Meniscus osculation and adsorption on geometrically structured walls

TL;DR

This paper investigates the meniscus osculation transition in fluid adsorption on structured walls, developing a scaling theory, confirming predictions with DFT, and identifying three distinct adsorption regimes near bulk coexistence.

Contribution

It introduces a new scaling theory for meniscus osculation on structured surfaces and confirms it with microscopic DFT models, linking geometric and interfacial phenomena.

Findings

The osculation transition is of fractional 7/2 order.

Adsorption exhibits three regimes: microscopic, mesoscopic, and unbinding.

Theoretical predictions are supported by DFT and sum-rule analysis.

Abstract

We study the adsorption of simple fluids at smoothly structured, completely wet, walls and show that a meniscus osculation transition occurs when the Laplace and geometrical radii of curvature of locally parabolic regions coincide. Macroscopically, the osculation transition is of fractional, $7/2$, order and separates regimes in which the adsorption is microscopic, containing only a thin wetting layer, and mesoscopic, in which a meniscus exists. We develop a scaling theory for the rounding of the transition due to thin wetting layers and derive critical exponent relations that determine how the interfacial height scales with the geometrical radius of curvature. Connection with the general geometric construction proposed by Rasc\'on and Parry is made. Our predictions are supported by a microscopic model density functional theory (DFT) for drying at a sinusoidally shaped hard-wall where we confirm the order of the transition and also an exact sum-rule for the generalized contact theorem due to Upton. We show that as bulk coexistence is approached the adsorption isotherm separates into three regimes: a pre-osculation regime where it is microscopic, containing only a thin wetting layer, a mesoscopic regime, in which a meniscus sits within the troughs, and finally another microscopic regime where the liquid-gas interface unbinds from the crests of the substrate.