CHAPTER 5

POLYMER

By
Dr.Vaishali Agme
➢Introduction: Definition- Polymer,
polymerization, Properties of Polymers_x0002_

➢Molecular weight (Number average and

Weight average), Numerical problems on
Molecular weight

➢ Effect of heat on polymers (glass transition

temperature),
➢Viscoelasticity,Conducting Polymers,

➢Classification-Thermoplastic and
Thermosetting polymers;

➢Compounding of plastic,
➢Fabrication of plastic by
Compression, Injection, Transfer and Extrusion
moulding,
➢Preparation, properties and uses of PMMA
and Kevlar.
➢A polymer is a large
macromolecule of high to
very high molecular
weight which consists of
many repeating units
called monomers
which are covalent bond
to one another.
➢In many cases,
monomers are linked
together in a row, like
links in a chain. However
branching and cross-
linking between chains
does occur.
Properties of Polymers
Physical Properties
As chain length and cross-linking increases the tensile
strength of the polymer increases.
Polymers do not melt, they change state from crystalline to
semi crystalline.
Chemical properties
Compared to conventional molecules with different side
molecules, the polymer is enabled with hydrogen bonding
and ionic bonding resulting in better cross-linking strength.
Dipole-dipole bonding side chains enable the polymer for
high flexibility.
Polymers with Van der Waals forces linking chains are
known to be weak, but give the polymer a low melting point.
Polymers are all created by the process of
polymerization wherein their constituent elements
called monomers, are reacted together to form polymer
chains i.e 3-dimensional networks forming the polymer
bonds.
Type of POLYMERIZATION
mechanism used depends on the type of
functional groups attached to the
reactants.
In biological contexts, almost all macro
molecules are either completely
polymeric or are made up of large
polymeric chains.
Natural polymer:
Polymers which occur in nature are called natural polymers. For
example: Natural
rubber, natural silk, cellulose, starch, proteins, etc.
Synthetic polymer:
Polymers which are synthesized in the laboratory are known as
synthetic polymers.
For example: polyvinyl alcohol, polyethylene, polystyrene, etc.
Semi synthetic polymer:
Natural polymers that are chemically modified are called semi synthetic
polymers.
For example: cellulose nitrate, methyl cellulose, etc
Linear polymers: The polymers, in which monomers are
linked in linear orientation (straight chains), are called
linear polymers.–M–M–M–M–M–M–
Branched polymers: Polymers in which monomers are
linked in branched fashion are called branched polymers.
–M–M–M–M–M–M–M-M-
Cross linked polymers: Polymers in which monomers are
linked to form a three dimensional structure. For example:
Bakelite, Melamine.
Types of polymers
Organic Polymers: Polymers with a carbon
backbone.

Inorganic Polymers: Polymers with a backbone

constituted by elements other than
carbon.
Elastomers: Polymers which undergo elongation on
application of stress and regain its original shape
when stress is released completely.
The polymeric chains are held by weak intermolecular
forces. For example, Natural and synthetic rubbers.
Fibres:
Polymers which have thread like structure and can be easily woven.The
intermolecular forces may be hydrogen bonds or dipole-dipole
interaction.
For example: Nylon-66.
Thermoplastic polymers:
Thermoplastic polymers are the materials which, at first soften on heating
above the glass transition temperature or melting and then after cooling
become hard.
For example: PVC, Teflon, polyethylene.

Thermosetting polymers:
Thermosetting polymers are the materials which become permanently hard
and rigid on cooling when heated above the glass transition temperature or
melting.
For example: Bakelite,epoxy resins, urea formaldehyde resin
Classification of Polymers Based on The Mode of
Polymerization
Addition polymers:
Polymers which are formed by addition polymerization
reaction which involves self-addition of monomers
without elimination of by products are called addition
polymers.
For example: PVC, polystyrene, Teflon, polyethylene, etc.

Polymers which are formed by condensation reaction

through functional groups of monomers with continuous
elimination of by products are called condensation
polymers.
For example: Nylons, polyesters, phenol-formaldehyde
resin, etc.
Glass Transition Temperature
▪ Glass transition temperature is abbreviated as Tg.
▪ It is the temperature at which higher molecular weight
amorphous polymers get transformed from glassy
state to viscous and rubbery state.
▪ It is the one of the most important property of
polymers (plastics/ rubbers) at a particular
temperature.
▪ When the polymer is cooled below this temperature, it
becomes hard and brittle and above this temperature
▪ it is soft and flexible.
▪ At this temperature the amorphous polymers
experience transition state from rubbery to rigid
states.
Crystallanity: Crystallanity is directly
proportional to Tg value. Higher the degree of
crystallanity, higher is the Tg value.

