UNIT FOUR

POLYMERS
Unit Description
This unit describes about polymers, polymer synthesis, structure of polymers, classification of
polymers, properties of polymers and polymer processing techniques
.

Objectives: After completing this unit the students will be able to:

Define polymers and understand about polymer synthesis

Classify polymers and identify polymer structure
Identify polymer properties and polymer processing techniques

Contents
4.1 polymers and polymer synthesis
4.2 Classification and structure of polymers
4.3 polymer properties and polymer processing techniques

4.1 Introduction to Polymers

Polymers are a large class of materials consisting of many small molecules (called monomers)
that can be linked together to form long chains, thus they are known as macromolecules. A
typical polymer may include tens of thousands of monomers. Because of their large size,
polymers are classified as macromolecules. Humans have taken advantage of the versatility of
polymers for centuries in the form of oils, tars, resins, and gums. However, it was not until the
industrial revolution that the modern polymer industry began to develop. In the late 1830s,
Charles Goodyear succeeded in producing a useful form of natural rubber through a process
known as "vulcanization." Some 40 years later, Celluloid (a hard plastic formed from
nitrocellulose) was successfully commercialized. Despite these advances, progress in polymer
science was slow until the 1930s, when materials such as vinyl, neoprene, polystyrene, and nylon
were developed. The introduction of these revolutionary materials began an explosion in polymer
research that is still going on today.

Unmatched in the diversity of their properties, polymers such as cotton, wool, rubber,
Teflon(tm), and all plastics are used in nearly every industry. Natural and synthetic polymers can
be produced with a wide range of stiffness, strength, heat resistance, density, and even price.
With continued research into the science and applications of polymers, they are playing an ever
increasing role in society. The following sections provide an introduction to the science of
macromolecules.

4.2 Polymer Synthesis

The study of polymer science begins with understanding the methods in which these materials
are synthesized. Polymer synthesis is a complex procedure and can take place in a variety of
ways.

4.2.1 Addition Polymerization

The most common type of addition polymerization is free radical polymerization. A free radical
is simply a molecule with an unpaired electron. The tendency for 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, learing 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. The following diagram shows the formation
of a radical from its initiator, in this case benzoyl peroxide.

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 active center is the location of the

unpaired electron on the radical because this is where the reaction takes place. In free radical
polymerization, the radical attacks one monomer, and the electron migrates to another part of the
molecule. This newly formed radical attacks another monomer and the process is repeated. Thus
the active center moves down the chain as the polymerization occurs.
There are three significant reactions that take place in addition polymerization: initiation (birth),
propagation (growth), and termination (death). These separate steps are explained below.
Initiation Reaction
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.
In a typical synthesis, between 60% and 100% of the free radicals undergo an initiation reaction
with a monomer. The remaining radicals may join with each other or with an impurity instead of
with a monomer. "Self destruction" of free radicals is a major hindrance to the initiation reaction.
By controlling the monomer to radical ratio, this problem can be reduced.
Propagation Reaction
After a synthesis reaction has been initiated, the propagation reaction takes over. In the
propagation stage, the process of electron transfer and consequent motion of the active center
down the chain proceeds. In this diagram, (chain) refers to a chain of connected monomers, and
X refers to a substituent group (a molecular fragment) specific to the monomer. For example, if
X were a methyl group, the monomer would be propylene and the polymer, polypropylene.

In free radical polymerization, the entire propagation reaction usually takes place within a
fraction of a second. Thousands of monomers are added to the chain within this time. The entire
process stops when the termination reaction occurs.
Termination Reaction
In theory, the propagation reaction could continue until the supply of monomers is exhausted.
However, this outcome is very unlikely. Most often the growth of a polymer chain is halted by
the termination reaction. Termination typically occurs in two ways: combination and
disproportionation.
Combination occurs when the polymer's growth is stopped by free electrons from two growing
chains that join and form a single chain. The following diagram depicts combination, with the
symbol (R) representing the rest of the chain.

