Improved calorimetric procedure for monitoring the approach to thermodynamic equilibrium in glassy polymers

Techniques for measuring the enthalpy change during isothermal aging of polymer glasses are discussed. Critical analysis of conventional scanning calorimetry reveals that its accuracy may be suspect under certain circumstances due to the thermal lag inherent in a temperature scanning experiment. An additional problem is that the conventional technique is restricted to certain kinds of paths for reaching the aging temperature. It is proposed that both problems can be overcome by analyzing the output of a scanning calorimeter not only during steady heating but also during the transients at the beginning and end of a heating scan. This data analysis method represents an extension of a method used previously by others in accurate measurements of the much larger heat of fusion of crystalline polymers. Practical feasibility of the improved technique is demonstrated by preliminary measurements of enthalpy relaxation during aging of well‐characterized polystyrene at 80°C. In particular, the initial departure from equilibrium of a glass prepared by 5°C/min cooling from the liquid state is found to be 6.9 ± 0.6 J/g. This measured value agrees with a value calculated on the basis of the glass transition temperature corresponding to 5°C/min cooling and heat‐capacity data from the literature.