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Using Kinetic Monte Carlo simulation, we model gas-liquid spinodaldecomposition in a size-polydisperse square well fluid, representing a'near-monodisperse' colloidal dispersion. We find that fractionation (demixing)of particle sizes between the phases begins asserting itself shortly after theonset of phase ordering. Strikingly, the direction of size fractionation can bereversed by a seemingly trivial choice between two inter-particle potentialswhich, in the monodisperse case, are identical -- we rationalise this in termsof a perturbative, equilibrium theory of polydispersity. Furthermore, ourquantitative results show that Kinetic Monte Carlo simulation can providedetailed insight into the role of fractionation in real colloidal systems.

Spinodal fractionation in a polydisperse square well fluid