Phase behaviour of colloidal superballs mixed with non-adsorbing polymers

Inspired by experimental work on colloidal cuboid-polymer dispersions (Rossi et al., Soft Matter, 7, 4139 (2011)) we have theoretically studied the phase behaviour of such mixtures. To that end, free volume theory (FVT) was applied to predict the phase behaviour of mixtures of superballs and non-adsorbing polymer chains in a common solvent. Closed expressions for the thermodynamic properties of a suspension of hard colloidal superballs have been derived, accounting for fluid (F), face-centred cubic (FCC) and simple cubic (SC) phase states. Even though the considered solid phases are approximate, the hard superballs phase diagram semi-quantitatively matches with more evolved methods. The theory developed for the cuboid-polymer mixture reveals a rich phase behaviour, which includes not only isostructural F₁-F₂ coexistence, but also SC₁-SC₂ coexistence, several triple coexistences, and even a quadruple-phase coexistence region (F₁-F₂-SC-FCC). The model proposed offers a tool to asses the stability of cuboid-polymer mixtures in terms of the colloid-to-polymer size ratio. Graphical abstract: [Figure not available: see fulltext.]