Capillary condensation between nonparallel walls.

We study the condensation of fluids confined by a pair of nonparallel plates of finite height H. We show that such a system experiences two types of condensation, termed single and double pinning, which can be characterized by one (single-pinning) or two (double-pinning) edge contact angles describing the shape of menisci pinned at the system edges. For both types of capillary condensation, we formulate the Kelvin-like equation and determine the conditions under which the given type of condensation occurs.

Kelvin equation for bridging transitions.

We study bridging transitions between a pair of nonplanar surfaces. We show that the transition can be described using a generalized Kelvin equation by mapping the system to a slit of finite length. The proposed equation is applied to analyze the asymptotic behavior of the growth of the bridging film, which occurs when the confining walls are gradually flattened.

Critical-point wedge filling and critical-point wetting.

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.

Critical behaviour of the contact angle within nonwetting gaps.

Recent density functional theory and simulation studies of fluid adsorption near planar walls in systems where the wall-fluid and fluid-fluid interactions have different ranges, have shown that critical point wetting may not occur and instead nonwetting gaps appear in the surface phase diagram, separating lines of wetting and drying transitions, that extend up to the critical temperature. Here we clarify the features of the surface phase diagrams that are common, regardless of the range and balance of the forces, showing, in particular, that the lines of temperature driven wetting and drying transitions, as well as lines of constant contact angleπ>θ>0, always converge to an ordinary surface phase transition at. When nonwetting gaps appear the contact angle either vanishes or tends toast≡(Tc-T)/Tc→0.

Surface Phase Diagrams for Wetting with Long-Ranged Forces.

Recent density functional theory and simulation studies of wetting and drying transitions in systems with long-ranged, dispersionlike forces, away from the near vicinity of the bulk critical temperature T_{c}, have questioned the generality of the global surface phase diagrams for wetting, due to Nakanishi and Fisher, pertinent to systems with short-ranged forces. We extend these studies deriving fully analytic results which determine the surface phase diagrams over the whole temperature range up to T_{c}. The phase boundaries, order of, and asymmetry between the lines of wetting and drying transitions are determined exactly showing that they always converge to an ordinary surface critical point.

Critical effects and scaling at meniscus osculation transitions.

We propose a simple scaling theory describing critical effects at rounded meniscus osculation transitions which occur when the Laplace radius of a condensed macroscopic drop of liquid coincides with the local radius of curvature R_{w} in a confining parabolic geometry. We argue that the exponent β_{osc} characterizing the scale of the interfacial height ℓ_{0}∝R_{w}^{β_{osc}} at osculation, for large R_{w}, falls into two regimes representing fluctuation-dominated and mean-field-like behavior, respectively. These two regimes are separated by an upper critical dimension, which is determined here explicitly and depends on the range of the intermolecular forces.

Phase behavior of fluids in undulated nanopores.

The geometry of walls forming a narrow pore may qualitatively affect the phase behavior of the confined fluid. Specifically, the nature of condensation in nanopores formed of sinusoidally shaped walls (with amplitude A and period P) is governed by the wall mean separation L as follows. For L>L_{t}, where L_{t} increases with A, the pores exhibit standard capillary condensation similar to planar slits.

Meniscus osculation and adsorption on geometrically structured walls.

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.

Capillary condensation and depinning transitions in open slits.

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/π, the condensation is of type I involving menisci which are pinned at the top edges at the ends of the capillary.

Edge Contact Angle, Capillary Condensation, and Meniscus Depinning.

We study the phase equilibria of a fluid confined in an open capillary slit formed when a wall of finite length H is brought a distance L away from a second macroscopic surface. 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. For long capillaries, with a<2/π, the condensation is of type I involving menisci which are pinned at the top edges at the ends of the capillary characterized by an edge contact angle.

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.

Height of a liquid drop on a wetting stripe.

Adsorption of liquid on a planar wall decorated by a hydrophilic stripe of width L is considered. Under the condition that the wall is only partially wet (or dry) while the stripe tends to be wet completely, a liquid drop is formed above the stripe. The maximum height ℓ_{m}(δμ) of the drop depends on the stripe width L and the chemical potential departure from saturation δμ where it adopts the value ℓ_{0}=ℓ_{m}(0).

Filling, depinning, unbinding: Three adsorption regimes for nanocorrugated substrates.

We study adsorption at periodically corrugated substrates formed by scoring rectangular grooves into a planar solid wall which interacts with the fluid via long-range (dispersion) forces. The grooves are assumed to be macroscopically long but their depth, width, and separations can all be molecularly small. We show that the entire adsorption process can be divided into three parts consisting of (i) filling the grooves by a capillary liquid; (ii) depinning of the liquid-gas interface from the wall edges; and (iii) unbinding of the interface from the top of the wall, which is accompanied by a rapid but continuous flattening of its shape.

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.

Bridging of liquid drops at chemically structured walls.

