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New insights into phase separation in colloidal suspensions are provided viaa new dynamical theory based on the Polydisperse Lattice-Gas model. The modelgives a simplified description of polydisperse colloids, incorporating ahard-core repulsion combined with polydispersity in the strength of theattraction between neighbouring particles. Our mean-field equations describethe local concentration evolution for each of an arbitrary number of species,and for an arbitrary overall composition of the system. We focus on thepredictions for the dynamics of colloidal gas-liquid phase separation after aquench into the coexistence region. The critical point and the relevantspinodal curves are determined analytically, with the latter depending only onthree moments of the overall composition. The results for the early-timespinodal dynamics show qualitative changes as one crosses a 'quenched' spinodalthat excludes fractionation and so allows only density fluctuations at fixedcomposition. This effect occurs for dense systems, in agreement with aconjecture by Warren that, at high density, fractionation should be genericallyslow because it requires inter-diffusion of particles. We verify thisconclusion by showing that the observed qualitative changes disappear whendirect particle-particle swaps are allowed in the dynamics. Finally, the richbehaviour beyond the spinodal regime is examined, where we find that theevaporation of gas bubbles with strongly fractionated interfaces causeslong-lived composition heterogeneities in the liquid phase; we introduce atwo-dimensional density histogram method that allows such effects to be easilyvisualized for an arbitrary number of particle species.

Phase separation dynamics of polydisperse colloids: a mean-field lattice-gas theory