A simple phenomenological approach to the thermal behavior of glasses during uniform heating or cooling

Abstract

Abstract Thermal behavior of glasses, as observed from the isobaric variations of volume, v , and enthalpy, H , is analyzed in terms of retardation kinetics. A phenomenological theory involving a single retardation time, τ, is developed, assuming that molecular mobility is controlled essentially by the actual free volume, or configurational entropy of the glassy specimen. The characteristic features of the v and H isobars, as derived from the theory, are examined as a function of the thermal history of a typical glassy specimen. The respective contributions of temperature and structural parameters to τ, are also discussed in terms of the characteristic parameters of the isobars. The theoretical predictions are compared with some dilatometric data obtained with an atactic polystyrene. The comparison reveals the limitations of the theoretical treatment and suggests that glass‐transition phenomena involve more than one retardation mechanism.