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. We highlight the importance of lines of maximally multicritical wetting and drying transitions, for which we determine the exact critical singularities.

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. For intermediate capillaries, with 2/π1, condensation is always of type II. In all regimes, capillary condensation is completely suppressed for sufficiently large contact angles. We show that there is an additional continuous phase transition in the condensed liquidlike phase, associated with the depinning of each meniscus as they round the upper open edges of the slit. Finite-size scaling predictions are developed for these transitions and phase boundaries which connect with the fluctuation theories of wetting and filling transitions. We test several of our predictions using a fully microscopic density functional theory which allows us to study the two types of capillary condensation and its suppression at the molecular level.

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. These are characterised by different contact angles due to interfacial pinning, with one larger and one smaller than the Cassie angle. We determine the triple point and predict two types of dispersion force induced Derjaguin-like corrections due to mesoscopic volume reduction and the singular free-energy contribution from nanodroplets and bubbles. We test these predictions using a fully microscopic density functional model which confirms their validity even for molecularly narrow slits. Analogous mesoscopic corrections are also predicted for two-dimensional systems arising from thermally induced interfacial wandering.

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. In particular, for a capillary made from completely dry walls patterned with completely wet stripes the condition for the triple point occurs when the aspect ratio takes its maximum possible value 8/π. These predictions are tested using a fully microscopic classical density functional theory and shown to be remarkably accurate even for molecularly narrow slits. The qualitative differences with local and global condensation in heterogeneous cylindrical pores are also highlighted.

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. The dependence of θ_{E} on the groove depth D relies, in turn, on whether corner menisci are formed at the bottom of the groove in the low density gaslike phase. While for macroscopically wide grooves these are always present when θ<45° we argue that their formation is inhibited in narrow grooves. This has a number of implications including that the local pinning of the meniscus and location of the condensation transition is different depending on whether the contact angle is greater or less than a universal value θ^{*}≈31°. Our arguments are supported by detailed microscopic density functional theory calculations that show that the modified Kelvin equation remains highly accurate even when L and D are of the order of tens of molecular diameters.

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. The surface adsorption at different compositions is examined in detail. At moderate hard-sphere concentrations, preferential adsorption of the spheres at the wall is found. However, at moderate to high pressure (density), we observe a crossover in the adsorption behavior with nematic layers of the rods forming at the walls leading to local demixing of the system. The presence of the spherical particles is seen to destabilize the surface nematization of the rods, and the degree of demixing increases on increasing the hard-sphere concentration.

Wetting properties of molecularly rough surfaces.

We employ molecular dynamics simulations to study the wettability of nanoscale rough surfaces in systems governed by Lennard-Jones (LJ) interactions. We consider both smooth and molecularly rough planar surfaces. Solid substrates are modeled as a static collection of LJ particles arranged in a face-centered cubic lattice with the (100) surface exposed to the LJ fluid. Molecularly rough solid surfaces are prepared by removing several strips of LJ atoms from the external layers of the substrate, i.e., forming parallel nanogrooves on the surface. We vary the solid-fluid interactions to investigate strongly and weakly wettable surfaces. We determine the wetting properties by measuring the equilibrium droplet profiles that are in turn used to evaluate the contact angles. Macroscopic arguments, such as those leading to Wenzel's law, suggest that surface roughness always amplifies the wetting properties of a lyophilic surface. However, our results indicate the opposite effect from roughness for microscopically corrugated surfaces, i.e., surface roughness deteriorates the substrate wettability. Adding the roughness to a strongly wettable surface shrinks the surface area wet with the liquid, and it either increases or only marginally affects the contact angle, depending on the degree of liquid adsorption into the nanogrooves. For a weakly wettable surface, the roughness changes the surface character from lyophilic to lyophobic due to a weakening of the solid-fluid interactions by the presence of the nanogrooves and the weaker adsorption of the liquid into the nanogrooves.

Orientational ordering and phase behaviour of binary mixtures of hard spheres and hard spherocylinders.

We study the structure and fluid-phase behaviour of binary mixtures of hard spheres (HSs) and hard spherocylinders (HSCs) in isotropic and nematic states using the NPnAT ensemble Monte Carlo (MC) approach in which the normal component of the pressure tensor is fixed in a system confined between two hard walls. The method allows one to estimate the location of the isotropic-nematic phase transition and to observe the asymmetry in the composition between the coexisting phases, with the expected enhancement of the HSC concentration in the nematic phase. This is in stark contrast with the previously reported MC simulations where a conventional isotropic NPT ensemble was used. We further compare the simulation results with the theoretical predictions of two analytic theories that extend the original Parsons-Lee theory using the one-fluid and the many-fluid approximations [Malijevský et al., J. Chem. Phys. 129, 144504 (2008)]. In the one-fluid version of the theory, the properties of the mixture are related to an effective one-component HS system, while in the many-fluid theory, the components of the mixtures are represented as separate effective HS particles. The comparison reveals that both the one- and the many-fluid approaches provide a reasonably accurate quantitative description of the mixture including the predictions of the isotropic-nematic phase boundary and degree of orientational order of the HSC-HS mixture.

Does surface roughness amplify wetting?

Any solid surface is intrinsically rough on the microscopic scale. In this paper, we study the effect of this roughness on the wetting properties of hydrophilic substrates. Macroscopic arguments, such as those leading to the well-known Wenzel's law, predict that surface roughness should amplify the wetting properties of such adsorbents. We use a fundamental measure density functional theory to demonstrate the opposite effect from roughness for microscopically corrugated surfaces, i.e., wetting is hindered. Based on three independent analyses we show that microscopic surface corrugation increases the wetting temperature or even makes the surface hydrophobic. Since for macroscopically corrugated surfaces the solid texture does indeed amplify wetting there must exist a crossover between two length-scale regimes that are distinguished by opposite response on surface roughening. This demonstrates how deceptive can be efforts to extend the thermodynamical laws beyond their macroscopic territory.