Disproportionation halts the propagation reaction when a free radical strips a hydrogen atom
from an active chain. A carbon-carbon double bond takes the place of the missing hydrogen.
Termination by disproportionation is shown in the diagram.
Disproportionation halts the propagation reaction when a free radical strips a hydrogen atom
from an active chain. A carbon-carbon double bond takes the place of the missing hydrogen.
Termination by disproportionation is shown in the diagram.

Disproportionation can also occur when the radical reacts with an impurity. This is why it is so
important that polymerization be carried out under very clean conditions.

4.2.2 Condensation Polymerization or Step-growth Polymerization

Condensation Polymerization is a chemical reaction in which polymer is formed and a small
molecule of by-product with a lower molecular weight is released. The by-product eliminated is
called as condensate. The reaction can take place between two similar or different monomers.
It is also called as step-growth polymerization.

4.3 Classification of polymers

Polymer is a generic name given to a vast number of materials of high molecular weight. These
materials exist in countless form and numbers because of very large number and type of atoms
present in their molecule. Polymer can have different chemical structure, physical properties,
mechanical behavior, thermal characteristics, etc., and on the basis of these properties polymer
can be classified in different ways, which are summarized in Table 1.1, whereas, important and
broad classification of polymers are described in the next section.
Table 4.1: Classification of Polymers
Basis of Classification

Polymer Type

Origin

Natural, Semi synthetic, Synthetic

Thermal Response

Thermoplastic, Thermosetting Mode

of formation

Addition, Condensation

Line structure

Linear, Branched, Cross-linked

Application and Physical Properties

Rubber, Plastic, Fibers

Tacticity

Isotactic, Syndiotactic, Atactic

Crystalline

Crystalline, Non crystalline(amorphous),

Semi-crystalline,

Polarity

Polar, Non polar

Chain

Hetro, Homo-chain

4.3.1 Origin
On the basis of their occurrence in nature, polymers have been classified in three types.
A. Natural p olym er : - Th e polymers, which occur in nature are called natural polymer also
known as biopolymers. Examples of such polymers are natural rubber, natural silk,
cellulose, starch, proteins, etc...

B. Semi synthetic polymer: - They are the chemically modified natural polymers such as
hydrogenated, natural rubber, cellulosic, cellulose nitrate, methyl cellulose, etc.
C. Synthetic polymer: - The polymer which has been synthesized in the laboratory is known
as synthetic polymer. These are also known as manmade polymers. Examples of such polymers
are polyvinyl alcohol, polyethylene, polystyrene, polysulfide, etc.
4.3.2 Thermal Response
A. Thermoplastic polymers:- They can be softened or plasticized repeatedly on
application of thermal energy, without much change in properties if treated with certain
precautions. Examples o f s u c h p o l y m e r s a r e Polyolefins, nylons, linear polyesters
and polyethers, PVC, sealing wax etc.
B. Thermosetting polymers: - Some polymers undergo certain chemical changes on heating
and convert themselves into an infusible mass. The curing or setting process involves
chemical reaction leading to further growth and cross linking of the

polymer

chain

molecules and producing giant molecules. For example, Phenolic, resins, urea, epoxy resins,
diene rubbers, etc.
4.3.3 Mode of Formation
On the basis of mode of formation, polymers can be classified as:A. Addition polymers: - They are formed from olefinic, diolefnic, vinyl and related

monomers. They are formed from simple addition of monomer molecules to each other in a
quick succession by a chain mechanism. This process is called addition polymerization.
Examples of such polymers are polyethylene, polypropylene, polystyrene.
B. Condensation polymer: - They are formed from intermolecular reactions between
bifunctional or polyfunctional monomer molecules having groups of reactive functional
such as OH, -COOH, -NH2, -NCO, etc.
4.3.4 Line Structure
On the basis of structure, polymers are of three types.
A. Linear polymer: - If the monomer units are joined in a linear fashion, polymer is said to be
linear polymer.

B. Branched polymer: - When monomer units are joined in branched manner, it is called
branched polymer.

C. Cross linked polymer: - A polymer is said to be a cross linked polymer, if the

monomer units are joined together in a chain fashion.

