thick tube of polymer attached,
which will form the body.

Step 2. Blowing
The preform mould opens and the core rod is rotated

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 and clamped into the hollow, chilled blow mould. The
core rod opens and allows compressed air into the
preform, which inflates it to the finished article shape.

Step 3. Ejection
After a cooling period the blow mould opens and the
core rod is rotated to the ejection position. The finished
article is stripped off the core rod and leak-tested prior
to packing. The preform and blow mould can have
many cavities, typically three to sixteen depending on
the article size and the required output. There are three
sets of core rods, which allow concurrent preform
injection, blow molding and ejection

3. Stretch blow molding

Stretch blow molding produces a part with biaxial molecular alignment. In the
process a preform, or parison, elongated mechanically in the mold and than
expanded radially in a blowing process. A desirable resulting molecular
orientation yields a material with increased strength. This means that products
that are strength-based designs can be produced using less material than if they
were to be produced using simpler blow molding techniques.

A-Stretch blow pin B-Air entrance C-Mold vents D-Preform E-stretch

rod extended F-Cooling channels

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 A goal in stretch blow molding is a designed work material developed by
producing desirable molecular orientation. In order to produce and retain desired
structure and specified properties the stretching and blowing processes need to
be carried out at temperature lower than in other blow molding processes and the
allowable temperature range will be smaller and so more difficult to control. A
temperature conditioning station in-line is required, or a re-heating operation
needed for preforms allowed to cool before use or for purchased preforms. This
increased the difficulty of process design and operation and material specification
since polymer properties depend on temperature history, e.g., on temperature,
time at temperature and number of temperature cycles

Process parameters

The main process parameters for extrusion blow molding are those that affect parison
geometry and mechanical properties. Parison geometry is determined by material flow
during extrusion and as the forming parison drops between the mold plates. The
machine parameters that affect material flow and so control parison formation are

Melt temperature
Extrusion ram speed or extrusion pressure
Mandrel and die bushing diameters, orifice size
o Change in orifice during extrusion - parison programming
Mandrel-die shape - exit angle
Mandrel tapered area surface area
Mandrel-die alignment
o Parison wall thickness can be altered slightly by offsetting
To account for part asymmetry
May result in parison curvature

Disadvantages:

Cycle times are slower than the injection molding.

Machines typically dedicated to a narrow range of sizes. Product change

can be difficult, especially when downstream trimming changeovers are
required.

High initial capital investment

Products from Blow Molding Process

Blow molding is used to make many plastic containers, including soft-drink bottles, jars,
detergent bottles, and storage drums.

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5.2.3 Roto Molding
Rotational molding is a process by which hollow objects can be manufactured from
thermoplastics and occasionally thermosets.

Roto molding is a cost-effective way to produce large parts. With roto-molding process it
is possible to create one piece, seamless and stress free plastic products with superior
surface finish of any size gigantic or small, in every possible shape and even exotic
nature.

Equipments design:

Roto molding process involve two different machines

Biaxial rotomolding machine

ARDC/CS/Internal 136
 Rock & roll machine

Process Steps. The Rotational Molding process is essentially split into four operations:
Step #1. Loading resin into the mold
The rotomolding process is begun by placing a pre-measured
amount of plastic material (in either liquid or powder form) in a
cavity. The mold is then closed and indexed into an oven where it
and its contents are brought up to the molding temperature. As the
mold is heated, it is rotated continuously about its vertical and

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 horizontal axes. This biaxial rotation brings all surfaces of the mold
in contact with the plastic material.

Step 2. Heating and fusion of resin

The mold is rotated within the oven until all the plastic material has
been picked up by the hot inside surfaces of the cavity and densifies
into a uniform layer. While continuing the rotation, the machine
moves the mold out of the oven and into the cooling chamber.

Step 3. Cooling before unloading

Air, or a mixture of air and water, cools the mold and the layers of
molten plastic material. This cooling process continues until the part
has cooled sufficiently to retain its shape. The machine then
indexes the mold to the loading and unloading station.

Step 4. Unloading/Demolding
When the polymer has cooled sufficiently to retain its shape and be
easily handled, the mould is opened and the product removed. At
this point powder can once again be placed in the mould and the
cycle repeated.

More than 80% of all the material used is from the polyethylene family. Cross-linked
polyethylene (PE); linear low density polyethylene (LLDPE); high density polyethylene
(HDPE). Other compounds are PVC plastisols, Nylons, and polypropylene

Process parameters:

Temperature: Temperature control is important if plastic is subjected to relatively high

temperatures, in the presence of air, for excessive periods of time can lead to thermal
and oxidative degradation at the inner free surface of the plastic, resulting in
deterioration in the performance of the molded part.

Mold pressure: A drawback of the rotational molding process has always been the
surface pinholes and internal bubbles that occur in the molded part. These occur
because, as the powder particles melt and coalesce, they trap pockets of air and it
takes a considerable time for these to disappear. It is known that factors such as the
viscosity of the polymer melt, the shape of the powder particles, the particle size and
size distribution, the mould release agent and the metal used for the mould all affect the
pin holing problem. However, the major factor that influences pinhole removal is mould
pressure.

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Advantages:

Unlike other plastic molding processes, roto-molding results in seamless parts

with uniform wall thickness and more material in corners, to absorb shocks and
stresses where they occur most.
The finished part is stronger as in thermoforming or pressure forming, the
material is not stressed. Plus the molds dont need to be designed to withstand
the high pressures of injection molding.
Tooling costs are lower in that regard and minor changes can be easily made to
existing molds as the mold has no internal core to manufacture, Roto-molding
also offers superb flexibility and precision.
Roto-molded plastic products are easy to handle and less expensive to ship due
to lighter weight than metal or fiberglass.
Roto-molded plastic products are tough, long lasting, and corrosion-proof.
Molds are typically simple & inexpensive (typically 1/5th that of injection molds)
Various molds may run simultaneously on same machine capable of producing a
wide range of sizes

Disadvantages

High energy consumption.

Low production rates due to high cycle time.

Low shear during processing leading to less compactness & hence inferior
mechanical properties compare to other blow molded products.

Applications: Rotational molding is incredibly versatile, able to handle a vast variety of

shapes and sizes. Many parts cannot be readily produced by any other method.
INDUSTRIAL & COMMERCIAL Agriculture, Health & Science, & Point of Sale (POS):

Specialty tanks and containers for fuel, water, and chemical processing

Livestock feeders
Drainage systems
Food service containers
Instrument housings
Vending machines
Highway barriers and road markers

CONSUMER PRODUCTS Recreational, Special Application, Toy, & Transportation:

Boats and kayaks

Childcare seats

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 Light globes
Tool carts
Planter pots
Playing balls
Playground equipment
Headrests
Truck/cart liners
Air ducts

5.3 Thermoforming
Thermoforming is a generic term for the process of producing plastic parts from a flat
sheet of plastic under temperature and pressure. In the highest expression of the
technology, thermoforming offers close tolerances, tight specifications, and sharp detail.
When combined with advanced finishing techniques, high-technology thermoforming
results in products comparable to those formed by injection molding. All of us are
exposed to many thermoformed plastics in our daily lives. They have replaced many
parts previously manufactured from wood, paper, glass, and metal.

ARDC/CS/Internal 140
Thermoforming is a manufacturing process for thermoplastic sheet or film. The sheet or
film is heated between infrared, natural gas, or other heaters to its forming temperature.
Then it is stretched over or into a temperature-controlled, single-surface mold. Cast or
machined aluminum is the most common mold material, although epoxy, wood and
structural foam tooling are sometime used for low volume production. The sheet is held
against the mold surface unit until cooled. The formed part is then trimmed from the
sheet. The trimmed material is usually reground, mixed with virgin plastic, and
reprocessed into usable sheet . There are several categories of thermoforming,
including vacuum forming, pressure forming, twin-sheet forming, drape forming, free
blowing, and simple sheet bending.

Vacuum Forming

Vacuum forming is a plastic thermoforming process that involves forming thermoplastic

sheets into three-dimensional shapes through the application of heat and pressure.

Pressure Forming

ARDC/CS/Internal 141
Pressure forming is a variation of vacuum forming that utilizes both vacuum and
compressed air to force the plastic sheet against the mold

Twin sheet forming

Twin-sheet thermoforming is a process of vacuum or pressure forming two sheets of

plastic essentially simultaneously, with a separate mold on the top and bottom platens

The process creates 3 dimensional parts with formed features on both sides. The parts
are typically very strong, stiff, and quite light-weight.

Step 1: Two preheated thermoplastic sheets are

simultaneously heated between the two molds till they are
are entirely plasticized.

