Unifying Physical Framework for Stretched-Exponential, Compressed-Exponential, and Logarithmic Relaxation Phenomena in Glassy Polymers

Abstract

We develop a simple yet comprehensive nonlinear model to describe relaxation phenomena in amorphous glass-formers near the glass transition temperature. The model is based on the two-state, two-(time)scale (TS2) framework and describes the isothermal relaxation of specific volume, enthalpy, or shear stress via a simple first-order nonlinear differential equation (the Trachenko-Zaccone [TZ] equation) for local cooperative events. These nonlinear dynamics of cooperatively rearranging regions naturally arise from the TS2 framework. We demonstrate that the solutions of the TZ equation comprehensively encompass the Debye exponential relaxation, the Kohlrausch–Williams–Watts stretched and compressed relaxations, and the Guiu–Pratt logarithmic relaxation. Furthermore, for the case of stress relaxation modeling, our model recovers, as one of its limits, the Eyring law for plastic flow, where the Eyring activation volume is related to thermodynamic parameters of the material. Using the example of polystyrene, we demonstrate how our model successfully describes the Kovacs’ “asymmetry of approach” specific volume and enthalpy experiments, as well as the stress relaxation. Other potential applications of the model, including the dielectric relaxation, are also discussed. The presented approach disentangles the physical origins of different relaxation laws within a single general framework based on the underlying physics.