4.3.5 Application and Physical Properties

Depending on its ultimate form and use a polymer can be classified as:A. Rubber (Elastomers):- Rubber is high molecular weight polymer with long
flexible chains and weak intermolecular forces. They exhibit tensile strength in the
range of 300-3000 psi and elongation at break ranging between 300-1000%. Examples
are natural and synthetic rubber.
B. Plastics: - Plastics are relatively tough substances with high molecular weight that
can be molded with (or without) the application of heat. These are usually much
stronger than rubbers. They exhibit tensile strength ranging between 4000-15000 psi
and elongation at break ranging usually from 20 to 200% or even higher. The
examples of plastics are, polyethylene, polypropylene, PVC, polystyrene, etc.
C. Fibers: - are long- chain polymers characterized by highly crystalline
regions resulting mainly from secondary forces. They have a much lower elasticity than
plastics and elastomers. They also have high tensile strength ranging between 20,000150,000 psi, are light weight and possess moisture absorption properties.

4.3.6 Tacticity:A. Isotactic polymer: - It is the type of polymer in which the characteristic group is
arranged on the same side of the main chain.

Isotactic Polypropene

B. Syndiotactic polymer:- A polymer is said to be syndiotactic if the side group

(characteristics group) are arranged in alternative fashion.

Syndiotatic Polypropene

C. Atactic polymer:- A polymer is said to be atactic, if the characteristic groups (side

group) are arranged in irregular fashion (randomness) around the main chain. It has
proper strength and more elasticity.

Atactic Polypropene

4.4 Molecular Weight and its Distribution

The molecular weight of a polymer is of prime importance in the polymers synthesis and
application. It is important because it determines many physical properties. The term molecular
weight is a ratio of the average mass per formula unit of substance to 1/12th of an atom.
Molecular weight (MW) and its distribution (MWD) have a considerable effect on macroscopic

properties of polymer such as toughness, tensile strength, adherence and environmental

resistance, etc. A simple chemical has fixed molecular weight but when we discuss about the
molecular weight of polymer, we mean something different from that which applies to
small sized compounds.

Since polymers are mixture of molecules of different molecular

weight, the molecular weight is expressed in the term of average value. This average
molecular weight is basically based on either average number of repeating units, known as
number average molecular weight, or average weight, known as weight average molecular
weight. The number average molecular weight is obtained from the number ni of
macromolecules for each degree of polymerization Pi by taking for each degree of
polymerization the product of the number of polymer molecules and their degree of
polymerization ni pi and dividing the sum of these product by the total number of monomers No:

Polydispersity
In order to give an idea how broad the distribution of molecular weights for a sample is, we can
define the polydispersity index:

The polydispersity does not give any information about the form of the distribution.
Properties of polymers, for example the ones mentioned below, dependent on Molecular Weight
and Molecular Weight Distributions (MWD).

Melt Viscosity

Tensile Strength

Toughness or Impact Strength

Resistance to heat

Corrosive properties

4.5 Properties of Polymers

4.5.1 Thermal transitions of polymers

Completely amorphous polymers: glass transition temperature (Tg) only

Completely crystalline: crystalline melting point (Tm) only
Semi-crystalline: Both Tg & Tm

Two major types of thermal transitions:

Crystalline melting point

Above Tm polymer is liquid
Below Tm, polymer forms flexible crystalline solids
Glass transition temperature (Tg).
Above Tg polymers are rubbery
Below Tg polymers are glassy
Glass Transition Temperature

In the study of polymers and their applications, it is important to understand the concept of
the glass transition temperature Tg. The glass transition is a phenomenon observed in linear
amorphous polymer. It occurs at fairly well defined temperature when the bulk material ceases to
be brittle and glassy in character and become less rigid and more rubbery. The knowledge of Tg
is essential in the selection of materials for various applications.
Many Physical properties change profoundly at the glass

transition

temperature,

including

mechanical properties and electrical properties. All of these are dependent on the relative degree
of freedom for molecular motion within a given polymeric material and each can be used to
monitor the point at which the glass transition occurs.

