Breaking Cassie's Law for Condensation in a Nanopatterned Slit.

We study the phase transitions of a fluid confined in a capillary slit made from two adjacent walls, each of which are a periodic composite of stripes of two different materials. For wide slits the capillary condensation occurs at a pressure which is described accurately by a combination of the Kelvin equation and the Cassie law for an averaged contact angle. However, for narrow slits the condensation occurs in two steps involving an intermediate bridging phase, with the corresponding pressures described by two new Kelvin equations.

Three-Phase Fluid Coexistence in Heterogenous Slits.

We study the competition between local (bridging) and global condensation of fluid in a chemically heterogeneous capillary slit made from two parallel adjacent walls each patterned with a single stripe. Using a mesoscopic modified Kelvin equation, which determines the shape of the menisci pinned at the stripe edges in the bridge phase, we determine the conditions under which the local bridging transition precedes capillary condensation as the pressure (or chemical potential) is increased. Provided the contact angle of the stripe is less than that of the outer wall we show that triple points, where evaporated, locally condensed, and globally condensed states all coexist are possible depending on the value of the aspect ratio a=L/H, where H is the stripe width and L the wall separation.

Symmetry-breaking morphological transitions at chemically nanopatterned walls.

We study the structure and morphological changes of fluids that are in contact with solid composites formed by alternating and microscopically wide stripes of two different materials. One type of the stripes interacts with the fluid via long-ranged Lennard-Jones-like potential and tends to be completely wet, while the other type is purely repulsive and thus tends to be completely dry. We consider closed systems with a fixed number of particles that allows for stabilization of fluid configurations breaking the lateral symmetry of the wall potential.

Scaling of wetting and prewetting transitions on nanopatterned walls.

We consider a nanopatterned planar wall consisting of a periodic array of stripes of width L, which are completely wet by liquid (contact angle θ=0), separated by regions of width D which are completely dry (contact angle θ=π). Using microscopic density functional theory, we show that, in the presence of long-ranged dispersion forces, the wall-gas interface undergoes a first-order wetting transition, at bulk coexistence as the separation D is reduced to a value D_{w}∝lnL, induced by the bridging between neighboring liquid droplets. Associated with this is a line of prewetting transitions occurring off coexistence.