A molecular based model for polymer viscoelasticity: Intra- and inter-molecular variability

Abstract

We develop dynamic equations for rubber viscoelasticity based on a stick-slip continuum molecular-based model. The model developed is a continuum tube reptation model in which a chemically cross-linked (CC) system of molecules act as constraint box per unit volume for a physically constrained (PC) system of molecules. The CC-system carries along the PC-system during instantaneous step deformations. The subsequent relaxation of the PC-system is determined by the configuration of the CC-system, its own configuration and confirmation, and external force fields. Conversely, the deformation of the PC-system acts as an internal variable affecting the deformations of the constraining CC-system. We model the relationship between these processes to derive a model of viscoelasticity in rubber deformation. In developing a relaxation process for the PC-system, we start from the fact that the PC-system is composed of long molecular chains. The dynamics of these molecular chains are developed by modelling them as chains of beads connected by springs, which represent inter-molecular potentials. Various segments of the molecular chains relax at different rates. In addition, variability in relaxation times across molecular chains is permitted.