A Molecular Based Model for Polymer Viscoelasticity: Intra- and Inter-Molecular Variability

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 modeling them as chains of beads connected by springs, which represent intermolecular potentials. Various segments of the molecular chains relax at different rates. In addition, variability in relaxation times across molecular chains is permitted.