Understanding liquid-liquid immiscibility and LCST behaviour in polymer solutions with a Wertheim TPT1 description

The aim of the work presented in this paper is to help in the understanding of the lower critical solution temperature (LCST) fluid phase behaviour exhibited by polymer solutions. It is well recognized that the LCST in polymer solutions is a consequence of density (compressibility) effects; the solvent is much more compressible than the polymer and the increasing difference in compressibility when the temperature is increased leads to a negative volume of mixing. The separate roles that the repulsive and attractive intermolecular interactions play in this regard are less well understood. In this study we use the Wertheim first-order thermodynamic perturbation theory (TPT1) [Wertheim, M. S., 1987, J. chem. Phys., 87, 7323; Chapman, W. G., Jackson, G., and Gubbins, K. E., 1988, Molec. Phys., 65, 1057] to describe the phase equilibria of model polymer solutions of hard spheres and hard-sphere chains where the diameter of the solvent and the polymeric segments are the same (symmetrical system). The thermodynamic functions (volume, enthalpy, entropy and Gibbs function) of mixing are determined to assess the possibility of a demixing instability in such a system. No fluid-fluid phase separation is found for the purely repulsive (athermal) system, regardless of the chain length of the polymer. The role of the attractive interactions is then investigated by incorporating attractive interactions at the mean-field level; the simplest system with equivalent (symmetric) solvent-solvent, solvent-polymer segment, and polymer segment-polymer segment interaction energies is examined. The attractive interactions are found to be essential in describing the liquid-liquid phase separation; LCST behaviour is found for mixtures with ‘polymer’ chains of seven segments or more. In this case we show that the phase behaviour is driven by an unfavourable (negative) entropy of mixing due to an increase in the density of the solvent on addition of small amounts of polymer. We also determine the thermodynamic properties of mixing for a system of spherical molecules of the same size with directional interactions that give rise to LCST and closed-loop behaviour. As expected the mechanism for phase separation in such systems is very different to that in polymer solutions.