COOPERATIVE FREE VOLUME RATE MODEL APPLIED TO THE PRESSURE-DEPENDENT SEGMENTAL DYNAMICS OF NATURAL RUBBER AND POLYUREA

Abstract

ABSTRACT We apply the cooperative free volume (CFV) rate model for pressure-dependent dynamics of glass-forming liquids and polymer melts, focusing on two new applications of the model, to natural rubber and to polyurea. In CFV, segmental relaxation times, τ, are analyzed as a function of temperature (T) and free volume (Vfree), where the latter provides an insightful route to expressing dynamics relative to using the system's overall total volume (V). Vfree is defined as the difference between the total volume and the volume at close packing and is predicted independently of the dynamics for any temperature and pressure using the locally correlated lattice equation-of-state analysis of characteristic thermodynamic data. The new results for natural rubber and polyurea are discussed in the context of results on a set of polymeric and small-molecule glass formers that had previously been modeled with CFV. We also discuss the results in the context of recent connections that we have made with the density-scaling approach.