Factors affecting Tg:

Chain length
Chain flexibility
Side groups
Branching
Cross-linking

4.5.2 Mechanical properties of polymers

To study the necessary set of valuable properties, polymers differing from one another by their
chemical structure and properties are usually mixed together, either homogeneously or
heterogeneously. The mechanical properties of inhomogeneous mixture are worse than those of
individual polymers, while the mechanical properties of homogeneous mixture are good.
Polymers can exhibit the features of glassy, brittle solid or an elastic rubber, or that of a viscous
liquid, depending on the temperature and time scale of measurement. The studies on mechanical
properties of polymer can, therefore, be carried out by subjecting them to some form of
mechanical stress either continuous or in a periodic manner at different rate. Some of the
important properties of polymers with regard to their use as engineering material are tensile
strength, compressive and flexural strength, hardness, creep, fatigue resistance and impact
resistance.
Toughness of a polymer is the ability to absorb mechanical energy without fracturing. The
property such as tensile strength is the maximum amount of tensile load per unit area a material
can withstand, while the tensile elongation gives the measure of increase in length in response to
a tensile load expressed as a percent of the original length. Elongation at break is the maximum
elongation the plastic can undergo.
Engineering applications of polymers are governed to a great extent by strain hardening
considerations. The designer using polymeric materials must, therefore, understand their
mechanical behaviour with respect to the maximum permissible strains to avoid failure. As for
most materials, a simple tensile stress-strain curve provides a good start towards understanding
the mechanical behaviour of a particular polymer. This curve is usually established by
continuously measuring the force developed as the sample is elongated at constant rate of

extension until it breaks. Portions of the curve in Fig.1.3 represent the stress-strain behaviour of
any polymer and are used to define several useful quantities. The initial slope provides a value
for Young's modulus (or the modulus of elasticity) which is a measure of stiffness. The curve
also gives yield stress, strength and elongation at break. The area under the curve or work to
break is a rough indication of the toughness of the polymeric material. The stress at the knee in
the curve (known as the yield point) is a measure of the strength of the material and resistance to
permanent deformation. The stress at the breaking point, commonly known as ultimate strength,
is a measure of the force required to fracture the material completely.
A hard, brittle material such as an amorphous polymer far below its Tg, usually has an initial
slope indicative of very high modulus, moderate strength, a low elongation at break, and a low
area under the stress-strain curve (Fig. 1.4). Polymeric materials showing hard brittle behaviour
at room temperature or below are polystyrene, poly (methyl methacrylate) and many phenolformaldehyde resins. Hard and strong polymers have high modulus of elasticity, high strength,
and elongation at break of approximately 5 percent. The shape of the curve often suggests that
the material has broken where a yield point might be expected. This type of curve is
characteristic of some rigid poly (vinyl chloride) formulations and polystyrene polyblends. Hard,
tough behaviour is shown by polymers such as cellulose acetate,

4.5.3 Electrical properties of polymer

Materials such as glass, ceramics, polymers and biocomposites are non conducting materials.
They prevent flow of current through them. When these types of non-conducting materials are
placed in an electric field, they modify the electric field and they themselves undergo
appreciable changes as a result of which they act as stores of electrical charges. When charge
storage is the main function, the materials are called dielectrics. For a material to be a good
dielectric, it must be an insulator. As good insulators, polymers posses excellent dielectric
properties. Many authors have reported theoretical and experimental work related to these
properties [29-52]. The common electrical properties of interest are discussed below:
Dielectric polarization
Polarization with the application of an electric field, due to the displacement of charge
particles inside the material forming dipoles, is known as internal polarization. Some of the
internal polarizations are electronic, orientational (dipolar), space charge and barrier
polarization.
Dielectric can also be charged by direct injection of charge carriers, when high electric field
5

(10 V/cm) is applied between the electrodes in intimate contact with it. Charges get sprayed
or deposited due to corona discharge or dielectric breakdown in the thin air gap between the
electrode and the dielectric. If the injected charge in the surface is of same sign as that of
electrode in contact, it is called homo-charge; if it is opposite in sign then it is called heterocharge. Polymers as dielectrics are known to store charge permanently when subjected to field
- temperature treatment; such quasi permanently charged dielectrics are known as Electret.
Dielectric strength

It measures the highest current that can be applied to a plastic before it allows current to pass. It
is expressed as the voltage just before this happens divided by the thickness of the sample (in
volts/m). It is affected by temperature, thickness, how the sample was conditioned,

rate of

voltage increase, test duration and contamination etc.

