The Coupling Model: A Fundamental Mechanism Governing Time Dependent Properties of Relaxations, Structural Recovery and Nonlinear Viscoelasticity

Abstract

AbstractThe recent renewal of interest in the time dependent response of complex material systems stems both from their increasing importance and from recent advances in theoretical tools and concepts. This paper describes one of these advances, the coupling model of relaxation. The coupling model proposes a view of how relaxation proceeds in time in which a primitive relaxation mode is coupled to its complex surroundings. Examples of the coupling model predictions for terminal relaxations, primary-segmental relaxations including physical aging, and secondary relaxations in polymers are described. It is able to confront and quantitatively explain several long-standing problems and anomalies for which traditional approaches, in their present form, such as distributions of relaxation times, free volume, configuration entropy and reptation are not successful. The coupling model response function is also appropriate for structural nonequilibrium and its predictions for volume recovery are described. The same coupling model response function is used as a timedependent kernal in a constitutive equation to discuss nonlinear viscoelasticity. The model incorporates the strain history dependence and allows for the evolution of material structure. Using information from strain-tickle experiments on polycarbonate and polyetherimide, we show that the coupling model reproduces the essential features observed experimentally for a variety of strain histories.