Step 2: On reaching the specific temperature the two molds

move together. The two sheets are deep-drawn and tightly
molded to each other in one step. No
adhesives are used. There are neither resulting pressure nor
strain.

Step 3: To achieve a high level of detail or precision, the

forming can be supported by high pressure or (and) vacuum

ARDC/CS/Internal 142
 Step 4: ... and the hollow body, without solvent, molding
additives and adhesives,
is finished. Furthermore, there are no inner strains.

Drape Forming

Drape forming is similar to straight vacuum forming except that after the sheet is framed
and heated, it is mechanically stretched, and a pressure differential is then applied to
form the sheet over a male mould.

Step 1. The plastic sheet is clamped in a frame and

heated. Heating can be timed or electronic sensors a
can be use to measure sheet temperature or sheet sag.

Step 2. Drawn over the mold - either by pulling it over

the mold and creating a seal to the frame, or by forcing
the mold into the sheet and creating a seal. The platen
can be driven pneumatically or with electric drive. In
some very small machines the platen can be manually
moved up or the clamped sheet can be manually
pushed over the mold.

Step 3. Then vacuum is applied through the mold,

pulling the plastic tight to the mold surface. A fan can
be used to decrease sheet cooling time.

Step 4. After the plastic sheet has cooled, the vacuum

is turned off and compressed air is sent to the mold to
help free it from the plastic. The platen then moves
down pulling the mold from the formed part. The formed
sheet is unclamped, removed, and a new cycle is ready
to start.

Many thermoplastics can be thermoformed; they include Polystyrene, Polypropylene,

PVC, etc. EVOH is commonly incorporated into a co-extrusion for its superior barrier
properties in food.

Applications: The largest application for thermoformed articles is for Food Packaging.
Other industries include Toiletries, Pharmaceuticals and Electronics.The modern food
supply chain uses many forms of thermoformed articles. Meat Trays, Microwave &

ARDC/CS/Internal 143
Deep Freeze Containers, Ice Cream and Margarine Tubs, Delicatessen Tubs, Snack
Tubs, Bakery and Patisserie packaging, Sandwich Packs and Vending Drink Cups are
just a few of the food related applications. Other non-food applications include
Manufacturing Collation trays, Blister packaging and Point of Sale display trays.

ARDC/CS/Internal 144
5.4 Trouble Shooting
Blown Film Extrusion Trouble Shooting

Problems Possible Remedies

Unmelts and Increase Processing Temperature within Cooling capabilities

Melt Fracture
Check and change if possible old wire mesh especially if the same is punctured or
from previous run with color masterbatches

High Haze, Low Increase Blow up ratio and Reduce Frost line Height
clarity and gloss
Improve the fusion of the melt by increasing barrel and die temperature

Remove multiple components (3 or more) in the mix.

Gels If process temperature has been increased to improve some other performance
wait till the line gels clear

Check with a reportedly cleaner Product to ensure that the Gels are a product
problem and not machine induced

If possible increase the Barrel Zone temperature within Cooling Limitations

Gauge Variation Check and ensure Die Gap uniformity and accurate Die Centering
and Bubble
Instability Reduce processing Temperature

Reduce Blow Up Ratio if possible

Inferior Strength Increase Blow Up ratio within Cooling Capabilities

Ensure proper Homogenization and Fusion

Remove Multiple component (3 or more) blends

Blocking and Reduce Melt Temperature if possible

poor Openability
Increase cooling air ensuring that Bubble Stability is not disturbed. If possible use
a chilled roll at the take up Nip and Increase the gap between the die and the nip

Reduce the winding Tension

Reduce Nip Roll Pressure

Avoid excessive Treatment Levels

Create a Air Bag by allowing some of the Blow Up air within the film Lay Flat at

ARDC/CS/Internal 145
 the winder Nip

Lower Output For a Fixed RPM Screw, temperature modification (negative profile) may help

Increase the Screw RPM (for a variable rpm screw) and to keep the motor load
constant, increase the Barrel temperature to reduce the melt viscosity

Tubular Quenched Film Extrusion

Problems Possible Remedies

Gels and Increase the processing temperature and if possible change the screen pack and
Unmelts clean the die

Blocking and Reduce the nip roll pressure and Create a air gap in the lay flat before the winder
Openability
If possible, mix Antiblock masterbatches

Reduce Winder Tension

Haze, Lower Ensure good fusion and melt homogenization by adjusting the processing
Clarity and temperature
Gloss
Increase the die temperature

Reduce the cooling water temperature to ~25 C or lower

Die Lines Increase the Processing Temperature

Clean the die of depositions from Prolonged run

Raffia, Cast Film Process

Problems Possible Remedies

Low Tenacity Increase stretch ratio. To maintain tape width, the spacer width may be increased.

Increase Stretch Bed/Oven temperature to ensure complete Stretching

Reduce the Quench Tank Temperature and the Air Gap

Reduce the processing temperature ensuring that no inhomogeneities are appearing in

the cast film. Maintain the film surface smoothness

Tape Breakage Ensure uniform fusion and smooth film surface. Increase processing temperature if
required to achieve this.

ARDC/CS/Internal 146
 Reduce Stretch Ratio and Line speed

Reduce Water Carryover

Check for and Eliminate incidence of unmelts from Masterbatch

Check and if Possible Change the Screen pack and clean the die

Avoid multiple (3 or more) component blend

Water Carry Reduce the Quench Tank Temperature

over
Remove the floating scum from the water surface

Reduce melt temperature without hampering the melt Homogeneity

Increase the nip roll pressure to squeeze out the carried over water and ensure correct
positioning of the knife

Improve the Cast Film surface if the same is rough (replace screen pack, clean die,
increase processing temperature)

Reduce line speed

Fibrillation / Incorporate an Antifibrillation Masterbatch if possible without deteriorating the Tenacity.

Tape Splitting Check the Sharpness of the Blades and use fresh set if required.

Check the guides of winder for Any Damages

If possible Reduce the Winder Tension

Reduce the Stretch Ratio

Try a 2 way blend

Low Output For a fixed (maximum) RPM extruder, temperature modification may be tried

Increase the screw RPM (for a variable rpm screw) and modify the temperature to adjust
the extruder motor load to normal

ARDC/CS/Internal 147
Extrusion Coating

Problems Possible Remedies

Unmelts and Delamination Increase the melt temperature to achieve a clean curtain.

Increase the nip roll pressure to ensure better adhesion

Ensure uniform tension in the substrate (fabric/paper/board) and

reduce any jerks or line speed fluctuations

Edge Fluctuation / Neck In Reduce die temperature

Use a two way blend with LDPE (4 MFI or 7 MFI)

Surging and Thickness Ensure uniform mixing if a Blend is being used. Avoid a multiple (3 or
Variation more) component blend.

If the thickness variation is localized then check and ensure the die gap
uniformity

Ensure uniform screw speed is maintained.

Maintain a Uniformly rising Gradient in the Barrel and Maintain a melt

Temperature in the Range of 290C

Ensure a uniform Temperature setting along the different die zones

Pipe Extrusion
Problems Possible Remedies

Thickness Variation Ensure uniform Die gap

Ensure Uniform Vacuum Sizing and no Air Leakage

Maintain Uniform Haul Off Speed

Low Throughput Increase the Screw RPM and Modify the Temperature Profile to avoid
increase in the Motor Load

Surface Finish Reduce the processing temperature in case outer surface has a pitted
appearance

Modify the mandrel temperature to remove any inner surface asperities

In case of Permanently Lubricated pipes, check the quality of the

Lubricating surface material and if possible check the stand alone pipe

ARDC/CS/Internal 148
 without the lubricating layer

Injection Molding
Problems Possible Remedies

Silver Streaking Reduce Processing Temperature and eliminate non uniform Processing
Temperature

Eliminate non uniform mixing of Pellets

Reduce injection speed and injection pressure

Increase mold temperature

Flash Reduce Process temperature and injection pressure

Reduce Shot size and eliminate erratic feed and erratic cycle time

Check mold surface finish If required, Reface Parting line or mating

surfaces & Check if machine clamping force is sufficient

Short Shot Increase Shot Size; Increase Injection Pressure

Increase Process temperature and Mold Temperature

Eliminate non uniformity in mold cooling If required rearrange mold

cooling water line

Increase plunger forward time, injection speed

Sink Marks Avoid Insufficient Material in the mold - Increase shot weight, injection
pressure, plunger forward time, injection speed

Reduce process temperature

Eliminate any unbalance in the gates

Maintain accurate and consistent mold open time use timer

Mold Sticking / Difficult Reduce Process Temperature, Shot weight, Plunger forward time
Demolding
Eliminate undercuts or rough surface Polish Mold Surface

