A mathematical model for the total heat flow obtained in differential scanning calorimetry (DSC) experiments from polymers with enthalpic relaxation is proposed. It is limited to the glass transition and enthalpic relaxation range of temperature and to the cases where the enthalpic relaxation is the only non-reversing process taking place. The model consists of a mixture of functions representing the heat capacity heat flow of the glassy and non-glassy fractions, the glass transition progress and the enthalpic relaxation heat flow.
Optimal fittings of the model were performed on the experimental total heat flow data, obtained from two thermoplastics with different aging times. Considering which functions of the mixture represent reversing and non-reversing processes, the reversing and non-reversing heat flows were also estimated. The estimated reversing and non-reversing signals were compared with the ones obtained by modulation. On the whole a good match was found, which was even better considering that the estimates are not affected by the frequency effect of the modulated temperature DSC (MTDSC) measurements. The model assumes linear trends for the heat capacity heat flow of the glassy and non-glassy structures. The glass transition progress is represented by a generalized logistic function and the enthalpic relaxation heat flow by the first derivative of another generalized logistic. It brings about a new approach to these phenomena, where the parameters of these functions represent the temperature at which each event is centered, the change of heat capacity (Cp) at the glass transition and the energy involved in the enthalpic recovery. Copyright © 2011 John Wiley & Sons, Ltd.