Phase separation of stable colloidal clusters

Abstract

This article presents a nonequilibrium thermodynamic theory for the mean-field precipitation, aggregation, and pattern formation of colloidal clusters. A variable gradient energy coefficient and the arrest of particle diffusion upon “jamming” of cluster aggregates in the spinodal region predicts observable gel patterns that, at high intercluster attraction, form system-spanning, out-of-equilibrium networks with glasslike, quasistatic structural relaxation. For reactive systems, we incorporate the free energy landscape of stable prenucleation clusters into the Allen-Cahn reaction equation. We show that pattern formation is dominantly controlled by the Damköhler number and the stability of the clusters, which modifies the autocatalytic rate of precipitation. As clusters individually become more stable, bulk phase separation is suppressed.