Maintain accurate and consistent mold open time use timer

Poor Surface Finish Increase process temperature and mold temperature

Increase Injection Speed

ARDC/CS/Internal 149
 Improve flow paths in the mold

Improve mold cavity finish

Warpage Avoid Differential Shrinkage arising out of Varying thickness in different

parts of the molded articles

Avoid high follow up pressure

Avoid Orientation of the melt during injection

Fractures, Cracks Eliminate internal Stresses in the molded article arising out of
unbalanced mold design

Avoid Degradation due to high shear heating Adjust processing

temperature

Blow Molding

Problems Possible Remedies

Rough Surface, Black Remove local Air Pockets with adequate venting
Specks
Avoid thermal degradation Reduce processing temperature

Increase blow pressure and blowing rate

Avoid Hold up / Blind regions of melt in the die head

Thoroughly purge the system of old material

Melt Fracture and Rough Increase processing temperature to reduce shear and melt fracture
Parison
Reduce Extrusion speed

If possible use higher flow Grade

Check the die shaping profile. Reduce Shaping depth and shaping land

Warping and Distortion Avoid shrinkage difference arising from varying wall thickness

Provide Sufficient Cooling time and Avoid non-uniform Cooling

Non Uniform Wall Improve melt strength to avoid sagging parison from the die
Thickness
Reduce Melt temperature

Review the length of the blown part and its suitability for molding in the

ARDC/CS/Internal 150
 given processing constraints

Weld Line Problem / Redesign pinch-off to prevent low material content at the weld
Thinning at Parting Line
Increase blowing pressure Avoid any constriction in the Blow air line

Remove air entrapment and provide sufficient Venting

Parison Cutting Problem Sharpen the cutting Knife

Avoid keeping the knife too far away from the die

Increase the knife speed and temperature

Low Gloss Increase the processing temperature

Ensure polished mold surface

Use a higher flow grade

Part Blow Out Avoid very high Blow up ratio If possible use a wider die

Avoid very sharp pinch off and ensure mold is not over heated

Avoid very fast blow If possible blow in stages

Roto Molding

Problems Possible Remedies

Bridging of Powder in Mold Avoid Improper rotation Rotate mold faster

Use accurate Roto molding grade with suitable MFI

Review mold design and if possible provide a more generous diameter

Mold Release Problem Incorporate a mold release agent (Calcium Stearate, GMS etc)

Increase mold cooling time to ensure complete cooling of mold and

sufficient Shrinkage

Avoid Undercuts in the mold

Warped Molding Avoid Sagging of Hot Plastics Reduce the oven temperature

Avoid any vacuum formation in the molded part Vent off before

ARDC/CS/Internal 151
 demolding

Use accurate Roto Molding Grade and Avoid excess of mold release
agent

Bubble/Pin Holes / Rough Avoid Inadequate melting / Fusion of the powder in the mold Increase
Exterior Interior Surface oven/furnace temperature or heating cycle time

Ensure mold is dry before charging the powder

Use accurate MFI/Density Rot Molding Grade

Check the welded corners and joints of the mold to avoid any
bubbles/defects in such areas

Discolored Molding Avoid Degradation of Material Decrease the oven/furnace

temperature

Long Molding Cycles Check the heating capacity of the heating oven Avoid any loss of heat
due to any shield

Improve air circulation in the oven

Ensure adequate rotation speed If possible increase he same

Thermoforming

Problems Possible Remedies

Adjust sheet gauge and polish roll openings to just provide enough material to fill nips
Lines and
Improve cooling.
bands in the
a. Reduce polish-roll temperature.
transverse
b. Eliminate thin spots in sheet.
direction of
c. Improve sheet contact with polish rolls by increasing line tension.
extrusion
d. Ensure nip gaps are the same on both sides of the sheet.
e. Reduce melt temperature

Reduce oven temperature or cycle time

Add vacuum holes in problem areas

Webbing Improve molding technique or part design.
a. Use plug or ring assist.
b. Use web blocks to minimize sag problems.
c. Redesign mold to improve cavity spacing or balance draw

ARDC/CS/Internal 152
 Reduce oven temperature or cycle time.
Excessive
sheet sag
Reduce melt flow of GPPS for blend or run on a narrower thermoformer

Eliminate air drafts in oven and fix faulty heaters.

Reduce part temperature.

Uneven sag a. Increase cooling cycle.

b. Reduce sheet temperature.

c. Lower mold temperature.

Eliminate sticking. a. Change heated plug temperature to equal sheet temperature.

b. Apply release coating to plug assist. c. Use lower stick material for basic plug
Stretch construction.
marks on
part Increase mold temperature or increase air cushion as part is formed.

Increase number of water channels or clean out plugged channels as necessary.

Eliminate trapped air.

Pock marks a. Slightly roughen large, flat mold surfaces with very fine grit blasting or glass
beading of problem area.
b. Clean out plugged vacuum holes.
c. Add vacuum holes or vents as required.
Try setting mold temperature at 100F (38C).

Clean plugged water channels or add channels as needed.

Improve wall distribution as suggested in previous troubleshooting

Part section above.
Warpage
Increase cooling cycle time, reduce mold temperature or reduce sheet
temperature.

Improve vacuum on part (see section under Poor part detail).

Add ribs and additional detail where possible.

ARDC/CS/Internal 153
 6.0 Polyolefin Grades of HPL
Haldia Petrochemicals Limited is one of the largest integrated Greenfield
Petrochemical Complex in India. Situated in the eastern region of the port town of
Midnapur, Haldia, it is one of the biggest Petrochemical plants that make use of the
latest technologies round the world.

The HPL complex is primarily engaged in the production of polyethylene (High Density
and Linear Low Density) and Polypropylene. The basic feedstock for producing
Ethylene and Propylene is low aromatic Naphtha, which is mostly imported. Along with
these polymer products, the complex also produces chemicals like Benzene, Butadiene,
Cyclopentane, Carbon black feed stock, Hydrogenated paralysis gasoline and C6
Raffinate. The different technology licensors and contractors along with the nameplate
capacity for the three polymer manufacturing units of HPL are tabulated below:

NAME
PLANT / PLATE
S.No. TECHNOLOGY CAPACITY LICENSOR CONTARCTOR
PRODUCT

CX, Slurry Mitsui

High Density Technimont,
1. 240KTA Chemicals,
Polyethylene Process Italy
Japan

Linear Low Spherilene

Technimont,
2. Density 260KTA Basell, Italy
Technology Italy
Polyethylene

Spheripol II Technimont,
3. Polypropylene 245KTA Basell, Italy
Technology Italy

ARDC/CS/Internal 154
6.1 Grade Nomenclature
The brand name for the polymer products of HPL is HALENE- derived from the
combination of HALdia and polyethylENE or polypropylENE. The polyethylene products
are marketed as HALENE H and HALENE L for High Density Polyethylene and Linear
Low Density polyethylene respectively whereas for polypropylene it is HALENE P.

HALENE H nomenclature:
The high density PE grades from Mitsui plant have five to six characters for
nomenclature. The first one is a letter indicating the probable area of application,
followed by four numbers in which the first two digits indicate the density while the last
two digits represents the melt flow index of the polymer. For example the grade R5801
represents

R: polymer for Raffia application

Similarly M: Injection Molding grade

P: Pipe grade

F: Film grade

B: Blow molding grade

58: density of 0.958 g/cc

01: MFI of 0.5 g/10 min @ 2.16 kg, 190oC

Sometimes an additional letter is attached, as in E5201S, where S stands for the

special additivation package used for that material.

The high density PE from the Spherilene plant has six characters. The first five have the
same meaning as those of the Mitsui products followed by an extra letter L
representing HDPE from the swing (Spherilene) plant. Sometimes U is used after L to
indicate UV stabilized grades.

HALENE L nomenclature:
Linear low density PE grades are produced only from the Spherilene plant. They are
designated by six characters starting with the number 7. The following three numbers
denote their density. MFI is indicated by the fifth number. The nomenclature ends with a
letter indicating the specialty additivation or application. For example:

ARDC/CS/Internal 155
72307E indicates LLDPE of 0.923 g/cc density and 7 g/10 min MFI meant for Extrusion
coating applications.

HALENE P nomenclature:
Polypropylene produced in the Spheripol II plant has three varieties: PP Homopolymer,
PP Impact Copolymer and PP Random Copolymer. They have four to five characters
for nomenclature. The first letter indicates the application followed by a number
indicating the type of PP. The last two digits imply the MFI of the grade. Examples are
as follows:

F110: F- Film grade,

similarly B - Blow molding grade

M - Injection Molding grade

R- Raffia Grade

T - Thermoforming Grade, etc.

