PRESSURE-VOLUME-TEMPERATURE PROPERTIES AND FREE-VOLUME PARAMETERS OF PEO PMMA BLENDS/

Melt-miscible polymer blends of poly(ethylene oxide)/atactic poly(meth yl methacrylate (PEO/a-PMMA) were prepared by melt-mixing and characte rized by pressure-volume-temperature (PVT) dilatometry in the pressure and temperature range of 0 to 200 Ma and 20 to 200 degrees C, respect ively. The PVT data were analyzed in terms of two equations of state ( EOS). The empirical Tait EOS was applied in the glassy, semicrystallin e, and equilibrium melt state, and the Simha-Somcynsky EOS theory was applied in the equilibrium melt and glassy state. The Simha-Somcynsky EOS theory contains a free volume function. The temperature, pressure, and composition dependence of the free volume fraction h calculated f rom the Simha-Somcynsky EOS theory was studied. As a function of blend composition we observe that the free volume fraction, thermal expansi vity, and compressibility all deviate mainly positively from linearity while the specific volume deviates mainly negatively from linearity, These findings are reconciled with composition-dependent free volume p arameters, the free volume and cell volume as well as with self-and cr oss-interaction parameters derived from the Simha-Somcynsky EOS theory as applied to polymer mixtures. Moreover, the pressure dependence of glass and melting transitions as well as crystallization kinetics have been investigated. (C) 1998 John Wiley & Sons, Inc.