Lecture 13

Structure of Solids

Recap
Long range arrangements in ionic solids:
NaCl, CsCl, ZnS
Crystalline and non-crystalline Silica
Role of modifiers (e.g. Na2O, CaO) in
lowering the viscosity of glass
Introduction of polymers

Classification of Polymers
Linear polymer/chain polymer
Arrangement of monomers in curvilinear
fashion

Network polymers
Arrangement of monomers in cross network
in 3 dimensions

Classification of Polymers
Thermoplast and thermosets:
Based on the behaviour with
temperature

Thermoplast
The polymers whose shape can be changed by the application
of heat and pressure is known as thermoplast.
Thermoplast: Long chain molecules held together by
secondary bonds
These soften on heating while harden on cooling
It can be easily pliable at high temperature, can be
reshaped easily
Examples: polyethylene, PVC (e.g. tubings, pipes, gramophone
record), PP (e.g. bumpers and dash boards of cars ), PMMA
(e.g. plexi glass, wind shield)

Thermosets
The polymers which after curing resist strongly to any
change of its shape by application of heat and pressure
Polymerization gets completed while heating which results in
hardened structure
Once having cured (or hardened) by a chemical reaction, will
not soften or melt when subsequently heated, cannot be
reshaped easily.
They degrade before melting
Examples: Bakelite, Melamine, Araldite

These materials are sold in market as partially polymerised

material

On the basis of arrangement of

long chains in space we will
talk about plastics and
elastomers in detail in the next
few slides
Also very common engineering
materials

Long chain polymers

Plastics: chains are placed in zig-zag manner, the bond along
the chain is strong covalent bond while the bond between the
chain is weak Vander Wall type
Fibres: chains of different lengths are aligned parallel to
one and other, the bond along the chain is strong covalent
while the bond between the chain is weak hydrogen type.
Very strong along the axis of fibers.
Elastomers: Long chain polymers with few cross links across
the chains. Importantly the cross links are of primary bond
between chains. Chains have translation mobility at RT .

Plastics

Structure of Long Chain Polymers

Degree of Polymerization:
No. of repeating monomers in a chain

On the basis of monomer unit other plastics

can be described

Monomer Unit
Side groups can be labelled as R1, R2, R3 and R4

Common Plastics
Name

R1 R2

R3

R4

Uses

PE

Containers, bags

PVC*

Cl

Piping's, tubing

PP

CH3

PMMA

CH3

COOCH3

Dash boards, bumpers

of cars, buckets
Plexiglass, window
pane

Polystyrene H

C6H5

PTFE

Styrofoam, packaging
material
Sliding and rotating
bearings

* Plasticisers are often added to make it soft

Common Plastics

Elastomers
Exhibit rubber like elasticity

Long chain molecules with some cross-link

Crosslinks are present at a distance of few hundred
monomers

Natural tendency for bending

and coiling

Mobile segments

Chain segments have

translational mobility
at room temperature

Cross-link points

The conditions listed in previous slide can

be found satisfied in the next few slides

Poly-isoprene (Natural Rubber)

Liquid natural
rubber (latex)
being collected
from the rubber
tree
Liquid state:

Translation point
confirmed

Isoprene molecule

commons.wikimedia.org

H H3C H
C=C-C=C

HH

CH3 H

CC

CC

Isoprene
molecule

Polymerization

CH3 H
CC
H

Polyisoprene
mer
Liquid
(Latex)

Bigger side group requires more space, since rotational

movement is difficult because of double bond it starts
bending, this provides natural tendency of bending and coiling

A natural rubber in the liquid state cannot

be used as rubber band, truck tyre or eraser
Then what we should do??

Provide few crosslinks (possible because of

double bond)
The process is known as Vulcanization

Vulcanisation
Heat the liquid with Sulphur

CC
H

CC
+ 2S

CC
H

CH3 H

CC
CH3 H

Weak
van der
Waals
bond

Vulcanisation

CC

CC
H

CH3 H

CC

H
H

Crosslinks

CC
CH3 H

Now this becomes solid mass!!

Effect of cross-linking on
polyisoprene
Natural
rubber
liquid

not
x-linked

Elastomer

Ebonite

Elastic
solid (soft
rubber)

Hard &
brittle

lightly
x-linked

heavily
x-linked

You may have seen tyres are more rigid

than tube. Why this is so because of
degree of vulcanization.
Note there are variety of rubbers.

Summary of key points

Note that by playing with degree of the
vulcanization one can generate various
possibilities.

After 100% crosslinking we call this as

ebonite.
Cross link after every few 100 monomers
gives soft rubber.

Mechanical behaviour of Elastomer

Mechanical behavior of
Elastomers
1. A few hundred percent of temporary
(recoverable) deformation on stretching.
2. The deformation is non linear, Stress strain

3. The stretched elastomers contracts on

heating

Elastomer sample
under tension

Elastomer
sample

heat

Tensile force

straight
chains

Coiled chains
Higher
entropy

Lower
entropy

Still lower
entropy

Contracts on
heating

Elastomers have ve thermal

expansion coefficient, i.e., they
CONTRACT on heating!!

EXPERIMENT after Minor-I

Section 10.3 of the textbook