Polymers

Course Coordinators
Dr. Anupama Kumar & Dr. Abhishek Banerjee

Department of Chemistry, VNIT, Nagpur

31.05.2022

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 Properties of polymers
The properties of high polymers are determined mainly by the magnitude and distribution of attraction forces
between the molecules
1)Primary or chemical land forces.
2)Secondary or intermolecular forces.

3) In straight chain & branched chain polymers the individual chains are held together by weak intermolecular
forces of attraction. The strength of which increases with the chain length or molecular Wt. Such polymers
exhibit mechanical strength only when chain length in greater than 150 to 200 atom.

1000

DP 500

0
Tensile strength
2) By controlling the chain length, it is possible to vary the physical properties of
the polymer from soft and flexible to hard & horn like substances
3) e.g. polymer with low MW are quite soft and gummy but they are brittle to
impact at low temperature but longer chain polymers an tougher & more her
resistant.
4) The intermolecular forces can be greatly increased by the presence of polar
groups like carboxyl, hydrogen chorine fluorine & nitrile along for length .

5) Strength of the straight chain polymer also depends on the slipping power of
one molecule over the other. shape of polymer molecule greatly effect the
resistance to slip & consequent deformation of a polymers e.g. The shape of
polymer molecule greatly affects the resistance to slip and consequent
deformation of a polymer.

5) In Cross linked polymer all structural units are connected by strong covalent
forces resulting in a giant solid molecules extending in three dimension.
Consequently they are more strong & tough since the movement of
intermolecular chain is totally restricted.
Plastic deformation :-

• The linear polymer without cross linking or branched structure show the greatest degree of plastic
deformation.

• Under pressure polymer deforms especially at high temperature because at high temperature the van
der waals forces acting between different molecules become more and more weak & hence are easily
overcome. These materials, are called thermoplastic polymers in heated state readily taken the shape
of the mould when it is injected in to it under pressure.

• On cooling the material become rigid in the molded shape because plasticity of the material decreases
with the fall of temperature.

• Thus the plasticity of polymer is reversible.

• In cross linked polymer deformation does not occur on heating because only primary covalent bonds
are present through out the entire structure & no slip in between the molecule can occur.

• In these so called thermosetting polymers, plasticity does not increase with increase in temperature.

• When considerable external force or temperature exceeding the stability of material is applied it
results in total destruction.
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So why is it that some polymers are highly crystalline and some are highly amorphous?
There are two important factors, polymer structure and intermolecular forces.

 If it's regular and orderly, it will pack into crystals easily. If
it's not, it won't. It helps to look at polystyrene to
understand how this works.

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 There are two kinds of polystyrene. There is atactic polystyrene, and there is 
syndiotactic polystyrene. One is very crystalline, and one is very amorphous.

Syndiotactic polystyrene is very orderly, with the phenyl groups falling on alternating sides of
the chain. This means it can pack very easily into crystals.
But atactic styrene has no such order. The phenyl groups come on any which side of the chain
they please. With no order, the chains can't pack very well. So atactic polystyrene is very
amorphous. 9
Chemical Resistance :-

The chemical nature of monomeric unit & their molecular arrangement determines
the chemical resistance of polymer. Usually chemical attach is internal causing
softening swelling & loss of strength of material.

General rule :- Like material attracts while unlike material repels. Thus polymer is
more soluble in structurally similar solvent.

Aliphatic – Aliphatic solvent

Aromatic – Aromatic Solvent

General Rule :- Tendency to swell in a particular solvent decreases with increase in

Mol wt of the polymer
i. High Mol wt polymer on dissolving gives solutions of high viscosity.
ii. Crystalline polymer (due to denser packing of the molecular chain) exhibit
higher chemical resistance than the less crystalline polymer of similar chemical
character. Denser packing makes the penetration of solvent in the polymeric
material non difficult.
iii. Greater the degree of cross linking leaser is its solubility.
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 Effect of Heat on Polymer

Amorphous polymer do not posses melting points, but softening points. At low temperature, polymer
exists as a glossy materials & at this state it tends to shatter if it is hit, because the molecular chain
cannot move at all easily. When the polymer is heated, it eventually soften & become more flexible.
This is glass transition temperature (Tg). After this, Crystalline & Amorphous thermoplastic polymers
behave differently. Heating has little effect on thermosetting polymers, until at high temperature, they
are destroyed.

a) Amorphous Polymer : Glass rubber gum liquid

Tg
Increasing temperature
b) Crystalline Polymer : Crystalline Glass region Flexible thermoplastic liquid
Tm
Tg
Increasing temperature
Softening indicates that the polymer chain has gained enough energy to move slightly.
 Mechanical properties of Polymers

• The mechanical behavior of a polymer is characterized by its stress-strain properties. As tensile stress is
applied on a polymer, it causes its elongation to a point of rupture and the behavior is seen in a plot of stress
vs strain (elongation).
• The stress is expressed in PSI (or kg m-2 ) & stress as the fractional increase in length of the polymer sample
(ΔL/L when L is the length of the unstretched sample). Generally high strength & low extensibility are
observed in polymer having cross-linking or high crystallinity.
• While high extensibility and low strength are with low degree of crystallinity and cross-linking.

• Apart from hard & very little polymer there are two key stages in the graph. At some stage (called necking),
the stress become so great that the polymer began to yield (i.e. it begins to stretch very easily for only a tiny
increase in stress) the next point (called break point) is when the stress becomes so large that the sample
breaks.
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