Cassie-Wenzel transition of a binary liquid mixture on a nano-sculptured surface

TL;DR

This study uses density functional theory to analyze the Cassie-Wenzel transition of a symmetric binary liquid mixture on nano-structured surfaces, revealing limitations of macroscopic predictions at nanoscales.

Contribution

It introduces a detailed microscopic analysis of the Cassie-Wenzel transition for binary mixtures on nano-corrugated surfaces, highlighting deviations from macroscopic theory.

Findings

Transition depends on multiple parameters, not just contact angle.

Microscopic effects alter the predicted transition points.

Macroscopic theory is insufficient for nanoscopic systems.

Abstract

The Cassie-Wenzel transition of a symmetric binary liquid mixture in contact with a nano-corrugated wall is studied. The corrugation consists of a periodic array of nano-pits with square cross sections. The substrate potential is the sum over Lennard-Jones interactions, describing the pairwise interaction between the wall particles $C$ and the fluid particles. The liquid is composed of two species of particles, $A$ and $B$, which have the same size and equal $A - A$ and $B - B$ interactions. The liquid particles interact between each other also via $A - B$ Lennard-Jones potentials. We have employed classical density functional theory to determine the equilibrium structure of binary liquid mixtures in contact with the nano-corrugated surface. Liquid intrusion into the pits is studied as a function of various system parameters such as the composition of the liquid, the strengths of various inter-particle interactions, as well as the geometric parameters of the pits. The binary liquid mixture is taken to be at its mixed-liquid-vapor coexistence. For various sets of parameters the results obtained for the Cassie - Wenzel transition, as well as for the metastability of the two corresponding thermodynamic states, are compared with macroscopic predictions in order to check the range of validity of the macroscopic theories for systems exposed to nanoscopic confinements. Distinct from the macroscopic theory, it is found that the Cassie - Wenzel transition cannot be predicted based on the knowledge of a single parameter, such as the contact angle within the macroscopic theory.