Long range ionic and short range hydration effects govern strongly anisotropic clay nanoparticle interactions

TL;DR

This study uses molecular dynamics simulations to uncover how long-range ionic effects and short-range hydration influence the highly anisotropic interactions between clay nanoparticles, impacting aggregation behavior.

Contribution

It provides detailed atomistic insights into the anisotropic electrostatic and hydration effects governing clay nanoparticle interactions, which were previously not well understood.

Findings

Electrostatic effects dominate at large separations (>1.5 nm).

Hydration structure critically influences interactions at smaller separations.

Interactions vary from attractive to repulsive depending on nanoparticle orientation.

Abstract

The aggregation of clay particles in aqueous solution is a ubiquitous everyday process of broad environmental and technological importance. However, it is poorly understood at the all-important atomistic level since it depends on a complex and dynamic interplay of solvent-mediated electrostatic, hydrogen-bonding, and dispersion interactions. With this in mind we have performed an extensive set of classical molecular dynamics simulations (included enhanced sampling simulations) on the interactions between model kaolinite nanoparticles in pure and salty water. Our simulations reveal highly anisotropic behaviour in which the interaction between the nanoparticles varies from attractive to repulsive depending on the relative orientation of the nanoparticles. Detailed analysis reveals that at large separation (>1.5 nm) this interaction is dominated by electrostatic effects whereas at smaller separations the nature of the water hydration structure becomes critical. This study highlights an incredible richness in how clay nanoparticles interact, which should be accounted for in e.g. coarse grained models of clay nanoparticle aggregation.