Free Volume and Finite-Size Effects in a Polymer Glass under Stress

Molecular dynamics simulations of the nonlinear creep response of a polymer glass under tension and compression have been performed at the glass transition temperature. The dynamics were measured as the deformation proceeds using the bond autocorrelation function, and the relaxation times measured as the system is compressed or elongated exhibit a universal response. In tension, the volume increases with strain rate and the relaxation times decrease. In compression, however, the volume decreases by approximately the same amount for all of the applied stresses. Thus, decreases in free volume take place alongside a decrease of the relaxation times by over a factor of 100. We find direct evidence that a characteristic length scale exists below which the deformation of the system exhibits distinct anomalies.