THERMAL APPLICATIONS NOTE

Polymer Heats of Fusion

Roger L. Blaine
TA Instruments,109 Lukens Drive, New Castle DE 19720, USA

The heat of fusion of 100 % crystalline polymer is required to obtain percent

crystallinity by differential scanning calorimetry (1). Polymer reference materials with
100 % crystallinity are rarely available for comparison purposes. Fortunately, the heats
of fusion values for 100 % crystalline polymers may be determined by indirect methods
such as extrapolation using the Flory equation (2). Wunderlich and co-workers (3) have
created tables of best estimate values for the heats of fusion for a wide variety of linear
polymers with values reported in joules per mole of repeat unit. To be useful for thermal
analysis purposes, these enthalpy values need to be normalized to mass. Table 1 includes
the mass normalized enthalpy of fusion values commonly used in DSC determinations.
REFERENCES
1.
2.
3.
4.

TA123, Determination of Polymer Crystallinity by DSC, TA Instruments, New

Castle, DE.
TA276, Determination of Polymer Crystal Molecular Weight Distribution by
DSC, TA Instruments, New Castle, DE.
B. Wunderlich, Thermal Analysis, Academic Press, 1990, pp. 417-431.
D1600, Abbreviated Terms Relating to Plastics, American Society for Testing
and Materials, West Conshohocken, PA.

KEYWORDS
differential scanning calorimetry, melting, thermoplastic polymers

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Table 1 Polymer Heats of Fusion

Acronym Name
(4)
PE
PP
PB
POM
PEOX
PA6
PA11
PA12
PA66
PA69
PA610
PA612
PVOH
PET
PBT
PVF
PVDF
PTFE
PVC
PCTFE
PEEK

Polyethylene
Polypropylene
Polybutene-1
Polymethylenoxide
Polyethyleneoxide
Polycaprolactam
Polyundecanolactam
Polylauryllactam
Poly(hexamethylene adipamide)
Poly(hexamethylene nonanediamide)
Poly(hexamethylene sebacamide)
Poly(hexamethylene dodecanediamide)
Polyvinyl alcohol
Polyethylene terephathalate
Polybutylene terephathalate
Polyvinyl fluoride
Polyvinylidene fluoride
Polytrifluoroethylene
Polytetrafluoroethylene
Polyvinyl chloride
Polychlorotrifluoroethylene
Polyetheretherketone

Enthalpy
(kJ/mol)
(3)
4.11
8.70
7.00
9.79
8.66
26.0
44.7
48.4
57.8
69
71.7
80.1
7.11
26.9
32.0
7.54
6.70
5.44
4.10
11.0
5.02
37.4

Repeat Unit
-CH2-CH2CH(CH3)-CH2CH(C2H5)
-CH2O-CH2CH2O-NH(CH2)5CO-NH(CH2)10CO-NH(CH2)11CO-NH(CH2)6NHCO(CH2)4CO-NH(CH2)6NHCO(CH2)7CO-NH(CH2)6NHCO(CH2)8CO-NH(CH2)6NHCO(CH2)10CO-CH2CH(OH)-O(CH2)2O2CC6H4CO-O(CH2)4O2CC6H4CO-CH2CH(F)-CH2CF2-CH(F)CF2-CF2-CH2CH(Cl)-CF2CF(Cl)-C6H4COC6H4OC6H4O-

TN048

Molecular
Weight
(g/mol)
14.03
42.08
56.1
30.03
44.05
113.2
183.3
197.3
256.3
268.4
282.4
310.5
44.05
192.2
220.2
46.04
64.03
82.0
50.0
62.50
116.5
288.3

Enthalpy
(J/g)
293
207
125
326
197
230
244
245
226
257
254
258
161
140
145
164
105
66.3
82.0
176
43.1
130