Critical-point wedge filling and critical-point wetting.

Abstract

For simple fluids adsorbed at a planar solid substrate (modeled as an inert wall) it is known that critical-point wetting, that is, the vanishing of the contact angle θ at a temperature T_{w} lying below that of the critical point T_{c}, need not occur. While critical-point wetting necessarily happens when the wall-fluid and fluid-fluid forces have the same range (e.g., both are long ranged or both short ranged) nonwetting gaps appear in the surface phase diagram when there is an imbalance between the ranges of these forces. Here we show that despite this, the convergence of the lines of constant contact angle, 0<θ<π, to an ordinary surface phase transition at T_{c}, means that fluids adsorbed in wedges (and cones) always exhibit critical-point filling (wedge wetting or wedge drying) regardless of the range and imbalance of the forces. We illustrate the necessity of critical-point filling, even in the absence of critical-point wetting, using a microscopic model density functional theory of fluid adsorption in a right angle wedge, with dispersion and also retarded dispersionlike wall-fluid forces. The location and order of the filling phase boundaries are determined and shown to be in excellent agreement with exact thermodynamic requirements and also predictions for critical singularities based on interfacial models.