Analysis of a Polystyrene–Toluene System through “Dynamic” Sorption Tests: Glass Transitions and Retrograde Vitrification

Exposing a glassy polymer to a fluid phase (in gaseous or liquid state) containing a low molecular weight compound results in the sorption of the latter within the polymer, inducing, among other effects, the plasticization of the material which also promotes a change in the glass transition temperature. The amount of sorbed penetrant is often related in a complex fashion to the temperature and pressure of the fluid, thus determining that the locus of glass transition, when represented in pressure–temperature coordinates, may display as well rather complex patterns. This is an issue of particular importance in several applications of glassy polymers. In particular, we investigated the behavior of polystyrene in contact with toluene vapor by performing several modes of dynamic sorption experiments, in which the rate of change of the temperature of the system and/or of the pressure of the vapor phase are controlled with high accuracy, with the aim of creating a map of rubbery and glassy states of the polymer...