CALORIMETRIC DETERMINATION OF VITRIFICATION TIME AND HEAT-CAPACITY OF A THERMOSETTING POLYMER

First observations of a decrease in heat capacity on isothermal vitrification of a thermosetting polymer are reported. The method developed for this study allows simultaneous measurements of both the heat capacity of a material and the enthalpy released as chemical reactions occur under virtually isothermal conditions. Control experiments have been done on a nonstoichiometric composition which does not vitrify and for which total enthalpy released can be measured. During isothermal curing, the heat capacity of a thermoset first increases slightly, undergoes an abrupt decrease in a narrow range of time, and thereafter slowly decreases. The abrupt decrease represents the transition of the liquid to a glassy solid, which is irreversible and which shifts to shorter times as the curing temperature is increased. This transition occurs at different extents of cure for different temperatures. The thermodynamic consequence of kinetic slowing on irreversible conversion of a molecular liquid to a macromolecule under isothermal conditions is similar to that observed on reversible clustering, as a result of decrease in the thermal energy on supercooling a molecular liquid.