Abstract
In order to interpret the change in heat capacity ΔCP at glass transition temperature and the excess enthalpy He of polymer liquids and glasses relative to the crystals, a hole theory is presented in which both the hole fraction and the state of chain conformation are assumed to be frozen-in in the glassy state. In this treatment, ΔCP and He are both divided into two parts: one associated with intersegmental and the other with intrasegmental interactions. The relations TV(Δα)2/ΔCpinterΔβ=1 and TV(Δα)2/ΔCpΔβ≤1 are derived, where T is temperature, V is volume, Δα and Δβ are the differences in the thermal expansion coefficient and compressibility between the liquid and glassy states respectively, and ΔCpinter is the part of ΔCp attributable to intersegmental interactions. Using the results of this theory, the experimental observations for ΔCp and He are compared and analyzed, bringing in at times the principle of corresponding states.
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Nose, T. A Hole Theory of Polymer Liquids and Glasses. III. Glass Transition and Glassy State; Heat Capacity Change at Glass Transition Temperature and Excess Enthalpy. Polym J 2, 437–444 (1971). https://doi.org/10.1295/polymj.2.437
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DOI: https://doi.org/10.1295/polymj.2.437