Thermal Transitions in Polymers

Lecture 2/3
What does Tg stand for?
• This temperature (measured in °C or °F) depends on the chemical structure
of the polymer and can therefore be used to identify polymers.

• Amorphous polymers only exhibit a Tg.

• Crystalline polymers exhibit a Tm (melt temperature) and typically a Tg
since there is usually an amorphous portion as well (“semi”-crystalline).

The value of Tg depends on the mobility of the polymer chain, and for most
synthetic polymers lies between 170 K to 500 K.
The transition from the glass to the rubber-like state is an important feature
of polymer behavior, marking a region of dramatic changes in the physical
properties, such as hardness and elasticity.
What does Tg stand for?
• At Tg, changes in hardness, volume, percent elongation to break and Young’s
modulus of solids are mainly seen.
Some polymers are used below their Tg (in glassy state) like
polystyrene, poly(methyl methacrylate) etc., which are hard and brittle. Their Tgs
are higher than room temperature.
Some polymers are used above their Tg (in rubbery state), for example, rubber
elastomers like polyisoprene, polyisobutylene. They are soft and flexible in
nature; their Tgs are less than room temperature.
Applications include:
Identifying the Tg of polymers is often used for quality control and research and
development. Also, it is an important tool used to modify physical properties of
polymer molecules.
Factors Affecting the Glass Transition
Temperature: Chain Flexibility
Long-chain aliphatic
groups — ether and
ester linkages —
enhance chain flexibility,
while rigid groups like
cyclic structures stiffen
the backbone.
Factors Affecting the Glass Transition
Temperature: Chain Flexibility
Enhancement of Tg by Steric
Hindrance
Bulky side groups that are stiff
and close to the backbone
cause steric hindrance,
decrease chain mobility, and
hence raise Tg
Factors Affecting the Glass Transition
Temperature: Chain Flexibility
Decrease of Tg with Increasing
Flexibility of Side Chains for
Polymethacrylate Series
The influence of the side group in enhancing
chain stiffness depends on the flexibility of the
group and not its size. In fact, side groups that
are fairly flexible have little effect within each
series; instead polymer chains are forced further
apart. This increases the free volume, and
consequently Tg drops.
Factors Affecting the Glass Transition
Temperature: Geometric Factors
Effect of Symmetry on Tg
• Polymers that have symmetrical structure
have lower Tg than those with asymmetric
structures.
• The additional groups can only be
accommodated in a conformation with a
“loose” structure. The increased free volume
results in a lower Tg.
Factors Affecting the Glass Transition
Temperature: Geometric Factors
Relative Effects of Cis-Trans
Configuration on Tg
• Another geometric factor affecting Tg is cis–
trans configuration.
• Double bonds in the cis form reduce the
energy barrier for rotation of adjacent bonds,
“soften” the chain, and hence reduce Tg.
Factors Affecting the Glass Transition
Temperature: Interchain Attractive Forces
Effects of Polarity on Tg
• The presence of strong intermolecular bonds
in a polymer chain, i.e., a high value of
cohesive energy density, will significantly
increase Tg
• The steric effects of the pendant groups in
series (CH3 , –Cl, and –CN) are similar, but the
polarity increases. Consequently, Tg is
increased in the order shown in the table.
Factors Affecting the Glass Transition
Temperature: Interchain Attractive Forces
Effects of Polarity on Tg on Some
Acrylic Polymers
• The same effect of increased Tg with
increasing CED (cohesive energy density) can
be observed when one considers going from
the intermolecular forces in poly(methyl
acrylate), an ester, through the strong
hydrogen bonds in poly(acrylic acid) to
primary ionic bonds in poly(zinc acrylate)
Cross-linking
Cross-linking reduces chain mobility,
so Tg will be increased.

It also affects the macroscopic viscosity of the polymer,

since if there are cross-links between the chains, then
they are fixed relative to each other, so will not be
able to slide past each other.
Tg depends on ----

• Each chain end has some free volume associated with

it.
• A polymer with shorter chains will have more chain
ends per unit volume, so there will be more free
volume.

• Hence Tg' for shorter chains will be lower than Tg for

long chains

The solid state properties of Polymers 12

13
Factors Affecting the Glass Transition
Temperature: Copolymers
• Isomorphous Systems (Homogeneous
Copolymers or Compatible Polyblends)
• For this system, if the glass transitions (Tg1
and Tg2) of the individual homopolymers (1
and 2) are known, it is possible to estimate
the Tg of the copolymer (or polyblend) using
the relation

• where V1 and V2 are the volume fractions of

components 1 and 2, respectively. This is
shown schematically in Fig.
Factors Affecting the Glass Transition
Temperature: Copolymers
• What is the Tg of butadiene–styrene
copolymer containing 10 vol%
styrene?
• Continued to next slide