Mixing properties of model polymer/solvent systems

Abstract

Monte Carlo calculations have been performed on two nominally athermal polymer/solvent mixtures to test molecular theories of mixing properties for these systems. We first used the incremental chemical potential concept to derive an equation of state in the spirit of the generalized Flory dimer theory, without resorting to the concept of excluded volume. The resulting generalized Flory dimer-like theory and a related model, statistical associating fluid theory, were tested against simulation results for the excess volume, excess Gibbs free energy and component activity coefficients. Good agreement was obtained between the statistical associating fluid theory and computer simulations for all properties studied. The generalized Flory dimer theory, when applied self-consistently, was also able to provide quantitative predictions for the thermodynamic properties of these mixtures. An important result that emerges from our calculations is that these polymer solutions behave ideally when examined on the basis of a ''Flory-like'' reference state augmented by density effects. This asserts that the effects of molecular size disparity on system thermodynamics are properly captured by this approach. By contrast, the incompressible Flory approach fails to capture the dependence of activity coefficients on composition.

Computer Simulations on the Free Energies and Phase Diagrams of Asymmetrically Interacting Blends

“…Since most polymer mixtures will be asymmetric in some aspect, we expect that these past works will not be representative of realistic systems. Here we build on previous work − and consider blends comprised of polymers of equal length which are energetically asymmetric. The Lennard−Jones parameters defining 1−1 monomer and 2−2 monomer interactions are selected so that: ε 22 /ε 11 = 0.8.…”