1: PP Homopolymer,

Similarly 2: PP Random Copolymer

3: PP Impact Copolymer

10 - MFI of 10 g/cc

ARDC/CS/Internal 156
6.2. Different Grades
6.2.1 Polyethylene Grades
6.2.1.1. HDPE Grades - Halene H

Extrusion Grade Applications

F5400 Thin films, Carry bags & Printed shopping bags

F5001 General Purpose Packaging Film and Extrusion

P5300 PE 112 Pipe Applications

R5801 Stretched tape / raffia for woven sacks and

tarpaulin
HD T6 Lamination film, GP Extrusion, Raffia for tarpaulin

HD T9 Raffia for woven sacks & tarpaulin

HD T10 & T10S Monofilaments for nets, twins & ropes

Molding Grade Applications

B5500 Medium to large bulk containers for chemicals,
detergents or lube oil - 5 to 120 Liters

B6401 Blow molded parts & containers

E5201 Blow molded parts & containers- High ESCR, GP

extrusion

E5201S Blow molded parts & containers

M5002L Injection Molded Caps and Closures

M5005L Large crates, Industrial application

M6007L Industrial Products, crates & bins

M6007LU Industrial Products, crates & bins - UV stabilized

ARDC/CS/Internal 157
 M5018L General purpose injection molded applications

M5025L General purpose injection molded applications

Halene H

Film Grades
F5400

Property Value Target Attributes

MFI 0.09 Strength

Processability and Throughput

Density 0.954 Stiffness in Film

MWD Broad Good Processability

Additivation 2 AO (Anti Processing stabilization at processing temp ~ 180-

Package oxidants)
220 C. Indicated by pellet color.

Lubrication for better gloss in films

Pigment dispersion
Stearates
Pellet Count Uniform Uniformity in feed & flow to avoid surging

ARDC/CS/Internal 158
 F5001

Property Value Target Attributes

MFI 1.1 Processability and Throughput

Density 0.950 Strength and Elongation in Tapes
Additivation Package Good Processability & strength

Pipe (PE 112) Grade

P5300
Property Value Target Attributes

MFI 0.25 (I5) Processability and Throughput

Strength & Hydr. Pressure resistance
ESCR
Density 0.948 (unannealed density at Balance of Rigidity, Strength & Hydr. Pressure
27C) resistance
ESCR
MWD Broad Processability
Additivation Anti oxidants High OIT (Oxidative Induction Time)
Thermal Stabilizers Ageing Resistance
Stabilization during processing in the range of
180 200C (melt temperature)
Satisfactory Surface Finish

ARDC/CS/Internal 159
 Raffia Grades
R5801
Property Value Target Attributes

MFI 0.50 Processability and Throughput

Strength in Tapes
Density 0.961 Strength and Elongation in Tapes
MWD Medium Stretchability
Additivation Package Process Stability at ~220C, High Speeds & Extended periods
of extrusion
Low Water Carry Over

HD T6
Property Value Target Attributes

MFI 0.50 Processability and Throughput

Lamination films, woven sacks and tarpaulin
Density 0.961 Strength and Elongation in Tapes
MWD Medium Stretchability
Additivation Package Good Processability & mechanical strength

ARDC/CS/Internal 160
 HD T9
Property Value Target Attributes

MFI 1.1 Processability and Throughput

Density 0.950 Strength and Elongation in Tapes
MWD Narrow High Stretchability
Low Denier
Additivation Package Process Stability at ~220C, High Speeds & Extended periods
of extrusion
Low Water Carry Over

Blow Molding Grades

E5201
Property Value Target Attributes

MFI 0.35 Container weight & Dimension Accuracy

(@2.16kg, Strength in Containers: Drop Test and Stackability
Processability
190C)

Density 0.952 High Stiffness: Strength and Stackability

Good ESCR

Additivation Package Processing in the range of 160-200 C (melt temperature)

Satisfactory surface finish

ARDC/CS/Internal 161
 E5201S
Property Value Target Attributes

MFI 0.35 Container weight & Dimension Accuracy

Strength in Containers: Drop Test and
Stackability

Density 0.958 Higher stiffness

MWD Broad Easy Processability

Additivation Package Processing in the range of 160 200C (melt temperature)

Satisfactory surface finish

B6401
Property Value Target Attributes

MFI 0.40 Container weight & Dimension Accuracy

(@2.16kg/ Strength in Containers : Drop Test and
Stackability
190C)
Processability
Density 0.964 Stiffness : Strength and Stackability

Additivation Package Processing in the range of 180 to 200 C (melt

temperature)
High Surface gloss in containers

ARDC/CS/Internal 162
 B5500

Property Value Target Attributes

MFI 0.4 Container weight & Dimension Accuracy

(@5kg,190C) Strength in Containers: Drop Test and
Stackability

Processability

Density 0.956 ESCR: For Packing of Surfactant Type

Chemicals

Stiffness: Strength and Stackability

MWD Broad Easy processability and melt strength
Excellent die swell for large containers

Additivation Package Processing in the range of 190 220C (melt

temperature)
Accommodate High Shear Rates in Accumulator type
machines
Excellent surface finish

ARDC/CS/Internal 163
 Monofilament Grades

HD T10
Property Value Target Attributes

MFI 1.1 Processability and Throughput

Density 0.950 Strength and Elongation in Tapes and Monofilaments
MWD Narrow High Stretchability
Additivation Package Process Stability at ~ 220C
Optimum Water Carry Over (for Indirect Warp Process of
HD T10)

HD T10S

Property Value Target Attributes

MFI 1.1 Processability and Throughput

Density 0.950 Strength and Elongation in Tapes and Monofilaments

MWD Narrow High Stretchability

Additivation Package Process Stability at ~ 220C

Optimum Water Carry Over (for Indirect Warp Process of
HD T10)
Low Die Build Up

ARDC/CS/Internal 164
 Injection Molding Grades
M5018L
Property Value Target Attributes

MFI 18 Weight in Molded Item & Dimension Accuracy

Strength in Containers
Processability and Cycle Time
Density 0.950 Stiffness and Impact Balance

Additivation Package Processing stability at high temperatures

Easy mold release

M5002L
Property Vaue Target Attributes

MFI 2.5 Superior processability & improved performance

Density 0.950 Stiffness and Impact Balance

Additivation Package Easy mold release

Good Processability

ARDC/CS/Internal 165
 M5005L
Property Value Target Attributes

MFI 4.5 Superior processability & improved performance

Density 0.950 Stiffness and Impact Balance
Additivation Package Processing stability at high temperatures
Easy mold release

M5025L
Property Value Target Attributes

MFI 30 Excellent Processability

Easy filler uptake Application in Filler Masterbatch
sector
Density 0.945 Stiffness and Impact Balance

Additivation Package Processing stability at high temperatures

Easy mold release

ARDC/CS/Internal 166
 M6007L/LU
Property Value Target Attributes

MFI 7.5 Weight in Molded Item & Dimension Accuracy

Strength in Containers
Processability, Mold Release (Shrinkage) and Cycle
Time

Density 0.950 Stiffness and Impact Balance

Additivation Package Processing stability at high temperatures

Easy mold release
M6007LU contains UV Stabilizers outdoor applications

6.2.1.2. LLDPE Grades Halene L

Extrusion Grades Applications

71601S General purpose packaging film- with slip & antiblock

71501S General Purpose Film Grade

71601W Adhesive lamination films- no slip & antiblock

71602S General purpose packaging films- with slip & antiblock

71602W Cast film for strech wrap- no slip & antiblock

ARDC/CS/Internal 167
LL T12 Wire & Cable Application

Molding Grades Applications

73204T Rotomolded tanks for industrial water storage, sanitation & agriculture

73005T Rotomolded tanks, toys & components

73005TU Rotomolded tanks, toys & components- UV stabilized

72307E Extrusion coating on fabrics, paper & allied substrate

ARDC/CS/Internal 168
 Halene L
Film Grades
71601S
Property Value Target Attributes

MFI 1.0 Strength

Processability and Throughput
Density 0.920 Sealing Performance
Surface Treatment Retention
Stiffness in Film
Additivation package Processing stabilization at 180-200 C (Melt temp)
(2 AO, PPA, Antiblock, Slip) Processability at high speed extrusion process
Openability in rolls
COF & Treatment retention in Films

71501S
Property Value Target Attributes

MFI 1.0 Strength

Processability and Throughput
Density 0.920 Sealing Performance
Surface Treatment Retention
Stiffness in Film
Additivation package Processing stabilization at 180-200 C (Melt temp)
(2 AO, PPA, Antiblock , Slip) Processability at high speed extrusion process
Openability in rolls
COF & Treatment retention in Films

