Enthalpy relaxation of polymers: comparing the predictive power of two configurational entropy models extending the AGV approach

The Tool-Narayanaswamy-Moynihan (TNM) phenomenological model is widely accepted in order to describe the structural relaxation of glasses. However several quantitative discrepancies can be found in the literature that cannot be entirely ascribed to the experimental errors. In this work we compare the predictive power of two recently proposed configurational entropy approaches extending the TNM formalism. Both of them change the treatment of non linearity by adding a free parameter. We use Differential Scanning Calorimetry (DSC) experiments in order to test the models in two different polymers. One of them is a commercial PMMA sample, the other is a side chain liquid crystal azo-benzene polymer properly synthesized for optical nanorecording purposes. Different results were found for the two systems. In the PMMA sample only one of the new models was able to improve the agreement between DSC experiments and theory with respect to the TNM model, whereas in the second polymer both the approaches were able to describe the experiments better than TNM model.