Molecular weight: Molecular weight of

polymers is directly proportional to Tg upto
20,000, beyond this no appreciable effect is
observed.
3)Presence of crosslinkage in polymers-
Presence of cross linkages between polymeric
chain , resists the rotational motion and
increases Tg value.
4) Presence of side group
The presence of larger side group on the
polymeric chain can restrict the rotational
bonds and increases Tg value.
 :
▪ It provides information about nature of polymer at
operating temperature.
▪ Polymers at a particular Tg will be soft and flexible
and below that would be hard and brittle, this
▪ knowledge about the polymers is beneficial for the
use of polymers at variable temperature.
▪ It is the parameter used to modify physical
properties of polymers.
▪ Helps in determining the optimum processing
temperature of the polymers.
▪ It provides convenient knowledge about rigidity,
flexibility and glassy or rubbery state of polymers.
Characteristics of Viscoelasticity
▪ Viscoelasticity is the mechanical property of polymeric materials.
▪ Because of this property, polymeric materials can exhibit both
viscous and elastic characters when undergoing deformation.
▪ It shows the combined effects of viscous and elastic behavior
under the applications of stress on polymers.
▪ It helps to determine the mechanical performance of polymeric
products during operations.
▪ Viscoelasticity is a temperature, pressure and time dependent
property of polymers.
▪ Viscoelastic state of polymers is when polymeric materials show
both viscous and elastic behaviour while undergoing
deformation.
Why are polymers viscoelastic?
One important characteristics of polymeric
materials is their viscoelastic behavior. This
means that polymer is elastic because after a
strain due to the application of a stress, it is
capable to recovers. On the other hand,
polymers are viscous because their capability
to creep after the strain.
Rubber is the most notable example of a
polymer which exhibits viscoelastic properties.
... The added material then forms additional
cross links between polymer chains.
Materials that exhibit both viscous and elastic
characteristics when deformed under stress are
known to be viscoelastic. And this would
include any polymeric material—from butter to
bicycle helmets.
What is viscoelastic material used for?
▪ Viscoelastic materials are used in
automobile bumpers, on computer drives to
protect from mechanical shock, in helmets
(the foam padding inside), in wrestling
mats, etc.
▪ Viscoelastic materials are also used in shoe
insoles to reduce impact transmitted to a
person's skeleton.
The polymeric materials which have conjugated
double bonds in their polymeric chains are
called as conducting polymers.
Examples
1) Polyacetylene
2) Polyphenylene vinylene
3) Polythiophene
4)Polyaniline

These polymers are capable to conduct

electricity due to presence of delocalized pi
electrons.
Polyphenylene vinylene

Polythiophene

Polyaniline
▪ Strong electrical and electrtochemical
properties
▪ high melting point
▪ high flexibility
▪ highly transparent
▪ light weight
▪ electrical stability
1) Intrinsically conducting polymers
2) Extrinsically
3) Doped
4) Coordination
Possess conjugated pi-electrons which get
more excited in the presence of electric field
and move through out the polymeric chain

They posses more flexibility.

E.g Polyaniline
Compounding of plastics
▪ A process of melt
blending plastics with other
additives.
▪ This process changes the
physical, thermal, electrical or
aesthetic characteristics of
the plastic.
▪ The final product is called
a compound or composite.
1) Binders
2) Fillers or Extenders
3) Plasticizers
4) Pigments & Dyes
5)Accelarators/ Catalyst
6)Lubricants
7) Stabilizers
1)Binders –
▪ Binders hold the other constituents together during manufacture. eg.
Natural or synthetic resins or cellulose derivatives, etc
▪ Binders influence the properties of plastics. The type of treatment during
moulding operation also depends upon binders.
▪ If a binders used has comparatively low molecular weight, then plastic
article gets moulded easily & vice versa.
2) Fillers or Extenders –
▪ Fillers impart better tensile strength, hardness, finish, workability,
opacity, etc to the plastic material. eg.
– Wood flour, cotton pulp, paper pulp, carbon black,
graphite, powdered rubber, etc.
asbestos, powdered mica, silicate clays, talc, Zn & Pb
oxides, Cd & Ba sulphides, Al, Fe, Cu, metal in powdered form, etc.
▪ They reduce shrinkage & brittleness.
▪ They also reduce cost of the plastic per unit weight.
Use of plasticizer:
Plasticizers are added to plastic during compounding to
impart flexibility to the plastics. There are low molecular
weight compounds when added, which weaken the
intermolecular forces
of attraction within polymeric chain and decrease the Tg
value.
Presence of cross linking: The presence of cross linkages
between polymeric chains, resist the rotational motion and
increase Tg.
Presence of side group:
Presence of larger side group on polymeric chain can
restrict the rotation of bond and increase Tg.
Amorphous polymers do not have sharp melting point. At
low temperature, these are hard and rigid where at high
temperature, these are flexible and rubbery.
This is the transition temperature, where this kind of
transition in polymers is observed.
3) Plasticizers – These help to increase the
plasticity of the plastics. eg. Vegetable oil,
camphor, esters of stearic, tri-phenyl
phosphate, diethyl phthalate, etc
These help to reduce the forces of
intermolecular attraction & thereby
increases tendency of sliding or moving.
Thus the plastics which are plasticized
possess high percentage of flexibility. They
are essentially used in thermo softening
plastics.
4) Pigments / Dyes –
These imparts desired colors to the plastic. eg. Organic dyestuffs &
inorganic pigments
The coloring matter used in plastics should be resistance to the action of
sunlight.
5) Catalysts or accelerators – These are used to increase the rate of
polymerization of fusible resin binder to form cross linked infusible form
during moulding operations. eg. Hydrogen peroxide, benzoyl peroxide,
metallic oxides, etc
6) Lubricants – lubricants help during moulding operations, especially
during low or room temperature moulding. eg. Soaps or esters of fatty
acids such as oleic & stearic acids or waxes.
The use of lubricants imparts flawlessness, & glossy finish to the plastic
products. They form a layer between they article & mould. This layer
prevents the plastic material from sticking to the surface of the mould, &
thereby facilitating the moulding operations.
7) Stabilizers -
Stabilizers helps to improve thermal stability of the plastic. eg. Salt of
lead, white lead, lead chromate, red lead, & transparent moulding
compounds are stearates of lead, cadmium & barium, etc.
These are required especially in the processing stage for plastic,
which have tendency to decompose or change their colours at
moulding temperatures.
 Fabrication of plastics
1. Compression- THERMOSETTING
2. Transfer-thermosetting
3. Injection and-thermoplastic
4. extrusion moulding-thermoplastic
Applications of compression moulding
Compression moulding find applications
in our daily lives such as in
manufacturing skateboards and
snowboards, electrical housings,
switches, iron handles, plugs etc.,
kitchenware, bottle caps, housing
appliances, cabinets for TV set and
buttons/knobs.
Advantages of compression moulding
•The articles produced by compression
moulding are stronger, stiffer, and corrosion
resistant.
•Complex parts can be manufactured
conveniently.
•Tools required for compression moulding are of
low costs.
• It is more beneficial for small production run.
•From the significantly bulk material it can
provide large production.
• Good dimensional accuracy and finishing.
•High rate of production
Disadvantages of compression
moulding
▪ During operation, mould can be
damaged.
•Not suitable for complex moulds.
•slow process.
▪ creates greater wastage of
materials.
2 Transfer Moulding
Advantages of transfer moulding
Advantages of transfer moulding are listed below:
• Intricate shapes can be prepared conveniently
• Products have high strength and durability.
• Products show minimum distortion and
shrinkage.
• Cost efficient.
• Delicate articles can be handled without any
distortion.
Applications of transfer moulding

