Theoretical representation of shear and pressure influence on the phase separation behavior of PVME/PS mixture

In the framework of lattice fluid model, the Gibbs energy and equation of state are derived by introducing the energy (E_s) stored during flow for polymer blends under shear. From the calculation of the spinodal of poly(vinyl methyl ether) (PVME) and polystyrene (PS) mixtures, we have found the influence of E_s on equation of state in pure component is inappreciable, but it is appreciable in the mixture. However, the effect of E_s on phase separation behavior is extremely striking. In the calculation of spinodal for the PVME/PS system, a thin, long and banana miscibility gap generated by shear is seen beside the miscibility gap with lower critical solution temperature. Meanwhile, a binodal coalescence of upper and lower miscibility gaps is occurred. The three points of the three-phase equilibrium are forecasted. The shear rate dependence of cloud point temperature at a certain composition is discussed. The calculated results are acceptable compared with the experiment values obtained by Higgins et al. However, the maximum positive shift and the minimum negative shift of cloud point temperature guessed by Higgins are not obtained. Furthermore, the combining effects of pressure and shear on spinodal shift are predicted.