Structural relaxation in poly(vinyl acetate)

Abstract

Abstract Structural relaxation in poly(vinyl acetate) (PVAc) in and slightly above the glass‐transition region has been studied by monitoring the time dependence of enthalpy using differential scanning calorimetry and the frequency dependence of electric polarization by dielectric loss measurements. The results have been analyzed to yield the kinetic parameters characterizing the structural relaxation and are compared with similar analyses of previously published shear compliance and volume relaxation experiments. Relaxation of enthalpy, electric polarization, volume, and shear stress in PVAc all appear to be characterized by somewhat different relaxation times. The difference between the volume and enthalpy relaxation times, coupled with the fact that PVAc exhibits a Prigogine–Defay ratio greater than unity, is evidence for a previously proposed connection between the thermodynamics and kinetics of structural relaxation in terms of an order parameter model.