Hysteresis, force oscillations and non-equilibrium effects in the adhesion of spherical nanoparticles to atomically smooth surfaces

TL;DR

This study uses molecular dynamics simulations to explore hysteresis, force oscillations, and non-equilibrium effects in nanoparticle adhesion to smooth surfaces, revealing how history-dependent forces and fluid structure influence particle behavior.

Contribution

It uncovers the role of fluid density changes and structural rearrangements in hysteresis and force oscillations during nanoparticle adhesion, highlighting non-equilibrium effects.

Findings

Hysteresis depends on particle history and fluid structure.

Force oscillations occur when nanoparticle lattice aligns with the wall.

Particle trapping and desorption are influenced by force and fluid rearrangements.

Abstract

Molecular dynamics simulations are used to examine hysteretic effects and distinctions between equilibrium and non-equilibrium aspects of particle adsorption on the walls of nano-sized fluidfilled channels. The force on the particle and the system's Helmholtz free energy are found to depend on the particle's history as well as on its radial position and the wetting properties of the fluid, even when the particle's motion occurs on time scales much longer than the spontaneous adsorption time. The hysteresis is associated with changes in the fluid density in the gap between the particle and the wall, and these structural rearrangements persist over surprisingly long times. The force and free energy exhibit large oscillations with distance when the lattice of the structured nanoparticle is held in register with that of the tube wall, but not if the particle is allowed to rotate freely. Adsorbed particles are trapped in free energy minima in equilibrium, but if the particle is forced along the channel the resulting stick-slip motion alters the fluid structure and allows the particle to desorb.