Critical phase behavior in multi-component fluid mixtures: Complete scaling analysis

We analyze the critical gas-liquid phase behavior of arbitrary fluid mixtures in their coexistence region. We focus on the setting relevant for polydisperse colloids, where the overall density and composition of the system are being controlled, in addition to temperature. Our analysis uses the complete scaling formalism and thus includes pressure mixing effects in the mapping from thermodynamic fields to the effective fields of 3D Ising criticality. Because of fractionation, where mixture components are distributed unevenly across coexisting phases, the critical behavior is remarkably rich. We give scaling laws for a number of important loci in the phase diagram. These include the cloud and shadow curves, which characterise the onset of phase coexistence, a more general set of curves defined by fixing the fractional volumes of the coexisting phases to arbitrary values, and conventional coexistence curves of the densities of coexisting phases for fixed overall density. We identify suitable observables (distinct from the Yang-Yang anomalies discussed in the literature) for detecting pressure mixing effects. Our analytical predictions are checked against numerics using a set of mapping parameters fitted to simulation data for a polydisperse Lennard-Jones fluid, allowing us to highlight crossovers where pressure mixing becomes relevant close to the critical point.Comment: 21 pages, 7 captioned figure

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

New insights into phase separation in colloidal suspensions are provided via a new dynamical theory based on the Polydisperse Lattice-Gas model. The model gives a simplified description of polydisperse colloids, incorporating a hard-core repulsion combined with polydispersity in the strength of the attraction between neighbouring particles. Our mean-field equations describe the local concentration evolution for each of an arbitrary number of species, and for an arbitrary overall composition of the system. We focus on the predictions for the dynamics of colloidal gas-liquid phase separation after a quench into the coexistence region. The critical point and the relevant spinodal curves are determined analytically, with the latter depending only on three moments of the overall composition. The results for the early-time spinodal dynamics show qualitative changes as one crosses a 'quenched' spinodal that excludes fractionation and so allows only density fluctuations at fixed composition. This effect occurs for dense systems, in agreement with a conjecture by Warren that, at high density, fractionation should be generically slow because it requires inter-diffusion of particles. We verify this conclusion by showing that the observed qualitative changes disappear when direct particle-particle swaps are allowed in the dynamics. Finally, the rich behaviour beyond the spinodal regime is examined, where we find that the evaporation of gas bubbles with strongly fractionated interfaces causes long-lived composition heterogeneities in the liquid phase; we introduce a two-dimensional density histogram method that allows such effects to be easily visualized for an arbitrary number of particle species.Comment: 20 pages; accepted for publication in Physical Chemistry Chemical Physic