ARDC/CS/Internal 169
 71601W
Property Value Target Attributes

MFI 1.0 Strength

Processability and Throughput
Density 0.916
Good adhesion to the substrate for adhesive lamination
purpose

Additivation package Processing stabilization at 180-200 C (Melt temp)

(2 AO, PPA) Processability at high speed extrusion process

71602S

Property Value Target Attributes

MFI 2.0 Strength

Processability and Throughput
Density 0.920 Sealing Performance
Surface Treatment Retention
Additivation package Processing stabilization at 180-200 C (Melt temp)
(2 AO, PPA, Antiblock , Slip) Processability at high speed extrusion process
Openability in rolls
COF & Treatment retention in Films

ARDC/CS/Internal 170
 71602W

Property Value Target Attributes

MFI 2.5 Strength

Processability and Throughput
Density 0.916 Sealing Performance
Surface Treatment Retention
Additivation package Processing stabilization at 180-200 C (Melt temp)
2 AO, PPA Processability at high speed extrusion process

Drip Lateral Pipe Grade

71601D

Property Value Target Attributes

MFI 1.0 Strength

Processability and Throughput
Density 0.920 Sealing Performance
Surface Treatment Retention
Additivation package Processing stabilization at 180-200 C (Melt temp)
2 AO Processability at high speed extrusion process
PPA

ARDC/CS/Internal 171
 Rotomolding Grades
73005T/U
Property Value Target Attributes

MFI 5 Processability and Throughput

Tensile and Impact Strength
Density 0.934 Strength and Elongation
Pulverisability
Additivation package Processing in the range of 180 200C (melt temperature)
Satisfactory Mold Release and Surface Finish
73005TU has uv stabilizer for outdoor application

73204T
Property Value Target Attributes

MFI 5 Processability and Throughput

Tensile and Impact Strength
Density 0.932 Strength and Elongation
Additivation package Processing in the range of 180 200C (melt temperature)
Satisfactory Mold Release and Surface Finish

ARDC/CS/Internal 172
 Extrusion Coating Grade
72307E
Property Value Target Attributes

MFI 7 Processability and Throughput

Density 0.926 Adhesion to substrate

Additivation package Processing in the range of 200 250C (melt temperature)

Good adhesion to substrate

Grade for Wire and Cable Insulation

LL T12
Property Value Target Attributes

MFI 3.7 Target MFI ensure optimum balance of mechanicals and

processability

Density 0.926 Narrow density range ensures consistent target performance

Additivation package Lean additive package helps improvisation in compounding recipe

Acid Neutralizer
Barefoot grade

ARDC/CS/Internal 173
6.2.2. Polypropylene Grades Halene P

PP Homopolymer Grades

Extrusion Grades Applications

F103 BOPP film grade- general purpose,
lamination & metalized films

R103 Raffia tapes, woven sacks for packaging

fertilizers, cement, polymers, carpet
backing, FIBC etc

T103 Thermoformed cups, containers & other

disposable items

F110 TQ & cast films for general purpose

packaging

E116 General purpose extrusion coating

E125 Extrusion coating of woven fabrics

Injection Molding Grades Applications

M103 General purpose injection molding

M106 General purpose injection molding

M108 General purpose injection molding

M110 General purpose injection molding.

Furniture etc.

ARDC/CS/Internal 174
PP Impact Copolymer

Injection Molding Grades Applications

M304 Automotive components, crates, pails,
furniture etc

M310 Battery boxes etc

M310S Furniture, pails, compounding, automotive

components etc.

M312 Compounding, industrial components,

automotive components, luggage, pails,
house wares, sanitary wares etc.

M311T Compounding, Automotive Components,

Luggage and Industrial Components

M325 Compounding, Automotive Components,

Houseware, Appliances parts, Extrusion
Coating

PP Random Copolymer

Blow molding Grades Applications

B202S Bottles & containers for medical &
transparent products ( e.g. fluid bottles)

B200 General purpose blow molded &

thermoformed items

ARDC/CS/Internal 175
 Halene P
PP Homopolymer Extrusion Grade
F103

Property Value Target Attributes

MFI (g/10min) 3 Excellent processability,

High tensile strength,
Impact Strength (J/m) 30 High clarity & gloss,
Excellent printability
Stiffness (MPa) 1400

R103
Property Value Target Attributes

MFI (g/10min) 3 Easy processability, low

water carryover, high
Impact Strength (J/m) 30 tenacity & toughness,
Stiffness (MPa) 1400 Good color & processing
stability

ARDC/CS/Internal 176
 T103
Property Value Target Attributes

MFI (g/10min) 3 Excellent Processability

& stiffness, High clarity &
Impact Strength (J/m) 40 gloss Disposable /
Stiffness (MPa) 1650 Thermoforming items

F110
Property Value Target Attributes

MFI (g/10min) 11 High melt strength,

Excellent processability,
Impact Strength (J/m) 30 High clarity & gloss
Stiffness (MPa) 1450

E116
Property Value Target Attributes

MFI (g/10min) 18 Easy processability

Impact Strength (J/m) 25

Stiffness (MPa) 1200

ARDC/CS/Internal 177
 E125
Property Value Target Attributes

MFI (g/10min) 25 Excellent processability &

flow characteristics, good
Impact Strength (J/m) 25 adhesion to substrate
Stiffness (MPa) 1250

PP Homopolymer Injection Molding Grade

M103
Property Value Target Attributes

MFI (g/10min) 3 Easy procesability, high

strength, excellent color
Impact Strength (J/m) 35 & processability
Stiffness (MPa) 1300

M 106
Property Value Target Attributes

MFI (g/10min) 6 Easy procesability & high

strength
Impact Strength (J/m) 35

Stiffness (MPa) 1300

ARDC/CS/Internal 178
 M108
Property Value Target Attributes

MFI (g/10min) 9 Easy procesability & high

strength
Impact Strength (J/m) 35

Stiffness (MPa) 1300

M110
Property Value Target Attributes

MFI (g/10min) 12 Excellent processability,

low cycle time, high gloss
Impact Strength (J/m) 30 & excellent color, good
Stiffness (MPa) 1400 processing stability

PP Impact Copolymer Injection Molding Grades

M304
Property Value Target Attributes

MFI (g/10min) 3.5 Easy processability, low

cycle time, good impact-
Impact Strength (J/m) 150 stiffness balance, high
Stiffness (MPa) 1050 gloss, low static charge
build up

ARDC/CS/Internal 179
 M310
Property Value Target Attributes

MFI (g/10min) 10 High flow, Easy

processability, low cycle
Impact Strength (J/m) 105 time, good impact-
Stiffness (MPa) 1250 stiffness balance, high
gloss, low static charge
build up

M310S
Property Value Target Attributes

MFI (g/10min) 12 High flow, Easy

processability, low cycle
Impact Strength (J/m) 135 time,good impact-
Stiffness (MPa) 1050 stiffness balance, high
gloss, low static charge
build up

ARDC/CS/Internal 180
 M312
Property Vaue Target Attributes

MFI (g/10min) 12 High flow, Easy

processability, low cycle
Impact Strength (J/m) 135 (min.) time, good impact-
Stiffness (MPa) 950 (min.) stiffness balance, high
gloss, low static charge
build up

M311T
Property Value Target Attributes

MFI (g/10min) 10 No break grade (with

high impact toughness)
Impact Strength (J/m) 500 used in automotive,
Stiffness (MPa) 900 luggage sectors and
industrial components

M325
Property Value Target Attributes

MFI (g/10min) 25 High MI material used in

compounding sector,
Impact Strength (J/m) 60 (min.) general purpose injection
Stiffness (MPa) 1300 (min.) molding and extrusion
coating applications

ARDC/CS/Internal 181
PP- Random Copolymer
B202S
Property Value Target Attributes

MFI (g/10min) 1.9 High melt strength, high

clarity, excellent
Impact Strength (J/m) 100 processability & impact
Stiffness (MPa) 800 strength

B200
Property Value Target Attributes

MFI (g/10min) 1.9 High melt strength &

easy processability
Impact Strength (J/m) 90

Stiffness (MPa) 800

ARDC/CS/Internal 182
7.0 Plastic Material Testing & Identification

The advent of modern science and technology has lead to the inclusion of testing as an
integral part of research and development activities. With time, the manners in which
things are done today are quite different from what it used to be. The emphasis is on
automation, high production, and cost reduction. There is also a growing demand for
intricately shaped, high tolerance parts. These coupled with consumer awareness has
made testing of materials extremely necessary and compulsory for each and every
production house. The following are some of the major reasons for testing:

1. To prove design concepts

2. To provide a basis for reliability
3. Safety
4. Production against product liability suits
5. Quality control
6. To meet standards and specifications
7. To verify the manufacturing process
8. To evaluate competitors products
9. To establish a history for new materials

In the last two decades, just about every manufacture has turned to plastics to achieve
cost reduction, automation, and high yield. The lack of history along with the explosive
growth and diversity of polymeric materials has forced the plastics industry into placing
extra emphasis on testing and on developing a wide variety of testing procedures.

