Gelation and phase coexistence in colloidal suspensions with short-range forces: Generic behavior versus specificity

Abstract

The interplay between physical gelation and equilibrium phase transitions in asymmetric binary mixtures is analyzed from the effective fluid approach, in which the big particles interact via a short-range effective attraction beyond the core due to the depletion mechanism. The question of the universality of the scenario for dynamical arrest is then addressed. The comparison of the phase diagrams of the hard-sphere mixture and the Asakura-Oosawa models at various size ratios shows that strong specificity is observed for nonideal depletants. In particular, equilibrium gelation, without the competition with fluid-fluid transition is possible in mixtures of hard-sphere colloids. This is interpreted from the specificities of the effective potential, such as its oscillatory behavior and its complex variation with the physical parameters. The consequences on the dynamical arrest and the fluid-fluid transition are then investigated by considering in particular the role of the well at contact and the first repulsive barrier. This is done for the actual effective potential in the hard-sphere mixture and for a square well and shoulder model, which allows a separate discussion of the role of the different parameters, in particular on the localization length and the escape time. This study is next extended to mixtures of "hard-sphere-like" colloids with residual interactions. It confirms the trends relative to equilibrium gelation and illustrates a diversity of the phase behavior well beyond the scenarios expected from simple models.