Traversing with quantitative fidelity through the glass transition of amorphous polymers: Modeling the thermodynamic dilatational flow of polycarbonate

Abstract

We follow the assumption that the dilatational response of glassy polymers can be characterized by a back-stress type analog that includes a thermal expansion for each elastic component and with a viscosity that is dependent on the expansion of the elastic back-stress component. To this, we add the assumption of an unloaded equilibrium temperature that correlates to the past processing through the viscous flow. After setting this in a thermodynamically consistent structure, elastic, elastic back-stress, thermal expansion, back-stress thermal expansion, heat capacity, and viscous damping are evaluated using existing experiments for the response of polycarbonate over the glassy and rubbery ranges. For the demonstration, this is done entirely using a WLF shift factor that is augmented to include, in addition, back strain superposition. We then examine the resulting model under different thermal and mechanical loadings that have the material passing through the glass transition.