An approach to thermodynamics of polymer flow based on internal state variables

Abstract

Abstract Two kinds of thermodynamic theories, which seem to be applicable to polymer deformation and flow, have been developed in the recent literature. One of these approaches utilizes entropy far from equilibrium as a primitive undefined concept. The alternate kind of theory involves the idea of a quasi‐static process as a primitive concept. In this work, an approach based on internal state variables (specifically, the micro structure of the polymeric material) is used to argue that both primitive concepts are in some sense legitimate on physical grounds. In particular, the legitimacy of the quasi‐static process concept is related to the smoothness of the function delivering the rate of change of the microstructure.