Glass Transition

Temperature

Anu Muthukamatchi
Doctoral Research Fellow
Department of Chemistry

24 May 2022
What is glass transition temperature (T g)?
Let us consider the flexibility of a garden hose in midsummer. It is quite flexible. Now consider it on a cold winter day
at -4°F (-20°C). You could likely break it with your bare hands! In the former case, the hose is above its T g, while in the
latter, it is significantly below.

Flexible garden hose in midsummer. Flexible garden hose in cold winter at -4°F (-20°C).

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Factors affecting Tg
Chain flexibility (Aliphatic groups)

• Highly flexible backbone -

Polyethylene (PE) permits the polymers to bend
and twist to move around each
Glass transition temperature of -120 °C other more easily
• Absence of side groups

Polydimethylsiloxane (PDMS)

Glass transition temperature of -123 °C Flexible

groups

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Factors affecting Tg
Rigid groups (Aromatic, unsaturated, heterocyclic groups)

Polycarbonate (PC)

Glass transition temperature of 150 °C

Rigid groups

Poly(m-phenylene isophthalamide) (Nomex)

Glass transition temperature of 273 °C

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Factors affecting Tg
Effect of side groups

Larger side groups can hinder bond rotation more than smaller ones, and therefore cause an increase in T g.

Polyethylene (PE) Polypropylene (PP) Polystyrene (PS)

Glass transition temperature of -120 °C Glass transition temperature of -20 °C Glass transition temperature of 100 °C

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Factors affecting Tg
Effect of side groups

Flexible side groups (or branching ): increase interchain distance, have more chain ends, so more free volume,
which reduces Tg.

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Factors affecting Tg
Polarity of side groups

Polarity of the side groups can hinder bond rotation and therefore cause an increase in T g.

• Polar groups increase interaction between chains and Tg increases.

• - Cl, CN or OH have the strongest effect.

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Factors affecting Tg
Effect of chain interactions

Hydrogen bonding

Polyhexamethylenediamine (Nylon-66)

Glass transition temperature of 50 °C

Polycaprolactum (Nylon-6)

Glass transition temperature of 47 °C

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Factors affecting Tg

Cross-linking

• Cross-linking reduces chain mobility. Tg increases with increasing cross-linking when the cross-linking degree.

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Factors affecting Tg
Plasticizers

What are plasticizers?

External plasticizers: Plasticizers are low

molecular weight non-volatile substances,
which when added to a polymer, improve its
flexibilty.

Plasticizer molecules penetrate into the polymer

matrix and reduces the cohesive forces between
polymer chains and increases segmental
mobility, thereby reducing the Tg.

Internal plasticizers: These are actually a part of

the polymer molecule-e.g., a second monomer
is copolymerized into the polymer structure.

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Glass Transition Temperature of
copolymers
Fox equation
The tg of pure nylon-66 is 50 °C. Calculate the
• The Tg of random copolymers depends on the tg of the weight (%) for the plasticizer with tg of -80 °C
individual homopolymers and on the ratio of the two which needed to be added to a film of nylon-66.
monomeric components. The tg of the plasticized nylon-66 is 25 °C.

Hint: Convert °C to Kelvin when calculating.

Fox equation,

= +
Tg(A) - Glass transition temperature of homopolymer A
Tg(B) - Glass transition temperature of homopolymer B
Tg(AB) - Glass transition temperature of copolymer AB
WA, WB - Weight fraction of homopolymer A and B
respectively

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Relationship between Tg and Tm

On basic considerations, that factors affecting T g will also affect Tm

Tg and Tm are interconnected as,

(for symmetrical polymers)

(for unsymmetrical polymers)

Which techniques can be used to determine Tg?

• Differential Scanning Calorimetry (DSC)

• Dynamic Mechanical Analysis (DMA)
• Thermo Mechanical Analysis (TMA) like Dilatometry

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Differential Scanning Calorimetry

• 30 °C to -90 °C (first cooling cycle)

• -90 °C to 30 °C (first heating cycle)
• 30 °C to -90 °C (second cooling cycle)
• -90 °C to 30 °C (second heating cycle)

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Free Volume Theory

The free volume can be defined simply as the volume unoccupied by the macromolecules.

In the glassy state (T < Tg) the free volume fraction is virtually constant. However, above the glass transition
temperature the free volume increases linearly.

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Gas permeability

Constant volume and Variable Pressure (CV-VP)

D is determined from time lag, θ

The amount of penetrant (Qt) passing through the

P is determined from the slope after steady state membrane in the time t
C is the concentration on the feed side
P=D*S l is the thickness of the membrane

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anum@uio.no

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