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)-C6H4COC6H4OC6H4OMolecular 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

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