Enhanced local viscosity around colloidal nanoparticles probed by Equilibrium Molecular Dynamics Simulations

TL;DR

This study uses equilibrium molecular dynamics simulations to investigate the increased local viscosity of nanolayers around colloidal nanoparticles, revealing its dependence on solid-liquid interactions and the breakdown of classical relations.

Contribution

It introduces a validated method to compute local nanolayer viscosity and demonstrates its dependence on interaction strength, highlighting structural effects beyond density.

Findings

Nanolayer viscosity exceeds bulk values and depends on solid-liquid interaction.

Density increase alone does not account for viscosity enhancement.

Failure of Stokes-Einstein relation near the nanoparticle surface.

Abstract

Nanofluids; dispersions of nanometer-sized particles in a liquid medium; have been proposed for a wide variety of thermal management applications. It is known that a solid-like nanolayer of liquid of typical thickness 0.5-1 nm surrounding the colloidal nanoparticles can act as a thermal bridge between the nanoparticle and the bulk liquid. Yet, its effect on the nanofluid viscosity has not been elucidated so far. In this article, we compute the local viscosity of the nanolayer using equilibrium molecular dynamics based on the Green-Kubo formula. We first assess the validity of the method to predict the viscosity locally. We apply this methodology to the calculation of the local viscosity in the immediate vicinity of a metallic nanoparticle for a wide range of solid-liquid interaction strength, where a nanolayer of thickness 1 nm is observed as a result of the interaction with the nanoparticle. The viscosity of the nanolayer, which is found to be higher than its corresponding bulk value, is directly dependent on the solid-liquid interaction strength. We discuss the origin of this viscosity enhancement and show that the liquid density increment alone cannot explain the values of the viscosity observed. Rather, we suggest that the solid-like structure of the distribution of the liquid atoms in the vicinity of the nanoparticle contributes to the nanolayer viscosity enhancement. Finally, we observe a failure of the Stokes-Einstein relation between viscosity and diffusion close to the wall, depending on the liquid-solid interaction strength, which we rationalize in terms of hydrodynamic slip.