Glass
transition temperature:
the glass transition temperature is the temperature
at which an amorphous solid becomes soft upon heating or brittle upon cooling.
The glass transition temperature is lower than the melting point of its
crystalline form, if it has one.
Melting
temperature:
The temperature response of
linear polymers may be viewed as divided into three distinctly separate
segments:
1. Above Tm :
In this segment, the polymer
remains as a melt or liquid whose viscosity would depend on molecular weight
and on the temperature of observation.
2. Between Tm and Tg :
This domain may range between
near 100% crystalline and near 100% amorphous chain molecular clusters
depending on the polymer structural regularity and on experimental
conditions. The amorphous part behaves
much like super cooled liquid in this segment.
The overall physical behaviour of the polymer in this intermediate
segment is much like a rubber.
3. Below Tg :
The polymer material viewed as
a glass is hard and rigid, showing a specified coefficient of thermal
expansion. The glass is closer to a
crystalline solid than to a liquid in behavioural pattern in terms of
mechanical property parameters. In
respect of molecular order, however, the glass more closely resembles the
liquid. There is little difference
between linear and cross linked polymer below Tg.
Tm and Tg
Values of Several Polymers:
Polymer
|
Repeat Unit
|
Tm, 0C
|
Tg, 0C
|
Polyethylene
|
– CH2 – CH2
–
|
137
|
-115,-60
|
Polyoxymethylene
|
– CH2 – O –
|
181
|
-85,-50
|
Polypropylene
(isotactic)
|
– CH2 – CH (CH3)
–
|
176
|
- 20
|
Polyisobutylene
|
– CH2 – C (CH3)2
–
|
44
|
- 73
|
Polybutadine (1, 4
cis)
|
– CH2 – CH = CH –
CH2 –
|
2
|
- 108
|
Polyisoprene (1, 4
cis), (NR)
|
– CH2 – C(CH3)
= CH – CH2 –
|
14
|
- 73
|
Poly (dimethyl
siloxane)
|
– OSi (CH3)2
–
|
- 85
|
- 123
|
Poly (vinyl acetate)
|
– CH2 – CH (OCOCH3)
–
|
---
|
28
|
Poly (vinyl chloride)
|
– CH2 – CH Cl –
|
212
|
81
|
Polystyrene
|
– CH2 – CH (C6H5)
–
|
240
|
95
|
Poly (methyl
methacrylate)
|
– CH2 – C(CH3)(
COOCH3) –
|
200
|
105
|
Poly
tetrafluoroethylene
|
– CF2 – CF2
–
|
327
|
126
|
Poly caprolactam
(Nylon 6)
|
– (CH2)5
CONH –
|
215
|
50
|
Poly(hexamethylene
adipamide)
(Nylon 66)
|
–HN(CH2)6-NHCO–(CH2)4CO
–
|
264
|
53
|
Poly (ethylene
terephthalate)
|
– O(CH2)2 –
OCO – (C6H4) CO –
|
254
|
69
|
Poly (ethylene
adipate)
|
– O(CH2)2 –
OCO – (CH2)4 CO –
|
50
|
-70
|
Cellulose triacetate
|
306
|
49-478
|
|
Cellulose trinitrate
|
700
|
53
|
|
Ethyl cellulose
|
43
|
||
Natural rubber
|
36
|
-73
|
|
Polybutyl acrylate
|
47
|
-54
|
|
Polyvinyl carbazole
|
>320
|
150
|
|
Polyvinylidene
chloride
|
190
|
-18
|
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