Dynamics of structural recovery and mechanical response of polymeric liquids near to the glass transition

Results from the NIST torsional dilatometer have indicated that after a temperature step from equilibrium, the volume (structure) and mechanical response (physical aging) can evolve at different rates, depending on the temperature history. The torsional dilatometer results have been modeled in two ways. First, it was assumed that the volume and mechanical response are governed by different clocks, with the principle of time-aging time superposition employed to evaluate an aging time shift factor a_te from the torsional response, which was then compared to a structural shift factor a_δ calculated from the evolution of the volume. These results were also investigated using a thermoviscoelastic model based on rational thermodynamics and configurational entropy; this model does not include an explicit assumption of separate time scales, but different time scales for the structure and mechanical properties appear to arise naturally from the formulation. The results from the thermoviscoelastic model show good qualitative agreement with the torsional dilatometer results, although more material data is needed to make an exact comparison.