Theoretical Predictions of Temperature-Induced Gelation in Aqueous Dispersions Containing PEO-Grafted Particles.

In this work, we utilize classical polymer density functional theory (DFT) to study gelation in systems containing colloidal particles onto which polymers are grafted. The solution conditions are such that the corresponding bulk system displays a lower critical solution temperature (LCST). We specifically compare our predictions with experimental results by Shay et al. (J. Rheol. 2001, 45, 913-927), who investigated temperature response in aqueous dispersions containing polystyrene particles (PS), with grafted 45-mer poly(ethylene oxide) (PEO) chains. Our DFT treatment is based on a model for aqueous PEO solutions that was originally developed by Karlström for bulk solutions. In this model, monomers are assumed to be in either of two classes of states, labeled A and B, where B is more solvophobic than A. On the other hand, the degeneracy of B exceeds that of A, causing the population of solvophobic monomers to increase with temperature. In agreement with experimental findings by Shay et al., we locate gelation at temperatures considerably below TΘ, and far below the LCST for such chain lengths. This gelation occurs also without any dispersion interactions between the PS particles. Interestingly, the polymer-induced interaction free energy displays a nonmonotonic dependence on the grafting density. At high grafting densities, bridging attractions between grafted layers take place (considerably below TΘ). At low grafting densities, on the other hand, the polymers are able to bridge across to the other particle surface. Shay et al. conducted their experiments at very low ionic strength, using deionized water as a solvent. We demonstrate that even minute amounts of adsorbed charge on the surface of the particles, can lead to dramatic changes of the gelation temperature, especially at high grafting densities. Another interesting prediction is the existence of elongated (chainlike) equilibrium structures, at low particle concentrations. We emphasize that our model does not rely upon any temperature-dependent interactions.