Testing of plastics can be segregated under the different type of properties that can be
tested. Mechanical Property testing

The mechanical properties, among all the properties of plastic materials, are often the
most important properties because virtually all service conditions and the majority of
end-use applications involve some degree of mechanical loading.

ARDC/CS/Internal 183
7.1. Mechanical Property Testing

a) Tensile Property Testing (ASTM D 638, ISO 527-1)

Tensile test is a measurement of the ability of a material to withstand forces that tend to
pull it apart and to determine to what extent the material stretches before breaking.
Tensile modulus, an indication of the relative stiffness of a material, can be determined
from a stress-strain diagram. Different types of plastic materials are often compared on
the basis of tensile strength, elongation and tensile modulus data.

Universal Tensile Testing Machine

Factors affecting the test results:

Specimen preparation and specimen size
Rate of straining
Temperature

b) Flexural Property Testing (ASTM D 790, ISO 178)

Flexural strength is the ability of the material to withstand bending forces applied
perpendicular to its longitudinal axis. The stress induced by the flexural load is a
combination of compressive and tensile stresses. The flexural modulus is a measure of
the stiffness during the first or initial part of the bending process. This value of the
flexural modulus is, in many cases, equal to the tensile modulus.
Factors affecting the test results:
Specimen Preparation
Temperature

ARDC/CS/Internal 184
 Test Conditions

c) Compressive Property Testing (ASTM D 695, ISO 75-1 and 75-2)

Compressive properties describe the behavior of a material when it is subjected to a

compressive load at a relatively low and uniform rate of loading.

d) Creep Property Testing

With more and more metals being replaced from their conventional field of application
by plastics, it has become highly important to thoroughly understand the behavior of
plastics under long-term load and varying temperatures. Such behavior is described in
terms of creep properties.
When a plastic material is subjected to a constant load, it deforms quickly to a strain
roughly predicted by its stress- strain modulus, and then continues to deform slowly with
time indefinitely or until rupture. This phenomenon of deformation under load with load
with time is called creep. All plastics creep to certain extent. The degree of creep
depends upon several factors, such as type of plastic, amount of load, temperature and
load.
The creep measurement technique involves the application of a fixed amount of load to
a specimen and then the measurement of the resulting deformation as a function of
time.
The creep values can be obtained by applying constant load to the test specimen in
tension, compression, or flexure and measuring the deformation as a function of time.
The values are most commonly referred to as tensile creep, compressive creep, and
flexural creep.

e) Testing of Stress Relaxation

Stress relaxation is defined as a gradual decrease in stress with time, under a constant
deformation (strain). This characteristic behavior of the polymers is studied by applying
a fixed amount of deformation to a specimen and measuring the load required to
maintain it as a function of time.

f) Impact Testing

The impact properties of the polymeric materials are directly related to the overall
toughness of the material. Toughness is defined as the ability of the polymer to absorb
applied energy. The area under the stress-strain curve is directly proportional to the
toughness of a material. Impact energy is a measure of toughness. The higher the
impact energy of a material, the higher the toughness and vice versa. Impact resistance
is the ability of the material to resist breaking under a shock loading or the ability to
resist the fracture under stress applied at high speed.
Factors affecting the impact strength are as follows:
Rate of loading

ARDC/CS/Internal 185
 Notch Sensitivity
Temperature
Orientation
Processing conditions and types
Degree of crystallinity, Molecular Weight
Method of loading

Types of Impact tests:

Pendulum impact tests
1) Izod Impact test (ASTM D 256, ISO 179)

Izod Impact Tester

2) Charpy Impact Test

3) Chip Impact Test (ASTM D 4508)
4) Tensile Impact Test (ASTM D 1822)

High-Rate Tension Test

Falling-Weight Impact Test (ASTM D 5420, D 1709, D 2444))
High Speed Impact Tests
Miscellaneous Impact Tests

g) Hardness Tests

Hardness is defined as the resistance of a material to deformation particularly

permanent deformation, indentation, or scratching.

ARDC/CS/Internal 186
Rockwell Hardness (ASTM D 785)

This measures the net increase in depth impression as the load on the indenter is
increased from a fixed minor load to a major load and then returned to a manor load.

Durometer Hardness (ASTM D 2240, ISO 868)

This is used for measuring the relative hardness of soft materials and is based on the
penetration of a specified indentor forced into the material under specified conditions.
Two types of durometers are most commonly used - Type A (for softer materials) and
Type D (for slightly harder materials).

Barcol Hardness (ASTM D 2583)

This test is devised for measuring hardness of both reinforced and non-reinforced rigid
plastics.

ARDC/CS/Internal 187
7.2. Thermal Property Testing

Heat Deflection Temperature (ASTM D 648)

Objective

To determine the temperature at which an arbitrary deformation of the given test

specimen occurs when it is subjected to a static load of either 66 or 264 psi.

HDT Fixtures

Significance

Heat Deflection Temperature (HDT) distinguishes between the materials, which lose
their rigidity over a narrow temperature range, and those, which are able to sustain light
loads at high temperatures.

ARDC/CS/Internal 188
Application

In screening and ranking the plastic materials for short term heat
resistance
For evaluating plastic profiles or sheets which are rigid at room
temperature

Vicat Softening Point (ASTM D 1525)

Objective

To determine the temperature at which a specified needle of 1 mm2 flat circular cross
section will penetrate to a depth of 1 mm in a plastic specimen subjected to controlled
rate of heating under fixed load.

Atlas DTUL/Vicat tester

ARDC/CS/Internal 189
Significance

The Vicat Softening Point of a plastic gives an indication that polymeric materials soften
or lose their rigidity when heated.

Application

In comparing heat softening qualities of thermoplastic materials

Brittleness temperature (ASTM D 746)

Objective

To determine the temperature at which plastic and elastomers exhibit brittle failure
under specified impact condition.

Apparatus A

Apparatus B

ARDC/CS/Internal 190
Significance

It gives an indication that at low temperatures all plastics tend to become rigid and
brittle. This happens because at low temperatures the mobility of polymer chains is
greatly reduced.

Application

In studying the behavior of plastic at various temperatures and evaluate

long term effects

Flammability (ASTM D 635)

Objective

This test method covers procedure for comparing the relative rate of burning and/or
extent of burning of self-supporting plastics in the form of bars, molded or cut sheets.

The 49CFR-571-302 test measuring flame rate

Significance

This test gives an idea about the expected fire hazards from a particular plastic item
depending upon its form an application.

Application

In establishing relative burning characteristics of plastic materials

ARDC/CS/Internal 191
Ignition Behavior of Some Typical Plastics

Sl Polymer Ignition Rate Flame Colour Odor

No.

1 PE Easy ignition, very slow Yellow with Burning paraffin

burning, material melts and blue base or candles
drips, not self-extinguishing

2 PP Easy ignition, very slow Yellow with Burning paraffin

burning, material melts and blue base or candles
drips, not self-extinguishing

3 PVC/PVDC Difficult ignition, self Yellow with Acrid

extinguishing, strongly acidic green base,
fumes, black residue slightly smoky
formation flame

4 PS Easy ignition, slow burning, Orange yellow, Floral, fruity

not self-extinguishing black dense characteristics,
smoke styrenic

5 ABS Easy ignition, slow burning, Yellow Resembling burnt

volatiles having alkaline hair
reaction yielding dark residue

6 Cellulosics Easy ignition, slow burning, Yellow green Burnt wood,

not self-extinguishing, chars, flame with paper, acetic acid
burns without melting, acidic sparks, sooty
fumes

7 Nylons Moderate ignition, self Blue with Burning

extinguishing, melts, drips, yellow tip vegetables, burnt
froths, melts can be drawn hair
into a fiber

8 Polycarbonates Difficult ignition, self Luminous Burnt paper,

extinguishing, melts, sooty flame burnt dry leaves
decomposes, chars

9 PMMA Easy ignition, not self- Yellow flame Sweet, fruity

extinguishing, spurting with blue edge acrylic smell
black smoke

10 PF resins Difficult ignition, self Bright yellow Phenolic

extinguishing smoky flame

ARDC/CS/Internal 192
7.3. Optical Property Testing
a) Refractive Index (ASTM D 542)

Objective

The test method aims in measuring the refractive index of a plastic material. Refractive
index of a sample may be defined as the ratio of the velocity of light in a vacuum (or air)
to its velocity in a transparent medium.

