POLYMERS

GLASS TRANSITION PHENOMENA

Melting
and
Phenomena

Glass

THEORY

Transition

The temp at which polymers become hard, brittle, glossy and

above which it is softer and flexible is known as glass transition
temp.
e.g.

Polyethylene has Tg 1200C and Tm 1300C, Polystyrene

Tg 1000C and Tm 2500C , Polysiloxane [osi(CH3)2]Tg
120 + Tm 900C.

The hard and brittle state is the glossy state and soft flexible state
is the rubbery or viscoelastic sate. If viscoelastic state is heated
further, the polymer become a viscous liquid and can flow. This
sate is known as viscofluid state.
Glossy state

Viscoelastic state

Viscofluid state

Hard and brittle

Soft and flexible

Viscous liquid

Tg

Temp

Tm

The temperature below which the polymer is in rubbery sate and

above which it is a liquid is called Tm.

POLYMERS

GLASS TRANSITION PHENOMENA

Above
Molecules
in
polymer do not
move apart and do
not
have
movements
with
molecular chains.

Below
Chain
segment
with in molecular
chain
move
internally but there
is no movements
from one position
Stress property to other.
is lost and it is
They
have
brittle.
flexibility or stress
transfer property.

THEORY

Above Tm
Kinetic energy of
polymeric molecule
is high enough to
cause movement
with in the chain
segment as well as
to move from one
position to another.
It has flow
character like liquid

Factors affecting (Tg) :

(i)

Higher molecular weight greater is Tg.

(ii)

A greater degree of crosslinked has higher Tg.

(iii) Greater flexibility, then smaller is Tg.

(iv) Adding a plasticizer to polymer decreases the Tg.
(v) Polymer having stronger intermolecular forces of attraction
have greater Tg.

POLYMERS

GLASS TRANSITION PHENOMENA

THEORY

Viscoelasticity of polymers :
Low molecular weight materials are either elastic solid of viscous
liquids.
Solid energy when external force is applied for
deformation and when released it regains original shape.
In viscous liquid there is no proper shape hence when external
like solid 7 are applied it flows out irreversibly.
Silicon rubber flows over of hours, fractures like solid and deforms
rapidly and also bounces like elastomers.