Using mesoscopic interfacial models and microscopic density functional theory we study fluid adsorption at a dry wall decorated with three completely wet stripes of width L separated by distances D_{1} and D_{2}. The stripes interact with the fluid with long-range forces inducing a large finite-size contribution to the surface free energy. We show that this nonextensive free-energy contribution scales with lnL and drives different types of bridging transition corresponding to the merging of liquid drops adsorbed at neighboring wetting stripes when the separation between them is molecularly small.

Geometry-induced interface pinning at completely wet walls.

We study complete wetting of solid walls that are patterned by parallel nanogrooves of depth D and width L with a periodicity of 2L. The wall is formed of a material which interacts with the fluid via a long-range potential and exhibits first-order wetting transition at temperature T_{w}, should the wall be planar. Using a nonlocal density functional theory we show that at a fixed temperature T>T_{w} the process of complete wetting depends sensitively on two microscopic length scales L_{c}^{+} and L_{c}^{-}.

Continuous condensation in nanogrooves.

We consider condensation in a capillary groove of width L and depth D, formed by walls that are completely wet (contact angle θ=0), which is in a contact with a gas reservoir of the chemical potential μ. On a mesoscopic level, the condensation process can be described in terms of the midpoint height ℓ of a meniscus formed at the liquid-gas interface. For macroscopically deep grooves (D→∞), and in the presence of long-range (dispersion) forces, the condensation corresponds to a second-order phase transition, such that ℓ∼(μ_{cc}-μ)^{-1/4} as μ→μ_{cc}^{-} where μ_{cc} is the chemical potential pertinent to capillary condensation in a slit pore of width L.

Demixing, surface nematization, and competing adsorption in binary mixtures of hard rods and hard spheres under confinement.

A molecular simulation study of binary mixtures of hard spherocylinders (HSCs) and hard spheres (HSs) confined between two structureless hard walls is presented. The principal aim of the work is to understand the effect of the presence of hard spheres on the entropically driven surface nematization of hard rod-like particles at surfaces. The mixtures are studied using a constant normal-pressure Monte Carlo algorithm.

Modified Kelvin Equations for Capillary Condensation in Narrow and Wide Grooves.

We consider the location and order of capillary condensation transitions occurring in deep grooves of width L and depth D. For walls that are completely wet by liquid (contact angle θ=0) the transition is continuous and its location is not sensitive to the depth of the groove. However, for walls that are partially wet by liquid, where the transition is first order, we show that the pressure at which it occurs is determined by a modified Kelvin equation characterized by an edge contact angle θ_{E} describing the shape of the meniscus formed at the top of the groove.

Scaling behavior of thin films on chemically heterogeneous walls.

We study the adsorption of a fluid in the grand canonical ensemble occurring at a planar heterogeneous wall which is decorated with a chemical stripe of width L. We suppose that the material of the stripe strongly preferentially adsorbs the liquid in contrast to the outer material which is only partially wet. This competition leads to the nucleation of a droplet of liquid on the stripe, the height h_{m} and shape of which (at bulk two-phase coexistence) has been predicted previously using mesoscopic interfacial Hamiltonian theory.

Edge contact angle and modified Kelvin equation for condensation in open pores.

We consider capillary condensation transitions occurring in open slits of width L and finite height H immersed in a reservoir of vapor. In this case the pressure at which condensation occurs is closer to saturation compared to that occurring in an infinite slit (H=∞) due to the presence of two menisci that are pinned near the open ends. Using macroscopic arguments, we derive a modified Kelvin equation for the pressure p_{cc}(L;H) at which condensation occurs and show that the two menisci are characterized by an edge contact angle θ_{e} that is always larger than the equilibrium contact angle θ, only equal to it in the limit of macroscopic H.

Crossover scaling of apparent first-order wetting in two-dimensional systems with short-ranged forces.

Recent analyses of wetting in the semi-infinite two-dimensional Ising model, extended to include both a surface coupling enhancement and a surface field, have shown that the wetting transition may be effectively first-order and that surprisingly the surface susceptibility develops a divergence described by an anomalous exponent with value γ_{11}^{eff}=3/2. We reproduce these results using an interfacial Hamiltonian model making a connection with previous studies of two-dimensional wetting, and we show that they follow from the simple crossover scaling of the singular contribution to the surface free-energy, which describes the change from apparent first-order to continuous (critical) wetting due to interfacial tunneling. The crossover scaling functions are calculated explicitly within both the strong-fluctuation and intermediate-fluctuation regimes, and they determine uniquely and more generally the value of γ_{11}^{eff}, which is nonuniversal for the latter regime.

Influence of intermolecular forces at critical-point wedge filling.

We use microscopic density functional theory to study filling transitions in systems with long-ranged wall-fluid and short-ranged fluid-fluid forces occurring in a right-angle wedge. By changing the strength of the wall-fluid interaction we can induce both wetting and filling transitions over a wide range of temperatures and study the order of these transitions. At low temperatures we find that both wetting and filling transitions are first order in keeping with predictions of simple local effective Hamiltonian models.