Dual Amici Prism Compensator @ 589nm (Sodium D Line) illumination

Significance

Refractive index values are important to design engineers involved in designing lenses
for cameras, microscopes, and other optical equipments.

Application

In establishing relative optical characteristics of different plastics

ARDC/CS/Internal 193
 b) Luminous Transmittance & Haze (ASTM D 1003)

Objective

To determine the capability of a given test specimen to allow the incident light rays to
pass through it.

BYK Gardner Spectrophotometer

Significance

Luminous transmittance is defined as the ratio of transmitted light to the incident light.
Haze is defined as the percentage of transmitted light, which in passing through a
specimen deviates from the incident beam, by forward scattering.

Application

In determining the quality of a product with respect to the desired optical

properties required for a specified application
In comparing the transparencies of various grades and types of plastics

ARDC/CS/Internal 194
 c) Color (ASTM E313)

Objective

Yellowness Index is a number calculated from spectrophotometric data that describes

the change in color of a test sample from clear or white toward yellow.

Significance

This test is most commonly used to evaluate color changes in a material caused by real
or simulated outdoor exposure.

Application

Color measurement is an important quality control method for polymer

manufactures
Color is an indication of the extent of degradation a material has undergone

d) Specular Gloss (ASTM D 2457, D 523)

Objective

To measure the amount of the light reflected by the surface of a material.

BYK Gardner Glossmeter

ARDC/CS/Internal 195
Significance

Gloss can be inherent in the material, a result of the molding process, or a result of
surface texture. Gloss can also be affected by environmental factors such as
weathering or surface abrasion.

Application

Gloss can be useful in product development, process development, and

end use performance testing.
Measurement of shiny appearance of films, surfaces of plastic articles

7.4. Electrical Property Testing

a) Dielectric Strength (ASTM D 149, IEC 243-1)

Objective

To measure the maximum amount of voltage required in producing a dielectric

breakdown in a given sample.

ARDC/CS/Internal 196
Significance

The dielectric strength of a material indicates the electrical strength of a material as an

insulator. It may vary with the structure and geometry of the material.

Application

In evaluating plastics to be used as insulators

As a quality control test for plastics wires and cables

b) Dielectric Constant and Dissipation Factor (ASTM D 150,

IEC 250)

Objective

Dielectric Constant is used to determine the ability of an insulator to store electrical

energy. The dielectric constant is the ratio of the capacitance induced by two metallic
plates with an insulator between them to the capacitance of the same plates with air or
a vacuum between them. Dissipation factor is defined as the reciprocal of the ratio
between the insulating materials capacitive reactance to its resistance at a specified
frequency.

QuadTech Precision RLC meter

ARDC/CS/Internal 197
Significance

When a material is to be used in electric applications where high capacitance is needed,

a higher dielectric constant is required. The test can be conducted at different
frequencies, often between the 10Hz and 2MHz range.

Application

In evaluating plastics to be used as insulators

For evaluating polymer capacitors
As a quality control test for plastics wires and cables

7.5. Chemical Property Testing

Environmental Stress Cracking Resistance (ASTM D 1693)
Environmental stress cracking is the formation of cracks in a material caused by
relatively low tensile stress and environmental conditions. Environmental Stress-
Cracking Resistance (ESCR) is the number of hours that 50% of the specimens tested
exhibit stress cracks.

This test helps is determining the suitability of plastics containers for liquid storage,
handling and transportation.

ESCR Specimen

ESCR testing is performed by slowly bending the test specimens and placing them in a
holding clamp. The clamp and specimens are then placed in a test tube and immersed
in a specified reagent. The test tube is sealed and placed in a constant-temperature
bath. Multiple test specimens are tested at one time.

ARDC/CS/Internal 198
 ESCR Specimens in Holder

Specimens are inspected periodically for failure. Cracks generally develop at the notch,
perpendicular to the notch, and run to the edge of the specimen. Any cracks constitute
failure, not just cracks that reach the edge of the specimen. Cracks sometimes appear
beneath the surface and are visible as surface depressions. If a depression develops
into a surface crack the time at which the depression was noted is taken as the time of
failure.

ESCR Test

Three test conditions are specified. Condition A is generally used for polyethylene with
densities between 0.910 and 0.925 g/cm. Condition B is used for polyethylene with
densities greater than 0.925 g/cm. Condition C is used for accelerated testing of
materials with extremely high ESCR values.
A summary of the differences in the different test conditions is listed below.

ARDC/CS/Internal 199
 ESCR Test Conditions

Condition Thickness (mm) Notch Depth (mm) Bath Temperature (C)

A min 3 0.5 50

max 3.3 0.65

B min 1.84 0.3 50

max 1.97 0.4

C min 1.84 0.3 100

max 1.97 0.4

7.6. Material Characterization Tests

a) Density Gradient Technique

Objective
This method is based on observing the level to which a test specimen sinks in a liquid
column exhibiting a density gradient.
Significance

All plastics are sold on a cost per weight basis not on a cost per unit volume basis. Such
a practice increases the significance of the density.

Application

Both for purchasing and production control

ARDC/CS/Internal 200
b) Apparent (Bulk) Density (ASTM D 1895)

Objective

Bulk density is defined as the weight per unit volume of material. Bulk density is
primarily used for powders or pellets.

Significance

The test can provide a gross measure of particle size and dispersion, which can affect
material flow consistency and reflect packaging quantity. It is the measure of fluffiness
of a material.

Application

It can be used as a quality control test during material purchase as well as

production

c) Melt Flow Index (ASTM D 1238)

Objective

To measure the rate of extrusion of molten resin through a capillary of a specified length
and diameter under prescribed conditions of temperature and load.

Significance

It provides a means of measuring flow of a melted material which can be used to

differentiate grades as with polyethylene, or determine the extent of degradation of the
plastic as a result of molding.

ARDC/CS/Internal 201
 A Melt Flow Tester
Application

A method for controlling material uniformity, particularly for the polymer

manufacturers

d) Viscosity Tests
Dilute Solution Viscosity of Polymers (ASTM D 2857)
Objective

Dilute Solution Viscosity is used as an indication of the molecular weight of polymers.

The results of the test are expressed as Relative Viscosity, Inherent Viscosity, or
Intrinsic Viscosity. It is used for polymers that dissolve
completely without chemical reaction or degradation and
can provide an excellent determination of lot-to-lot
consistency or be used to compare molded parts to original
resin for determinations of degradation from molding.

ARDC/CS/Internal 202
Ubbelohde calibrated viscometer tube in a constant temperature water bath

Significance
It is basically a measure of the average size or extension in space of polymer
molecules. It is empirically related to the average molecular weight of linear polymer.
The presence of additives has a significant influence on the viscosity of the polymer.
Application

In determining the average molecular weight of the polymer

ARDC/CS/Internal 203
7.7. Thermal Analysis Techniques
Thermal analysis consists of a family of analytical techniques in which a property of the
sample is monitored against time or temperature while the temperature of the sample is
programmed.

a) Differential Scanning Calorimetry (ASTM D 3417, ASTM D 3418)

Objective

Differential scanning calorimetry or DSC is a thermoanalytical technique in which the

difference in the amount of heat required to increase the temperature of a sample and
reference are measured as a function of temperature. Both the sample and reference
are maintained at nearly the same temperature throughout the experiment.

Differential Scanning Calorimeter

Significance

The basic principle underlying this technique is that, when the sample undergoes a
physical transformation such as phase transitions, more (or less) heat will need to flow
to it than the reference to maintain both at the same temperature. Whether more or less
heat must flow to the sample depends on whether the process is exothermic or
endothermic. For example, as a solid sample melts to a liquid it will require more heat
flowing to the sample to increase its temperature at the same rate as the reference. This
is due to the absorption of heat by the sample as it undergoes the endothermic phase
transition from solid to liquid. Likewise, as the sample undergoes exothermic processes

ARDC/CS/Internal 204
(such as crystallization) less heat is required to raise the sample temperature. By
observing the difference in heat flow between the sample and reference, differential
scanning calorimeters are able to measure the amount of heat absorbed or released
during such transitions. DSC may also be used to observe more subtle phase changes,
such as glass transitions

Application

DSC curves can reveal information about the following:

Crystallization temperature
Fusion temperature (Melting point/range)
Oxidation Induction Time (Degradation study)
Cross linking of polymer molecules

ARDC/CS/Internal 205
b) Thermogravimertic Analysis (TGA)

Objective

Thermogravimetric Analysis or TGA is a type of testing that is performed on samples to

determine changes in weight in relation to change in temperature. Such analysis relies
on a high degree of precision in three measurements: weight, temperature, and
temperature change.

