Influence of interfacial adhesion and the nonequilibrium glassy structure of a polymer on the enthalpy of mixing of polystyrene-based filled composites

For composites based on polystyrene, the styrene-butadiene copolymer, and polybutadiene filled with various kinds of zinc oxide powder, the enthalpy of mixing is calculated in the entire range of filler contents on the basis of calorimetric measurements with the use of the thermochemical cycle. It is shown that, when the polymer is in excess in the composites based on polystyrene and its copolymer, the enthalpy of mixing is negative, whereas at a high content of the filler, this value is positive. The alternating-sign pattern of the concentration dependence of the enthalpy of mixing is interpreted in terms of the superposition of the negative contribution of the enthalpy of the interfacial-adhesion interaction of a polymer matrix with the filler and the positive contribution due to a gain in the level of nonequilibrium of the glassy matrix near the surface. A thermodynamic model that makes it possible to separate these contributions and to describe the experimental curves of the enthalpy of mixing for the composites is advanced.