GLASS TRANSITION TEMPERATURE

Introduction-
A polymer is a large molecule, or macromolecule,
composed of many repeated subunits. A well ordered polymer is
considered crystalline. The opposite is an amorphous polymer.
Almost all amorphous polymer posses a temperature boundary.
Above this temperature the substance remain soft ,rubbery and
flexible and below this temperature it become hard , glossy and
brittle.

The temperature below which a polymer is hard and above

which it is soft is called the glass transition temperature. It is
denoted by Tg .
For example-
When an ordinary rubber ball if cooled below -70 C , it become
so hard that it will break into pieces like a glass.
This happens because there is a temperature boundary for
amorphous. The transition from the rubber to the glass like state
is an important featured of polymer behavior. The hard glossy
state is known as the glossy state and the soft flexible state is the
rubbery state.
Glossy state Rubbery state visco fluid State
(Brittle plastic) ( tough plastic) (polymer melt)

Tg Tf Commented [1]:

Temperature
Change of state with temperature in polymeric material

Determination of glass transition temperature-

It can be determined by following method-
1. Dilato matric method- It is used to determine the expansion
coefficient of the polymer sample. Under a constant rate of
heating, the dilatometer measure the change in volume of
the sample.

Plot between change in V against temperature

 2. Thermomechanical method- It is used to accurate
measurements of dimensional change of polymer sample as
a function of temperature. The sample polymer expands
with increase in temperature. It actuates an extension
probe and Change in dimension ( L) is directly recorded
against temperature.

Plot between change in dimension against temperature

3. Calorimetric method- It is used to measure the heat

capacity of the polymer as a function of temperature. The
sample of polymer and a reference sample are heated at a
programmed rate of heating. The heat capacity of the
sample is measured as a function of the differential heat
flow rate between the sample and reference material.

Factors affecting glass transition temperature-

1) Molecular weight
2) Cross-linking
3) Intramolecular hydrogen bonding
 4) Plasticizers
5) Aromatic ring
6) Chemical structure

Effect of molecular weight-

The molecular weight of a polymer effects on glass transition
temperature at least up to around a value of 20,000;
Above this value, the effect of the molecular weight does not
account. The mathematical relation between Tg and molecular
weight average of a polymer (Mn) is –
1/Tg = 1/ The + A/M n
A is arbitrary constant.

Effect of cross linking-

When cross linking are introduced into a polymer, the molecular
motion in the sample is restricted and Tg rises.

Effect of intramolecular hydrogen bonding-

If the intramolecular hydrogen bonding is present between the
polymer chains, restrict the rotations which increase the Tg.
Example- Nylon- 6 is polyamide have high glass transition
temperature i. e, 50 C due to presence of a large no. Of polar
groups in the molecules having intra molecular hydrogen
bonding.

Effect of chemical structure-

The chain repeat units, intramolecular forces, chain stiffness,
symmetry, stiff bonds, hindrance to free rotation along the
polymer chain and bulky side groups effect glass transition
temperature.

Effect of aromatic ring-

If the aromatic rings are present in chain of polymer, it decrease
the flexibility of the chain, therefore the glass transition is high.

Effect of plasticizers-
Plasticizers are low molecular weight non volatile substance.
When these are mixed in polymer , improve flexibility and utility
but reduce Tg due to reduction in cohesive forces of attraction
between polymer chain.
 Importance of glass transition temperature -
 It is used to know whether a polymer molecule is flexible or
rigid or brittle.
 Tg informed about right processing temperature.
 Tg is used to measure the type of response of the polymer
whether it exhibits mechanical stress.
 Glass transition temperature gives an idea about polymeric
material.
 Tg along with Tm value provide an indication of the
temperature region at which a polymer transform from
solid rigid state to soft viscous state.
 Various processing technique such as moulding calendaring
and extrusion can be used to convert polymeric material
into finished product by knowing their temperature
regions.
Contents –
1. Introduction
2. Determination of glass transition temperature
1) Dilatometry method
2) Thermo mechanical method
3) Calorimetric method
3. Factors effecting glass transition temperature
1) Molecular weight
2) Cross linking
3) Intermolecular hydrogen bonding
4) Plasticizers
5) Aromatic ring
6) Chemical structure
4. Importance of glass transition temperature