Gelation in mixtures of polymers and bidisperse colloids

We investigated the effects of varying the volume fraction of large particles (r) on the linear rheology and microstructure of mixtures of polymers and bidisperse colloids, in which the ratio of the small and large particle diameters was alpha = 0.31 or alpha = 0.45. Suspensions formulated at a total volume fraction of phi(T) = 0.15 and a constant concentration of polymer in the free volume c/c* approximate to 0.7 contained solid-like gels for small r and fluids or fluids of clusters at large r. The solid-like rheology and microstructure of these suspensions changed little with r when r was small, and fluidized only when r > 0.8. By contrast, dense suspensions with phi(T) = 0.40 and alpha = 0.31 contained solid-like gels at all concentrations of large particles and exhibited only modest rheological and microstructural changes upon varying the volume fraction of large particles. These results suggest that the effect of particle-size dispersity on the properties of colloid-polymer mixtures are asymmetric in particle size and are most pronounced near a gelation boundary.