Transfer moulding is used extensively in

making spark plug wires, wind turbine
blades, car bodies,
helmets and truck panels
Injection Moulding
Advantages of injection moulding
▪ Products have good tolerance capacity.
▪ Requires low cost.
▪ Good product uniformity.
▪ Good dimensional control.
▪ Very small parts can be produced easily.

Applications of injection moulding

Injection moulding finds its application in the
making of articles such as automotive dash boards,
electronic components, toys and dental and
medical products etc.
Extrusion Moulding
Advantages of extrusion moulding
•High flexibility in manufactured products.
•Cost-efficient process.
•High rate of production.
•Continuous type of products can be
manufactured.
•Easy material handling

Applications of extrusion moulding

Extrusion moulding finds its application into
manufacturing hollow pipes and tubes, rods,
strips, cables,
sheets, rectangular pieces, rollers, sliding stands
and insulation of electrical wires
Advantages of extrusion moulding
•High flexibility in manufactured products.
•Cost-efficient process.
•High rate of production.
•Continuous type of products can be
manufactured.
•Easy material handling

Applications of extrusion moulding

Extrusion moulding finds its application into
manufacturing hollow pipes and tubes, rods,
strips, cables,
sheets, rectangular pieces, rollers, sliding stands
and insulation of electrical wires
▪ Strong and tough.
•Light weight material.
•Good impact strength.
•Excellent light transmission.
•Resistance for UV rays.
• Weather resistant.
•Transparent polymer.
{CH2=C-COOCH3} ------> -[CH2-C-COOCH3]-n
▪ PMMA finds its application in
manufacturing automobiles and
transportation, furniture and design,
▪ lighting application, electronic displays,
cosmetic packaging, sheets of light weight
alternatives to soda lime glass,
architecture and construction, contact
lenses and display racks, luminous
ceilings and bathtubs.
▪ Kevlar is an infusible, aromatic polymer with
a very high thermal stability and light weight.
▪ It was originally manufactured as a light
weight but strong material for tyres.
▪ It is manufactured as a fibre by solution
spinning. However, it is expensive to
synthesize.
▪ Monomers:
▪ Terphthallic acid dichloride and 1,4 di amino
benzene
•Very high thermal stability.
•Very high strength and toughness.
•It is stronger than steel and aluminum.
•Easy to integrate.
•Shows strong resistance to chemicals,
temperature and flame.
•Relatively light weight.
Kevlar finds its application in manufacturing
bicycles tyres, bullet proof jackets, knife
proof body armor,military helmets, car’s
breaks and tyres and fire resistant
mattresses.
 Injection

https://youtu.be/b1U9W4iNDiQ
https://youtu.be/k7lb-w7o06s
 Compression

https://youtu.be/YR31Q6nPMPk
Extrusion

https://youtu.be/k7lb-w7o06s
 transfer

https://youtu.be/NzpHCjL_AnE
https://youtu.be/b1U9W4iNDiQ