Capillary Condensation and Depinning Transitions in Open Slits

TL;DR

This paper investigates the complex phase transitions of a fluid in an open capillary slit, revealing how aspect ratio and contact angle influence condensation types, meniscus depinning, and phase transition orders.

Contribution

It provides a detailed analysis of capillary condensation and meniscus depinning transitions, including new scaling theories and phase boundary characterizations based on aspect ratio and wetting conditions.

Findings

Three distinct condensation regimes depending on aspect ratio.

Identification of a third-order depinning transition for complete wetting.

Explicit conditions under which capillary condensation is suppressed.

Abstract

We study the low temperature phase equilibria of a fluid confined in an open capillary slit formed by two parallel walls separated by a distance $L$ which are in contact with a reservoir of gas. The top wall of the capillary is of finite length $H$ while the bottom wall is considered of macroscopic extent. This system shows rich phase equilibria arising from the competition between two different types of capillary condensation, corner filling and meniscus depinning transitions depending on the value of the aspect ratio $a=L/H$ and divides into three regimes: For long capillaries, with $a<2/\pi$, the condensation is of type I involving menisci which are pinned at the top edges at the ends of the capillary. For intermediate capillaries, with $2/\pi<a<1$, depending on the value of the contact angle the condensation may be of type I or of type II, in which the menisci overspill into the reservoir and there is no pinning. For short capillaries, with $a>1$, condensation is always of type II. In all regimes, capillary condensation is completely suppressed for sufficiently large contact angles which is determined explicitly. For long and intermediate capillaries, we show that there is an additional continuous phase transition in the condensed liquid-like phase, associated with the depinning of each meniscus as they round the upper open edges of the slit. Meniscus depinning is third-order for complete wetting and second-order for partial wetting. Detailed scaling theories are developed for these transitions and phase boundaries which connect with the theories of wedge (corner) filling and wetting encompassing interfacial fluctuation effects and the direct influence of intermolecular forces.