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. We construct the global phase diagram revealing a reentrant phenomenon pertinent to the change of the capillary condensation type upon varying the inclination of the walls. Asymptotic properties of the system are discussed and a link with related phase phenomena in different systems is made. Finally, we show that the change from a single- to a double-pinned state is a continuous transition, the character of which depends on the wetting properties of the walls.

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. This phenomenon is characterized by a power-law divergence with geometry-dependent critical exponents that we determine for a wide class of walls' geometries. In particular, for a linear-wedge model, a covariance law revealing a relation between a geometric and Young's contact angle is presented. These predictions are shown to be fully in line with the numerical results obtained from a microscopic (classical) density functional theory.

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., 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.

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 temperatureTc. 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 atTc. When nonwetting gaps appear the contact angle either vanishes or tends toπast≡(Tc-T)/Tc→0. More specifically, when the wall-fluid interaction is long-ranged (dispersion-like) and the fluid-fluid short-ranged we estimateπ-θ∝t0.16, compared withθ∝t0.77when the wall-fluid interaction is short-ranged and the fluid-fluid dispersion-like, allowing for the effects of bulk critical fluctuations. The universal convergence of the lines of constant contact angle implies that critical point filling always occurs for fluids adsorbed in wedges.

Critical point wedge filling.

We present results of a microscopic density functional theory study of wedge filling transitions, at a right-angle wedge, in the presence of dispersionlike wall-fluid forces. Far from the corner the walls of the wedge show a first-order wetting transition at a temperature T(w) which is progressively closer to the bulk critical temperature T(c) as the strength of the wall forces is reduced. In addition, the meniscus formed near the corner undergoes a filling transition at a temperature T(f)

Sedimentation of a two-dimensional colloidal mixture exhibiting liquid-liquid and gas-liquid phase separation: a dynamical density functional theory study.

We present dynamical density functional theory results for the time evolution of the density distribution of a sedimenting model two-dimensional binary mixture of colloids. The interplay between the bulk phase behaviour of the mixture, its interfacial properties at the confining walls, and the gravitational field gives rise to a rich variety of equilibrium and non-equilibrium morphologies. In the fluid state, the system exhibits both liquid-liquid and gas-liquid phase separation. As the system sediments, the phase separation significantly affects the dynamics and we explore situations where the final state is a coexistence of up to three different phases. Solving the dynamical equations in two-dimensions, we find that in certain situations the final density profiles of the two species have a symmetry that is different from that of the external potentials, which is perhaps surprising, given the statistical mechanics origin of the theory. The paper concludes with a discussion on this.

Does adsorption in a single nanogroove exhibit hysteresis?

A simple fluid, in a microscopic capillary capped at one end, is studied by means of fundamental measure density functional. The model represents a single, infinitely long nanogroove with long-range wall-fluid attractive (dispersion) forces. It is shown that the presence or absence of hysteresis in adsorption isotherms is determined by wetting properties of the wall as follows: Above wetting temperature, T(w), appropriate to a single wall of the groove, the adsorption is a continuous process corresponding to a rise of a meniscus from the capped to the open end of the groove. For a sufficiently deep capillary, the meniscus rise is shown to be a steep, yet continuous process taking place near the capillary condensation of a corresponding slit. However, for temperatures lower than T(w) the condensation exhibits a first-order transition accompanied by hysteresis of the adsorption isotherm. Finally, it is shown that hysteresis may occur even for T > T(w) as a consequence of prewetting on the side and bottom walls of the groove.

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. In contrast, for L

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. Connection with the general geometric construction proposed by Rascón and Parry is made. Our predictions are supported by a microscopic model density functional theory for drying at a sinusoidally shaped hard wall where we confirm the order of the transition and also an exact sum rule for the generalized contact theorem due to Upton. We show that as bulk coexistence is approached the adsorption isotherm separates into three regimes: A preosculation regime where it is microscopic, containing only a thin wetting layer; a mesoscopic regime, in which a meniscus sits within the troughs; and finally another microscopic regime where the liquid-gas interface unbinds from the crests of the substrate.

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 ß_{osc} characterizing the scale of the interfacial height ℓ_{0}∝R_{w}^{ß_{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. In the fluctuation-dominated regime, representing the universality class of systems with short-range forces, the exponent is related to the value of the interfacial wandering exponent ζ by ß_{osc}=3ζ/(4-ζ). In contrast, in the mean-field regime, which was not previously identified and which occurs for systems with longer-range forces (and higher dimensions), the exponent ß_{osc} takes the same value as the exponent ß_{s}^{co} for complete wetting, which is determined directly by the intermolecular forces. The prediction ß_{osc}=3/7 in d=2 for systems with short-range forces (corresponding to ζ=1/2) is confirmed using an interfacial Hamiltonian model which determines the exact scaling form for the decay of the interfacial height probability distribution function. A numerical study in d=3, based on a microscopic model density-functional theory, determines that ß_{osc}≈ß_{s}^{co}≈0.326 close to the predicted value of 1/3 appropriate to the mean-field regime for dispersion forces.

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. For intermediate capillaries, with 2/π1, 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. We test several of our predictions using a fully microscopic density functional theory which allows us to study the two types of capillary condensation and its suppression at the molecular level for different aspect ratios and contact angles.