Glass transition and reversible gelation in asymmetric binary mixtures: A study by mode coupling theory and molecular dynamics.

Abstract

The glass transition and the binodals of asymmetric binary mixtures are investigated from the effective fluid approach in the mode coupling theory and by molecular dynamics. Motivated by previous theoretical predictions, the hard-sphere mixture and the Asakura-Oosawa models are used to analyze experimental results from the literature, relative to polystyrene spheres mixed either with linear polymers or with dense microgel particles. In agreement with the experimental observations, the specificity of the depletant particles is shown to favor lower density gels. It further favors equilibrium gelation by reducing also the tendency of the system to phase separate. These results are confirmed by a phenomenological modification of the mode coupling theory in which the vertex functions are computed at an effective density lower than the actual one. A model effective potential in asymmetric mixtures of hard particles is used to further check this phenomenological modification against molecular dynamics simulation.