Electrical conduction
The electrical conductivity of polymer, x, measures the presence of free ions not connected
chemically with the macromolecules. It also depends on presence of low molecular weight
impurities that can serve as source of ions. The chemical constitution has only an indirect
effect on the mobility of the ions.

4.6 Processing of Polymers

Once a polymer with the right properties is produced, it must be manipulated into some useful
shape or object. Various methods are used in industry to do this. Injection molding and
extrusion are widely used to process plastics while spinning is the process used to produce
fibers.
Conversion of plastic materials in to finally finished products is termed plastics processing.
Depends on melt flow behaviour and thermal properties of materials. Three steps are involved in
converting plastics granules/power in to the required shapes.
1. Pre processing
a) Compounding of additives with different formulation
b) Drying
2. Primary processing
3. Post processing
a) welding
b) Joining and Machining
c) Decoration of products by printing
d) Surface treatment
e) Thermoforming
f) Biaxially oriented film.
Plastics processing involves 3 key stages:
1. Heating to liquid state T > Tm or Tg (amorphous polymers).

2. Forming to required shape under pressure p up to 108 Pa (1 kbar)

3. Cooling to solidify
Generally quenched-in nonequilibrium structure (chain orientation, orientation and fraction of
crystallities ...)
Aim: Correct shape + property enhancing microstructure
Heating
Shaping
Cooling

Raw materials
Most polymers are supplied in particulate form (pellets, beads, granulate) which is convenient
transport and handle blend (with additives) and compound store feed and process.
1

m < Size < mm

Mixing
Additives - a wide range of second phases added to polymers for processing and/or properties
Stabilizers (degradation), Colors (pigments and dies), Plasticizers (molecular level) Fillers and

Reinforcements, Lubricants (granule level). Other polymers (co-extrusion, co-injection molding

etc)

4.6.1 Extrusion
Extrusion is similar to injection molding except that the plastic is forced through a die rather than
into a mold. However, the disadvantage of extrusion is that the objects made must have the same
cross-sectional shape. Plastic tubing and hose is produced in this manner.

Fig: the forcing of a plastic or molten material through a shaped die by means of pressure.

The zones in an extruder

1. Feed zone
Preheat polymer and convey it to the subsequent zones.
screw depth is constant
2. Compression zone (transition zone)
channel depth
expel air trapped between original granules
heat transfer from the heated barrel walls is improved coz material thickness

1
3. Metering zone
Constant screw depth
homogenize the melt
supply to the die region material which is of homogeneous quality at constant T & P
4. Die zone

Breaker plate - screen pack (perforated steel plate)

a) Sieve out extraneous material, e.g. ungeled polymer, dirt and foreign bodies
b) allow head P to develop by providing a resistance for the pumping action of the metering zone
c) remove turning memory from the melt
Flow mechanisms: Conveying
Drag flow
dragging along by the screw of the melt as the result of the frictional forces

 Equivalent to viscous drag between stationary and moving plates separated by a viscous
medium.
Constitute output component for the extruder.
Pressure flow

P gradient along the extruder (high P at the output end, low at the feed end
Leak flow

Finite space between screw and barrel through which material can leak backwards.
Total flow = drag flow pressure flow leak flow

Injection Molding
One of the most widely used forms of plastic processing is injection molding. Basically, a plastic
is heated above its glass transition temperature (enough so that it will flow) and then is forced
under high pressure to fill the contents of a mold. The molten plastic in usually "squeezed" into
the mold by a ram or a reciprocating screw. The plastic is allowed to cool and is then removed
from the mold in its final form. The advantage of injection molding is speed; this process can be
performed many times each second.

