Phase behavior of binary mixtures of hard convex polyehdra

TL;DR

This study investigates how shape differences in binary mixtures of convex polyhedral nanoparticles influence their phase behavior, revealing that miscibility and phase separation depend on shape similarity, size, and pure component properties.

Contribution

It provides a systematic analysis of the phase behavior of binary mixtures of convex polyhedra, highlighting how pure component properties predict miscibility and phase separation.

Findings

Phase separation occurs at high pressures due to incompatible crystal structures.

Solubility in mixtures correlates with differences in order-disorder transition pressures.

Qualitative trends in miscibility are linked to pure component properties.

Abstract

Shape anisotropy of colloidal nanoparticles has emerged as an important design variable for engineering assemblies with targeted structure and properties. In particular, a number of polyhedral nanoparticles have been shown to exhibit a rich phase behavior [Agarwal et al., Nature Materials, 2011, 10, 230]. Since real synthesized particles have polydispersity not only in size but also in shape, we explore here the phase behavior of binary mixtures of hard convex polyhedra having similar sizes but different shapes. Choosing representative particle shapes from those readily synthesizable, we study in particular four mixtures: (i) cubes and spheres (with spheres providing a non-polyhedral reference case), (ii) cubes and truncated octahedra, (iii) cubes and cuboctahedra, and (iv) cuboctahedra and truncated octahedra. The phase behavior of such mixtures is dependent on the interplay of mixing and packing entropy, which can give rise to miscible or phase-separated states. The extent of mixing of two such particle types is expected to depend on the degree of shape similarity, relative sizes, composition, and compatibility of the crystal structures formed by the pure components. While expectedly the binary systems studied exhibit phase separation at high pressures due to the incompatible pure-component crystal structures, our study shows that the essential qualitative trends in miscibility and phase separation can be correlated to properties of the pure components, such as the relative values of the order-disorder transition pressure (ODP) of each component. Specifically, if for a mixture A+B we have that ODP_B <ODP_A and \Delta ODP = ODP_A - ODP_B, then at any particular pressure where phase separation occurs, the larger the \Delta ODP the lower the solubility of A in the B-rich ordered phase and the higher the solubility of B in the A-rich ordered phase.