Stochastic theory for the glassy state. 1. Influence of formation history on the glass transition temperature and equation of state

S.M. Vleeshouwers, E. Nies

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    Abstract

    A stochastic theory is developed to describe the influence of glass formation history on the equation of state of polymer glasses and on the glass transition temp. The theory is based on the assumption of a spatial distribution of free vol. and hence mobility in the polymer system. The free vol. is identified with the order parameter h in the Holey-Huggins theory. The response of the system to a change in pressure and/or temp. is formed by a change of the actual free vol. distribution to the new equil. All requisite parameters but 1 can be obtained from independent expts. on the equil. polymer melt. The remaining parameter is presently detd. from a nonequil. relaxation expt. For poly(vinyl acetate), the calcd. cooling rate and pressure dependence of the glass transition temp. and the calcd. dependence of the equation of state of the polymer glass on formation pressure are compared to exptl. data. In general, good agreement is obtained. [on SciFinder (R)]
    Original languageEnglish
    Pages (from-to)6921-6928
    JournalMacromolecules
    Volume25
    Issue number25
    DOIs
    Publication statusPublished - 1992

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