Significance

A TGA derivative weight loss curve can be used to tell the point at which weight loss is
most apparent such as thermal or oxidative degradation. Hence it provides us the data
on thermal and oxidative stability, composition analysis, reaction kinetics, aging stability,
degradation profile, percentage of volatiles, etc.

Typical TGA Curves

Application

TGA is commonly employed in research and testing to determine

characteristics of materials such as polymers
To determine degradation temperatures, absorbed moisture content of
materials, the level of inorganic and organic components in polymeric
materials

ARDC/CS/Internal 206
c) Thermomechanical Analysis (TMA)

Objective

To measure the dimensional changes of the polymer as a function of stress applied on

a sample with reference to temperature

TMA Instrument

ARDC/CS/Internal 207
Significance

TMA measurements provide data on the following:

Transition temperature
Expansion coefficient
Softening point
Heat Deflection Temperature
Thermal reorientation
Mold Shrinkage, etc.

ARDC/CS/Internal 208
7.8. Spectroscopy

Spectroscopy is the most significant tool to identify the polymer materials. It identifies
the functional groups, chemical linkage and geometrical isomerism. Widely used
spectroscopic techniques are Infra-Red spectroscopy and UV Visible Spectroscopy.

a) Infra Red (IR) Spectroscopy

Infra red spectroscopy studies vibrational modes of molecules. An infra red spectrum
arises when molecules undergo transition between different internal energy levels. The
energy difference between the states represents the frequency of the radiation emitted
or absorbed. The IR wavenumber range is 350 to 5000 cm-1.

Fourier transform infrared (FTIR) spectroscopy is a measurement technique for

collecting infrared spectra. Instead of recording the amount of energy absorbed when
the frequency of the infra-red light is varied (monochromator), the IR light is guided
through an interferometer. After passing the sample the measured signal is the
interferogram. Performing a mathematical Fourier transform on this signal results in a
spectrum identical to that from conventional (dispersive) infrared spectroscopy.

Features:

Samples can be tested in the form of film, solution or solid/pellet. Samples should be
preferably transparent or semi-transparent. Moreover, the sample thickness should be
as minimum as possible.

Application

Used for qualitative as well as quantitative analysis by identifying chemical

linkages or groups
Detection of polymer crystallinity
Qualitative measurement of comonomer content
Quantitative measurement of constituents of a compounded resin and
polymer blends

ARDC/CS/Internal 209
 Typical IR Spectra

ARDC/CS/Internal 210
b) UV Visible Spectroscopy

The absorption of UV or visible radiation corresponds to the excitation of outer

electrons. There are three types of electronic transition which can be considered;

1. Transitions involving p, s, and n electrons

2. Transitions involving charge-transfer electrons
3. Transitions involving d and f electrons (not covered in this Unit)

When an atom or molecule absorbs energy, electrons are promoted from their ground
state to an excited state. In a molecule, the atoms can rotate and vibrate with respect to
each other. These vibrations and rotations also have discrete energy levels, which can
be considered as being packed on top of each electronic level.

Absorbing species containing , , and n electrons

Absorption of ultraviolet and visible radiation in organic molecules is restricted to certain

functional groups (chromophores) that contain valence electrons of low excitation
energy. The spectrum of a molecule containing these chromophores is complex. This is
because the superposition of rotational and vibrational transitions on the electronic
transitions gives a combination of overlapping lines. This appears as a continuous
absorption band.

ARDC/CS/Internal 211
Possible electronic transitions of , , and n electrons are shown below:

Double-beam UV/Visible spectrometer

ARDC/CS/Internal 212
 Significance

Here the spectral peaks are corresponding to the energy difference between two
transition levels and since each transition level has its own internal energy levels, the
UV visible spectra is shallow as compared to the infra red spectrum.

Application

Used for quantitative as well as qualitative analysis

Used for analyzing copolymers
Detecting any special substituent in the polymer, etc.

7.9. Identification of Plastics from End Use Products

Sl
End Product Distinguishing Characteristics Plastics
no.

1 Films/ shopping Flexible, transparent, waxy feel, LDPE

bags/ Pouches easily stretched

2 Films/ shopping Flexible, transparent-translucent, LLDPE

bags less waxy, stronger

3 Films/ shopping Semi rigid, translucent-opaque, HMHDPE

bags non-waxy, paper like feel,
stronger

4 Films/ bags Semi rigid, transparent, non waxy PP (TQ)

If very thin, strong

PP (BO)

5 Pouches-snack Mostly stand-up, metallized Multilayer films,

foods, oils, tea, etc. LDPE/LLDPE/HDPE/PP/PET,
etc.

ARDC/CS/Internal 213
6 Housewares- Rigid, good impact, opaque, HDPE
buckets, mugs, medium scratch resistance
drums, etc.

7 Crates, transport Rigid, good impact, opaque, HDPE

containers medium scratch resistance

8 Luggage, Brief Rigid, good impact, opaque, HDPE

cases medium scratch resistance

High scratch resistance, harder

PP (CP), ABS

9 Woven sacks Translucent, non-splitting, good HDPE

tenacity

More transparent, splitting

characteristics, higher tenacity PP

10 Monofilaments/Nets Medium hardness and strength HDPE

/Ropes
Higher hardness and strength PP

Very high strength Nylon

11 Vegetable oil Rigid, high impact, HDPE

containers/Bottles for translucent/opaque
lubricating oil, grease,
cleaning powder,
talcum powder/
Agrochemicals &
pesticide containers

12 Shampoo, cosmetics, Transparent low/ normal impact Unplasticized PVC

mineral water bottles

13 Vegetable oil, Transparent, high impact, lower PET

cosmetics provision thickness
containers

14 Jerry cans, Drums of Opaque, rigid, high impact HMHDPE

high capacity

15 Pipes Rigid, high scratch resistance, UPVC

medium impact

Rigid, medium scratch resistance,

ARDC/CS/Internal 214
 high impact, smaller sizes can be HDPE
coiled

16 Profiles, Claddings, Rigid, high scratch resistance, UPVC

Doors & Windows medium impact

17 Electric conduits Rigid, self-extinguishing UPVC

18 Water storage tanks, Rigid, high impact, non-corrosive LLDPEW, MLDPE, HDPE
Chemical tanks

19 TV cabinets, Rigid, high impact, smooth & glossy HIPS

telephone sets, surface
computer housings, PPICP
audio/video cassettes ABS
& covers, two-in one
cabinets, etc.

20 Mixies, washing Rigid, high impact, high strength HIPS

machines, refrigerator
liners, kitchen PPICP
appliances, etc. ABS

21 Automobile Rigid, high impact, high strength PPICP

components, battery
containers, bumpers, Reinforced PP
dash boards, steering
wheels, radiator fans,
etc.

22 Lighting fixtures, Rigid, transparent, glossy Polycarbonates, PS

louvers, etc.

23 Furniture Items Rigid, high impact, resilient PP

ARDC/CS/Internal 215
 References
1. Polymer Handbook by J. Brandrup, Edmund H. Immergut, Eric A. Grulke

2. Plastic Materials by by John Andrew Brydson

3. Physical Chemistry of Polymer by A. Tager, David Sobolev, Nicholas Bobrov

4. Handbook of Plastics Elastomers & Composites by Charles.A. Harpe

5. Handbook of Analytical Instrument by R S Khandpur

6. Polymer Extrusions by Rauwendal

7. How to assure quality in Plastics by Merry Keating

8. Rotational Molding by Glenn L. Beall

9. Advanced Petrochemicals by Dr G N Sarkar

10. Handbook of Petrochemicals Production Process by Robert A Meyers

11. Plastics Processing - An Introduction by Walter Michaeli

12. Simple Methods for Identification of Plastics by D .Braun

13. Polymer Melt Rheology by Cogswell

14. Handbook of Plastics Testing (Second Edition) by Vishu Shah

15. Plastics Additives Handbook(5th Edition) by Hans Zwiefel

16. Thermoplastic Troubleshooting Guide

17. Blow Molding Troubleshooting Guide

18. 1995 Annual Book of ASTM Standards(Book II- D957 to D3028)

19. 1995 Annual Book of ASTM Standards(Book III-D3029 to D5630)

20. Mitsui Petrochemicals Industries Ltd by MITSUI

21. Training in Plastics Technology by Michaeli/Greif/Kaufmann/Vosseburger

22. Guide for Trouble Shooting by MITSUI

23. http://en.wikipedia.org/wiki

24. http://pslc.ws/macrogcss

ARDC/CS/Internal 216