The order of condensation in capillary grooves
Abstract
We consider capillary condensation in a deep groove of width L. The transition occurs at a pressure pco(L) described, for large widths, by the Kelvin equation psat - pco(L) = 2σcosθ/L, where θ is the contact angle at the side walls and σ is the surface tension. The order of the transition is determined by the contact angle of the capped end θcap it is continuous if the liquid completely wets the cap, and first-order otherwise. When the transition is first-order, corner menisci at the bottom of the capillary lead to a pronounced metastability, determined by a complementary Kelvin equation Δp(L) = 2σsinθcap/L. On approaching the wetting temperature of the capillary cap, the corner menisci merge and a single meniscus unbinds from the bottom of the groove. Finite-size scaling shifts, crossover behaviour and critical singularities are determined at mean-field level and beyond. Numerical and experimental results showing the continuous nature of condensation for θcap = 0 and the influence of corner menisci on adsorption isotherms are presented.
- Publication:
-
Journal of Physics Condensed Matter
- Pub Date:
- May 2013
- DOI:
- 10.1088/0953-8984/25/19/192101
- Bibcode:
- 2013JPCM...25s2101R