Structural relaxation of an unentangled polymer in terms of a simple phenomenological approach

The enthalpy relaxation mechanism of a low molecular weight synthesis of polymethylmethacrylate was investigated by means of calorimetric experiments. The data were analyzed in terms of a kinetic approach treating nonlinearity in a different manner with respect to the Tool-Narayanaswamy-Moynihan model. The relaxation isotherms recorded at four different temperatures were well reproduced by this approach that, however, failed in describing the relaxation asymmetry towards the equilibrium after opposite temperature jumps. A modification of the model was proposed with an additional free parameter accounting for the stretching of the relaxation function. In this way all the experimental data were reproduced fairly well.