Glass Transition

(T
Temperature
g)
 Conte
nts
• Brief Information About Crystallinity
• Glass Transition Temperature (Tg)
• Free Volume Theory For Tg
• Factors Influencing Glass Transition
Temperature (Tg)
• Sources

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 Crystalli
nity
• One of the significant characteristics of polymers is crystallinity, or the
degree of structural order in a polymer.
• When the macromolecular chains of a polymer sample are
arranged in an orderly fashion, it is known as a crystalline
polymer.
• When the chains are not arranged in ordered crystals and are
disordered, even though they are in solid state, the polymer is
identified as amorphous.
• In most cases, there are no fully crystalline polymers; therefore, we
have semi-crystalline polymers, which are composed of both
amorphous and crystalline regions. This is why the same sample of a
polymer can have both a glass transition temperature and a melting
temperature.

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 Crystalli
• Crystalline nity
• Ordered

• Amorphous
• Random

• Semi-crystalline
• Consists of both

Amorphous
Crystalline
Region
Region
3
 Glass Transition Temperature
• Glass transition temperature is a temperature at which the polymer
experiences the transition from the glassy state to the rubbery state.
• Glassy state is hard & brittle state of material which is consist of short-
range vibrational & rotational motion of atoms in polymer chain, while
Rubbery state is soft & flexible state of material which is a long-range
rotational motion of polymer chain segments.

Glassy State Rubbery State

Hard & Brittle Soft & Flexible
Tg

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• Some polymers are used above their glass transition
temperature, and some are used below.
• Hard plastics like polystyrene and poly methyl methacrylate
are used below their glass transition temperature; that is in
their glassy state. Their Tg’s are well above room
temperature.
• Elastomers like polyisoprene and polyisobutylene are used
above their Tg’s, that is in the rubbery state, where they are
soft & flexible.

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 Heating Through Tg Leads
To Following
• Break down of Van Der Waals Forces.
• Onset of large scale molecular motion.
• Polymer goes from glassy/rigid to rubbery behaviour.
• Upper service temperature in amorphous polymers.

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 Free Volume Theory
• One of the most useful approaches to analysing the glass transition
temperature of polymer is to use the concept of Free Volume.
• The free volume is the space in a solid or liquid sample that is not
occupied by molecules, that is the ‘empty space’ between molecules.
• Free volume is high in liquid state than solid, so molecular motion is able
to take place relatively easy because the unoccupied volume allows the
molecules to move.
• The theory was originally developed for amorphous polymers and the
glass-transition in those polymers.

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8
• But semi-crystalline polymers also consist of
amorphous regions, so this theory can
also be applied to semi-crystalline polymers.
• An amorphous polymer can be considered to be made up
of occupied volume and free volume. As the temperature is
changed, the free volume and the occupied volume both
will change.
• As the temperature of the melt is lowered, the free volume
will be reduced until eventually there will not be enough free
volume to allow molecular motion or transition to take place.

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 Greater local Free
motion volume

Restricted
local motion
V

Tg
T

Brittle and glassy Soft and Flexible

10
Schematic illustration of the total, free,
and occupied volume

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• The total sample volume V therefore consists of volume occupied by
molecules V0 and free volume Vf such that
V= Vf +Vo
• At any given temperature, the fraction of the free volume is
Where, the
approximation is based on
Vf << V0.
• Around Tg and above Tg, the fraction of free volume can be expressed as,

• Where fg is the fraction of free volume at Tg and αf is an expansion coefficient for

the fraction free volume. αf is approximately αm – αg, or the difference between the
thermal expansion coefficients of the polymer above and below Tg.
• αm stands for melt
• αg stands for glass
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 Factors Influencing Glass
Transition Temperature
• From the previous discussion we know that at the glass
transition temperature there is a large scale cooperative
movement of chain segments. Therefore it is expected that
any structural features or externally imposed conditions that
influence chain mobility will also affect the value of Tg.

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• Some of these factors are shown below.

1. Chain Flexibility & Rigidity

2. Steric Effects

3. Effect of Intermolecular Forces

4. Copolymerization

5. Cross linking & Crystallinity

6. Plasticizer
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 1. Chain Flexibility & Rigidity
• As Tg depends on the ability of a chain to undergo internal rotations, we expect
chain flexibility to be associated with low glass transitions.
• For Example, Poly(dimethyl siloxane) is an extremely flexible polymer due to the
large separation between the methyl substituted silicon atoms. As compared to
other polymeric materials, poly(dimethyl siloxane) has the lowest glass transition
temperature (Tg = -123.15°C)

-93.15°C
-67.15°C

89.85°C

79.85°C
n

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• As shown in previous slide, polymers that contain
−CH2−CH2− sequences and ether linkages in the main-
chain have relatively easy internal rotations and therefore
low Tg values.
• While substitution of ethylene groups with p-phenylene units
leads to increased chain rigidity and high glass transition
temperature.

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 2. Steric Effects
• The presence of bulky side groups hinders rotation of the backbone
atoms due to steric hindrance, and therefore results in an increase in
Tg. The magnitude of this effect depends on the size of the side
groups.
• This is illustrated in the following Table for vinyl polymers
having the general structure,
—[CH2 — CHX ]—
-93.15°C

-20.15°C

99.85°C

134.85°C 17
 3. Effect of
Intermolecular Forces
• The presence of polar side groups leads to strong intermolecular
attractive interactions between chains which hinders molecular motion
thus causing an increase in Glass transition temperature.
• This effect is illustrated in the following table for the polymers of type −
[CH2−CHX ]−

-20.15°C

80.85°C

84.85°C

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 4. Copolymerization
• It is possible to alter the glass transition of a homo polymer by copolymerisation
with a second monomer. If the two homo polymers prepared from the
monomers have different Tgs, then it is reasonable to expect that their random
copolymer should have a glass transition which is intermediate between the Tgs
of the homo polymers. This is observed experimentally.
• The glass transition of a random copolymer is related to the Tgs of the homo
polymers, Tg1 and Tg2, as follows

1/Tg = w1/Tg1 + w2/Tg2*

• Where w1 is the weight fraction of homo polymer 1 and w2 is the weight

fraction of homo polymer 2.

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 5. Cross-linking &
Crystallinity
• Both cross-linking and crystallinity cause an increase of the glass
transition temperature.
• It is very easy to explain why cross-linking increases Tg since the
presence of covalent bonding between chains reduces molecular
freedom and thus the free volume.
• Similarly, the presence of crystalline regions in an semi-
crystalline material restricts the mobility of the disordered
amorphous regions; thus the glass transition temperature
increases which is totally depends on the percentage of
crystallinity.

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 6. Plasticizer
• Sometimes, a polymer has a high Tg than our requirement. To tackle
this proble we just mix something in it called a plasticizer.
• Plasticizers are small molecules which will get in between the
polymer chains, and space them out from each other. Thus
the free volume will increase. When this happens they can slide past
each other more easily. When they slide past each other
more easily, they can move around at lower temperatures than they
would without the plasticizer.
• By this way, the Tg of a polymer can be lowered, to make a
polymer more applicable, and easier to work with.

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 Sour
ces
• Practical Polymer Analysis By T.R. Crompton (595-629)
• Polymer Chemistry - The Basic Concepts By Paul C.
Hiemenz (199)
• Polymer Physics By ULF W. Gedde (77-95)
• Text Book Of Polymer Science By Fred W. Billmeyer (320)
• Polymer Science By V.R. Gowariker (113-130)

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