Multiphase Coexistence in Binary Hard Colloidal Mixtures: Predictions from a Simple Algebraic Theory.

A general theoretical framework is proposed to quantify the thermodynamic properties of multicomponent hard colloidal mixtures. This framework is used to predict the phase behavior of mixtures of rods with spheres and rods with plates taking into account (liquid) crystal phases of both components. We demonstrate a rich and complex range of phase behaviors featuring a large variety of different multiphase coexistence regions, including two five-phase coexistence regions for hard rod/sphere mixtures, and even a six-phase equilibrium for hard rod/plate dispersions. The various multiphase coexistences featured in a particular mixture are in line with a recently proposed generalized phase rule and can be tuned through subtle variations of the particle shape and size ratio. Our approach qualitatively accounts for certain multiphase equilibria observed in rod/plate mixtures of clay colloids and will be a useful guide in tuning the phase behavior of shape-disperse mixtures in general.