G LA S S TRA NS I TI O N

T EM PER ATU RE

Tg
G L A S S T R A N S I T I O N T E M P E R AT U R E

Definition
The thermal expansion, heat capacity, modulus, and many
other properties of inorganic glasses show a relatively
sudden change at the glass transition temperature. Any
such step or kink can be used to define Tg. To make this
definition reproducible, the cooling or heating rate must be
specified.

Measurement of Tg by DSC Measurement of Tg by Dilatometry 2

G L A S S T R A N S I T I O N T E M P E R AT U R E

Definition
i) Polymer melt changes on cooling to glass or a polymer
glass changes on heating to a rubbery state

ii) Part of main chain becomes mobile

iii) Amorphous polymer become soft on heating

iv) Temperature at which there is transition from glassy

to rubber phase

Important determinant STIFFNESS OR SOFTNESS

I. Aliphatic Groups
II. Aromatic Groups 3
G L A S S T R A N S I T I O N T E M P E R AT U R E

The Effect of Main Chain

The Chain stiffness affects chain
mobility.
•If there are bulky groups, such
as benzene rings, in the backbone
of the polymer chain, there is a
high energy barrier to rotations,
which then only occur at higher
temperatures.
Polymer PE PP PVC PS PC
Tg -80 ⁰C -20 ⁰C 80 ⁰C 100 ⁰C 150⁰C

Inreasing Chain Stiffness

Tg increases 4
G L A S S T R A N S I T I O N T E M P E R AT U R E

THE EFFECT OF BULKY SIDE GROUPS

The presence of bulky pendant groups attached
to the polymer backbone raises the Tg,
through steric hindrance to bond rotations. As
the pendant group gets larger, the Tg
increases.
The effect of attaching a methyl group to the
main chain of PS, to give poly(_-methyl
styrene), is greater than increasing the size of
the aromatic unit, because the close proximity
of this group to the polymer backbone
introduces a higher degree of steric hindrance.
Compare PaMS, PVN and PVBP.
5
G L A S S T R A N S I T I O N T E M P E R AT U R E

THE EFFECT OF flexible SIDE GROUPS

Tg decreases with increasing side-chain length.
Substituents closest to the chain, the methyl and ester
group, provide the bulk of the steric hindrance. The
rest of the attached side chain can "get out of the
way“ of motions of the main chain through rotations
around side-chain bonds. Because these side chains
increase the free volume through their effect on the
packing of the chains, the Tg is lowered.
Increasing length of flexible side group

6
G L A S S T R A N S I T I O N T E M P E R AT U R E

The Effect of Main Chain

O O

C R C O CH2 CH2 O

Increasing Chain Stiffness

When R is as under Tm
R= CH2

Tm increases
4 50 ⁰C

R= 270⁰C

350 ⁰C
R=

R= CH2 CH2
220 ⁰C

420⁰C
R= CH CH

7
G L A S S T R A N S I T I O N T E M P E R AT U R E

The Effect of Molecular Weight

The ends of a chain have more

Glass Transition Temperature Tg

freedom of motion than the
segments in the center of a chain
and, crudely, can be thought of
as having "more free volume".

Low molecular weight chains have more ends per unit volume than
long chains, hence a higher free volume, hence a lower Tg.
Fox and Flory used such simple free volume arguments to obtain
the following equation:
8
G L A S S T R A N S I T I O N T E M P E R AT U R E

The effect of intermolecular attraction Crosslinking

Strong intermolecular attractions
also act as to raise the Tg.
•The chlorine atom and methyl
group have approximately the same effect on bond rotations.
•The polar character of the Cl atom leads to stronger forces of
attraction between chains, however, so that on average these groups
are closer.
•The free volume is less and the Tg is higher (reality is probably a bit
more complicated than this
•Similarly, cross-linking decreases free volume, because parts of the
chain
9
•Are tied more closely together, hence Tg increases.
G L A S S T R A N S I T I O N T E M P E R AT U R E

The effect of Diluents and Copolymerization

Schematic diagram depicting the intermediate Tg observed in a
miscible mixture, relative to one that is phase separated
Q: what would you expect for a random copolymer vs. a
block copolymer ?
The Tg of a mixture can
Be simply rationalized on
The basis of free volume
arguments to give the
Fox equation

10
G L A S S T R A N S I T I O N T E M P E R AT U R E

The effect of Isomerism

Tacticity
Syndiotacticity and isoltacticity increases Tg

a-PMMA = 45 ⁰C
s-PMMA = 105 ⁰C
i-PMMA = 105 ⁰C

Cis and Trans isomers

Trans isomer always has higher Tg than cis isomer Tg

11
G L A S S T R A N S I T I O N T E M P E R AT U R E

The effect of Symmetry CH3

CH2 CH CH2 C
n n
CH3 CH3

Polypropylene Polyisobutylene
Tg =-20 ⁰C Tg =-70 ⁰C
Cl

CH2 CH CH2 CH2

n n
Cl Cl

Polyvinyl Chloride Polyvinylidene Chloride

T = 89 ⁰C T = -17 ⁰C 12
G L A S S T R A N S I T I O N T E M P E R AT U R E

The effect of Steric Hinderance CH2 CH

n

CH2 CH2 CH2 CH

n n
CH3
Polyethylene Polypropylene Polystyrene
Tg =-120 ⁰C Tg =-20 ⁰C Tg =100 ⁰C
CH2 CH
n CH2 CH
n

CH3

O-methyl Polystyrene Polynephthalene

T = 119 ⁰C T = 135⁰C 13
G L A S S T R A N S I T I O N T E M P E R AT U R E

The effect of Polarity

CH2 CH CH2 CH
n n
CH3 Cl

Polyvinyl Chloride
Polypropylene
Tg = 89 ⁰C
Tg =-20 ⁰C
CH2 CH
n

Polyacrylonitrile
T = 100 ⁰C 14
G L A S S T R A N S I T I O N T E M P E R AT U R E

The effect of hetero atom in polymer chain

Incorporation of any hetro atom like oxygen in
main chain increases flexibility & capable of
large scale motion even at low temperature

15