Dynamic mechanical properties of poly(n‐butyl methacrylate) near its glass transition temperature

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Abstract
The storage and loss shear compliances (J′, J″) of poly(n‐butyl methacrylate) (number‐average molecular weight 320,000) were measured at frequencies between 0.08 and 1.0 cycle/sec. in the temperature range of 18–33°C., encompassing the glass transition. Data were obtained both at voluminal equilibrium and as a function of time during the slow isothermal contraction which follows a quench to a temperature near the transition. The latter data were supplemented by dilatometric measurements on similar samples to determine the magnitude of the volume contraction. Correlation of the dependences of J′ and J″ on temperature and on elapsed time (at constant frequency) indicated that the relaxation mechanisms are controlled primarily by free volume. The method of reduced variables was successfully applied to the dependence of J′ on temperature and elapsed time using shift factors aT,t calculated from the modified Doolittle equation and the magnitudes of volume contraction measured dilatometrically. The dependence of J″ on both temperature and elapsed time was more complicated, indicating a change in the shape of the retardation spectrum with free volume. The behavior is qualitatively very similar to that of poly(vinyl acetate), previously studied, except that the magnitudes of J′ are considerably larger and the thermal expansion coefficient of the free volume is smaller.

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