Bridging and depletion mechanisms in colloid-colloid effective interactions: A reentrant phase diagram

TL;DR

This paper introduces a class of nonadditive sticky-hard-sphere binary mixtures to analyze effective interactions and phase behavior, revealing reentrant fluid-fluid instability driven by depletion, pulling, and bridging mechanisms.

Contribution

It develops analytical models for nonadditive mixtures, identifying physical mechanisms and phase diagram features, extending understanding of colloid-colloid interactions with tunable parameters.

Findings

Reentrant fluid-fluid phase instability observed.

Depletion, pulling, and bridging mechanisms identified.

Analytical solutions for specific nonadditivity cases provided.

Abstract

A general class of nonadditive sticky-hard-sphere binary mixtures, where small and large spheres represent the solvent and the solute, respectively, is introduced. The solute-solute and solvent-solvent interactions are of hard-sphere type, while the solute-solvent interactions are of sticky-hard-sphere type with tunable degrees of size nonadditivity and stickiness. Two particular and complementary limits are studied using analytical and semi-analytical tools. The first case is characterized by zero nonadditivity, lending itself to a Percus-Yevick approximate solution from which the impact of stickiness on the spinodal curves and on the effective solute-solute potential is analyzed. In the opposite nonadditive case, the solvent-solvent diameter is zero and the model can then be reckoned as an extension of the well-known Asakura-Oosawa model with additional sticky solute-solvent interaction. This latter model has the property that its exact effective one-component problem involves only solute-solute pair potentials for size ratios such that a solvent particle fits inside the interstitial region of three touching solutes. In particular, we explicitly identify the three competing physical mechanisms (depletion, pulling, and bridging) giving rise to the effective interaction. Some remarks on the phase diagram of these two complementary models are also addressed through the use of the Noro-Frenkel criterion and a first-order perturbation analysis. Our findings suggest reentrance of the fluid-fluid instability as solvent density (in the first model) or adhesion (in the second model) is varied. Some perspectives in terms of the interpretation of recent experimental studies of microgels adsorbed onto large polystyrene particles are discussed.