Thermal history and temperature dependence of viscoelastic properties of polymer glasses: Relation to free volume quantities

The dependence of physical properties on temperature and thermal history of glassy polycarbonate is examined. The average stress relaxation time increases during isothermal aging and with decreasing cooling rate. The temperature dependence of the stress relaxation time was compared with a free volume function calculated from specific volume data reported by Zoller by means of the Simha‐Somcynsky theory and with a fractional free volume measured by ortho‐positronium annihilation. We report in addition comparisons between free volume fractions extracted from volume data, and creep measurements for polystyrene, and stress relaxation data for poly(vinyl acetate) given by Kovacs et al., Schwarzl and Zahradnik, and Meyer et al. These investigations suggest that in the glassy state the Doolittle equation is valid only in isothermal aging experiments. It follows that in expressing the polymer mobility not only a temperature‐dependent free volume but additional temperature‐dependent processes need to be considered.