Free Isotropic-Nematic Interfaces in Fluids of Charged Platelike Colloids

TL;DR

This study uses density-functional theory to analyze the properties and free interfaces of charged platelike colloids, revealing how charge influences phase behavior, interfacial structure, and electrostatic profiles.

Contribution

It introduces a model for charged platelike colloids using density-functional theory, exploring phase diagrams, interfacial profiles, and electrostatic effects with novel insights.

Findings

Phase diagrams show isotropic and nematic phases separated by a first-order transition.

Increasing particle charge shifts phase boundaries to higher densities.

Interfacial width and correlation lengths are approximately equal to the Debye length.

Abstract

Bulk properties and free interfaces of mixtures of charged platelike colloids and salt are studied within density-functional theory. The particles are modeled by hard cuboids with their edges constrained to be parallel to the artesian axes corresponding to the Zwanzig model. The charges of the particles are concentrated in their center. The density functional is derived by functional integration of an extension of the Debye-H\"uckel pair distribution function with respect to the interaction potential. For sufficiently small macroion charges, the bulk phase diagrams exhibit one isotropic and one nematic phase separated by a first-order phase transition. With increasing platelet charge, the isotropic and nematic binodals are shifted to higher densities. The Donnan potential between the coexisting isotropic and nematic phases is inferred from bulk structure calculations. Non-monotonic density and nematic order parameter profiles are found at a free interface interpolating between the coexisting isotropic and nematic bulk phases. Moreover, electrically charged layers form at the free interface leading to monotonically varying electrostatic potential profiles. Both the widths of the free interfaces and the bulk correlation lengths are approximately given by the Debye length. For fixed salt density, the interfacial tension decreases upon increasing the macroion charge.