ch 1 notes (3)

Thermal transitions
• Polymeric materials are characterized by two major types of transition

temperatures—the crystalline melting temperature Tm and the glass transition
temperature Tg.
• The crystalline melting temperature is the melting temperature of the crystalline

domains of a polymer sample. The glass transition temperature is the
temperature at which the amorphous domains of a polymer take on the
characteristic properties of the glassy state—brittleness, stiffness, and rigidity.
Glass Transition Temperature (Tg)
The temperature below, which a polymer is hard and above
which it is soft, is called the glass transition temperature (Tg).
Or
The molecular mobility is just starts above that temperature
or below which mobility arrested called Tg
Tg is unique to amorphous thermoplastics. It occurs at a
specific temperature that depends on pressure and specific
volume and is lower than melting point.
Tg
• The glass transition temperature is a measure of evaluating
the flexibility of polymer molecules and the type of response
the polymeric material would exhibit to mechanical stress.
•The Tg value along with Tm helps in choosing the right

processing temperature, the temperature region the material
can be converted into finished product through different
processing techniques.
• The glass transition temperature depends on the structure

and polarity of a polymer, which affects both chain flexibility
and intermolecular interaction.
• Since non-polar polymers have lower potential energy
barrier for rotation, their chain remains flexible and they have
low Tg. On the other hand, introduction of ring structure into
main chain has a marked stiffening effect which results in
higher Tg of such polymer.
• The presence of polar groups or atoms will result in high

glass transition temperature. Hydrogen bonding has a similar
effect to that of a polar group.
Glass Transition Temperature and Molecular Weight
 K
Tg  Tg 
Mn
Where, Tg is the glass transition temperature at
infinite molecular weight and K and A are arbitrary constants.
1 1 A
 
Tg Tg Mn
For a given weight of the polymer, a low molecular weight

sample will have more chain end segments than a high
molecular weight sample.
The chains are less restricted. This gives greater mobility
and require low thermal energy for segmental motion (tow
Tg)
Glass Transition Temperature and Plasticizer
1. The plasticizer substantially reduces the brittleness of

many amorphous polymers because its addition even in
small quantities markedly reduces the Tg of the polymer.
2. The effectiveness of plasticizer in lowering the Tg of a
polymeric composition is directly proportional to its Tg
(Tg1 and Tg2) and volume fractions (V1 and V2) of
plasticizer
Tg  V1Tg1  V2Tg 2
1 w w
 1  2
Tg Tg1 Tg 2
The extent of reduction in the glass transition values is

called as’plasticizer efficiency'. The extent of reduction is
depends on factors such as solubility parameter, polarity
and density
Effect of Co-polymerization on Glass Transition Temperature
1 wA wB
 
Tg( AB ) Tg( A) Tg( B )
Where Tg(A), Tg(B) and Tg(AB) are the glass transition

temperature of homo polymers A and B and the copolymer
AB respectively. Wa and Wb are the weight fractions of the
homopolymers. that the glass transition temperature of a
copolymer will be in between those· of the. respective homo
polymers
Glass Transition Temperature and Melting Point
1
Tg  Tm For symmetrical polymers
2
2
Tg  Tm For unsymmetrical polymers
3
A combined version of these two equations, in which the

effect of molecular symmetry is not taken into account, is
also in vogue, as now shown:
1 Tg 2
 
2 Tm 3
Since this relation gives a range for Tg/Tm (rather than a
sharp value), it may more realistically reflect the thermal
behavior of polymers.
Glass Transition Temperature and Processability
• Below Tg, polymer may be cut, machined or hardened by

adhesives, but changing their shape by actual flow is
difficult.
• Stretching is usually carried out above Tg where reasonably
large segments of polymer have enough freedom to slip
past each other under mechanical stress.
Plastic identification code
It is a set of symbols appearing on plastic products that identify
the polymer out of which the product is made. It also gives
information about whether the plastic material can be recycled.
Number 1, 2, and 3 are picked up through most recycling
programs.
Number 7 plastics are generally not recycled.
Viscosity of polymer
• High molecular weight polymers greatly increase the viscosity of liquids in which they are dissolved.
• Viscosity of a polymer solution depends on concentration and size (i.e., molecular weight) of the dissolved
polymer. The extended contact between their long molecular chains leads to enhanced intermolecular
attractions that contribute to a resistance to flow.
• Viscosity is related to molecular weight via Mark-Houwink equation: here ‘ita’ is intrinsic viscosity.
• Intrinsic viscosity can be calculated from Huggins and kraemers equation.
What is copolymerization? Explain the types of copolymerization. Also,
explain copolymer composition.
• The term ‘copolymerization’ includes the simultaneous polymerization of

two or more types of monomer. Copolymers may be synthesized by chain
growth and step growth condensation polymerization processes.
• Chain growth copolymerizations may be done using various active centers,
including free radical, ionic and Ziegler–Natta processes.
• Step growth copolymerization can be done using ring opening, poly
condensation.
• Copolymerizations may be performed using heterogeneous as well as
homogeneous processes (such as solution, bulk, suspension, emulsion,
slurry and gas phase processes)
• There are four basic copolymer structures: random, alternating, block and
graft.
Block copolymerization
• Ring opening copolymerization
Glycidyl phenyl ether (GPE) Poly-lactone (PL)

Alternating copolymer
Chain growth copolymerization: free radical copolymerization
Random copolymer
Chain growth copolymerization: free radical copolymerization
Graft copolymer
Coplymerization via click chemistry

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Thermal transitions

• Polymeric materials are characterized by two major types of transition

• The crystalline melting temperature is the melting temperature of the crystalline

•The Tg value along with Tm helps in choosing the right

• The glass transition temperature depends on the structure

• The presence of polar groups or atoms will result in high

For a given weight of the polymer, a low molecular weight

1. The plasticizer substantially reduces the brittleness of

The extent of reduction in the glass transition values is

Where Tg(A), Tg(B) and Tg(AB) are the glass transition

A combined version of these two equations, in which the

• Below Tg, polymer may be cut, machined or hardened by

• The term ‘copolymerization’ includes the simultaneous polymerization of

Glycidyl phenyl ether (GPE) Poly-lactone (PL)

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