Injection Moulding Process includes

1. Screw Plasticating
2. Moulding: - refers to shaping of plastic melt inside the mould
Mould Filling

fountain flow

complex flow history, containing shear and elongational components

complex orientation distribution

There are many different polymeric materials that are familiar to us and find a wide variety of
applications; in fact, one way of classifying them is according to their end use. Within this
scheme the various polymer types include plastics, elastomers (or rubbers), fibers, coatings,
adhesives, foams, and films. Depending on its properties, a particular polymer may be used in
two or more of these application categories. For example, a plastic, if cross linked and utilized
above its glass transition temperature, may make a satisfactory elastomer. Or a fiber material

may be used as a plastic if it is not drawn into filaments. This portion of the chapter includes a
brief discussion of each of these types of polymer.

1. Plastics:
Possibly the largest number of different polymeric materials come under the plastic
classification. Plastics are materials that have some structural rigidity under load, and are used in
general-purpose applications. Polyethylene, polypropylene, poly(vinyl chloride), polystyrene,
and the fluorocarbons, epoxies, phenolics, and polyesters may all be classified as plastics. They
have a wide variety of combinations of properties. Some plastics are very rigid and brittle.
Others are flexible, exhibiting both elastic and plastic deformations when stressed, and
sometimes experiencing considerable deformation before fracture
Polymers falling within this classification may have any degree of crystallinity, and all molecular
structures and configurations (linear, branched, isotactic, etc.) are possible. Plastic materials may
be either thermoplasticor thermosetting; in fact, this is the manner in which they are usually sub
classified. However, to be considered plastics, linear or branched polymers must be used below
their glass transition temperatures (if amorphous) or below their melting temperatures (if
semicrystalline), or must be cross linked enough to maintain their shape. Several plastics exhibit
especially outstanding properties.
For applications in which optical transparency is critical, polystyrene and poly (methyl
methacrylate) are especially well suited; however, it is imperative that the material be highly
amorphous or, if semicrystalline, have very small crystallites. The fluorocarbons have a low
coefficient of friction and are extremely resistant to attack by a host of chemicals, even at
relatively high temperatures. They are utilized as coatings on nonstick cookware, in bearings and
bushings, and for high-temperature electronic components.
The advantages of plastics:The grate increase in the use of plastics is due to

their many useful properties,

couples with comparatively low cost,
their low densities,
their high resistance to chemical attack,
their thermal and electrical insulation properties,

 their ease of fabrication in to a wide variety of both simple and complex shapes.
The disadvantages of plastics:The main disadvantages of plastics are:
The low strength and elastic modulus values, in compression with those of metals
The low softening and thermal degradation temperature
Their comparatively high thermal expansion coefficients.
2. Fibers:
The fiber polymers are capable of being drawn into long filaments having at least a 100:1
length-to-diameter ratio. Most commercial fiber polymers are utilized in the textile industry,
being woven or knit into cloth or fabric. To be useful as a textile material, a fiber polymer must
have a host of rather restrictive physical and chemical properties. While in use, fibers may be
subjected to a variety of mechanical deformations stretching, twisting, shearing, and abrasion.
Consequently, they must have a high tensile strength (over a relatively wide temperature range)
and a high modulus of elasticity, as well as abrasion resistance. These properties are governed by
the chemistry of the polymer chains and also by the fiber drawing process.
The molecular weight of fiber materials should be relatively high or the molten material will be
too weak and will break during the drawing process. Also, because the tensile strength increases
with degree of crystallinity, the structure and configuration of the chains should allow the
production of a highly crystalline polymer. That translates into a requirement for linear and
unbranched chains that are symmetrical and have regular repeat units. Polar groups in the
polymer also improve the fiber-forming properties by increasing both crystallinity and the
intermolecular forces between the chains.
Convenience in washing and maintaining clothing depends primarily on the thermal properties of
the fiber polymer, that is, its melting and glass transition temperatures. Furthermore, fiber
polymers must exhibit chemical stability to a rather extensive variety of environments, including
acids, bases, bleaches, dry cleaning solvents, and sunlight. In addition, they must be relatively
nonflammable and amenable to drying.