Abstract
The Narayanaswamy model for vitrification is modified to deliver local information about the underlying equilibrium trace of calorimetric response in an Arrhenius plot. The analysis of a simple differential scanning calorimetry (DSC) thermogram for polystyrene reproduces the calorimetric equilibrium trace from heat capacity spectroscopy with an accuracy of few tenths of a frequency decade. Further, contour maps for linear dielecric, heat capacity, and shear response in the crossover region of dynamic glass transition in poly( n-hexyl methacrylate) are presented. The calorimetric map has a saddle between the death of the high-temperature process ( a) and the onset of the low-temperature process ( α). The sigmoid bend in the equilibrium trace near this peculiarity can independently be confirmed by the modified Narayanaswamy model evaluation of a simple DSC thermogram. A speculative, free-volume physical picture of the crossover region is described.
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