Sub-sub T g structural relaxation in glassy polymers

Abstract

Structural relaxation in a temperature range from 32 to 62° K glass transition has been investigated, for the first time, for a nearly monodisperse polystyrene using a differential scanning calorimeter and a thermal mechanical analyzer. Low temperature anneals in the vicinity of 320 K stabilize the glassy structure and lead to volume contraction. Upon heating, the annealed samples show an excess endothermic peak and exhibit a gradual expansion associated with structural recovery above the annealing temperature. Significantly, the samples recover the initial heat content and volume without reheating through the glass transition temperature. This sub‐T_g structural relaxation behavior is in many respects distinct from that commonly observed near the glass transition. Kinetics of relaxation processes are also discussed.