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.

Abrupt onset of the capillary-wave spectrum at wall-fluid interfaces.

Surfaces between 3D solids and fluids exhibit a wide variety of phenomena both at equilibrium, such as roughening transitions, interfacial fluctuations and wetting, and also out-of-equilibrium, such as the surface growth of driven interfaces. These phenomena are described very successfully using lower dimensional (2D) effective models which focus on the physics associated with emergent mesoscopic lengths scales, parallel to the interface, where the 2D-like behaviour is physically transparent. However, the precise conditions under which this dimensional reduction is justifiable have remained unclear. Here we show that, for a wall-fluid interface, a dimensional reduction from 3D-like to 2D-like behaviour - identified via the decay of density correlations - occurs abruptly at a specific value of the contact angle, and indicates the beginning of interfacial-like 2D behaviour and the spontaneous onset of the capillary-wave spectrum. The reduction from 3D to 2D is characterised by the divergence of a correlation length perpendicular to the interface revealing a morphological change in the nature of density correlations. Counter-intuitive effects occur, including that 3D behaviour can persist up to the wetting temperature and also that 2D behaviour can begin when no wetting layer is present and the adsorption is negative.

Correction: Abrupt onset of the capillary-wave spectrum at wall-fluid interfaces.

Correction for 'Abrupt onset of the capillary-wave spectrum at wall-fluid interfaces' by Andrew O. Parry et al., Soft Matter, 2023, 19, 5668-5673, https://doi.org/10.1039/D3SM00761H.

Casimir Contribution to the Interfacial Hamiltonian for 3D Wetting.

Previous treatments of three-dimensional (3D) short-ranged wetting transitions have missed an entropic or low-temperature Casimir contribution to the binding potential describing the interaction between the unbinding interface and wall. This we determine by exactly deriving the interfacial model for 3D wetting from a more microscopic Landau-Ginzburg-Wilson Hamiltonian. The Casimir term changes the interpretation of fluctuation effects occurring at wetting transitions so that, for example, mean-field predictions are no longer obtained when interfacial fluctuations are ignored. While the Casimir contribution does not alter the surface phase diagram, it significantly increases the adsorption near a first-order wetting transition and changes completely the predicted critical singularities of tricritical wetting, including the nonuniversality occurring in 3D arising from interfacial fluctuations. Using the numerical renormalization group, we show that, for critical wetting, the asymptotic regime is extremely narrow with the growth of the parallel correlation length characterized by an effective exponent in quantitative agreement with Ising model simulations, resolving a long-standing controversy.

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.

Geometry-induced capillary emptying.

When a capillary is half-filled with liquid and turned to the horizontal, the liquid may flow out of the capillary or remain in it. For lack of a better criterion, the standard assumption is that the liquid will remain in a capillary of narrow cross-section, and will flow out otherwise. Here, we present a precise mathematical criterion that determines which of the two outcomes occurs for capillaries of arbitrary cross-sectional shape, and show that the standard assumption fails for certain simple geometries, leading to very rich and counterintuitive behavior. This opens the possibility of creating very sensitive microfluidic devices that respond readily to small physical changes, for instance, by triggering the sudden displacement of fluid along a capillary without the need of any external pumping.

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.

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)

Intrinsic fluid interfaces and nonlocality.

We present results of an extensive molecular dynamics simulation of the structure and fluctuations of a liquid-gas interface, close to its triple point, in a system with cutoff Lennard-Jones interactions. The equilibrium density profile, averaged and (shape dependent) constrained intrinsic density profiles together with the fluctuations of the interfacial shape are extracted using an intrinsic sampling method. The correlation between fluctuations in the interfacial shape and in the intrinsic density show that the latter is not due to rigid translations of some underlying profile, as is most commonly assumed. Instead, over the whole range of wavelengths from the system size down to the molecular diameter, we see wave-vector dependent behavior in good agreement with a nonlocal interfacial Hamiltonian theory specifying the shape dependence of the intrinsic profiles.

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.

Intermittent attractive interactions lead to microphase separation in nonmotile active matter.

Nonmotile active matter exhibits a wide range of nonequilibrium collective phenomena yet examples are crucially lacking in the literature. We present a microscopic model inspired by the bacteria Neisseria meningitidis in which diffusive agents feel intermittent attractive forces. Through a formal coarse-graining procedure, we show that this truly scalar model of active matter exhibits the time-reversal-symmetry breaking terms defining the Active Model B+ class. In particular, we confirm the presence of microphase separation by solving the kinetic equations numerically. We show that the switching rate controlling the interactions provides a regulation mechanism tuning the typical cluster size, e.g., in populations of bacteria interacting via type IV pili.

Fluid adsorption at the base of a cylinder.

We consider the adsorption of fluid at a cylinder protruding from a flat substrate. For small contact angles θ, a liquid drop condenses at the base, the size of which is determined by macroscopic arguments. The adsorption exhibits scaling behavior related to a number of phase transitions and, for systems with short-ranged forces, shows a remarkable property: for small θ, the height and width of the drop are near identical to expressions for the thickness and parallel correlation length for microscopic wetting films. The only difference is that the bulk correlation length is replaced by the cylinder radius. This geometrical amplification of the microscopic lengths occurs for second-order, first-order, and complete wetting transitions, and is specific to three dimensions. Similar phenomena occurs for long-ranged forces, and shows crossover scaling behavior.

The self-interaction of a fluid interface, the wavevector dependent surface tension and wedge filling.

We argue that whenever an interface, separating bulk fluid phases, adopts a non-planar configuration (induced by a confining geometry or thermal fluctuations, say), the energy cost of it will contain a non-local self-interaction term. For systems with short-ranged forces and Ising symmetry, we determine the self-interaction by integrating out bulk-like degrees of freedom from a more microscopic Landau-Ginzburg-Wilson model. The self-interaction can be written in a simple diagrammatic form involving integrals over effective two-body forces acting at the interface and consistently accounts for a number of known features of the microscopic model, including the wavevector dependence of the surface tension describing the fluctuations of a near planar interface. When applied to wedge filling transitions, the self-interaction describes the attraction between the wetting films on either side of the wedge. We show that, for sufficiently acute wedges, this can alter the order of the filling phase transition.

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.

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. We determine the surface phase diagram and show that this exhibits two triple points, where isolated drops, double drops, and triple drops coexist. For the symmetric case, D_{1}=D_{2}≡D, our results also confirm that the equilibrium droplet configuration always has the symmetry of the substrate corresponding to either three isolated drops when D is large or a single triple drop when D is small; however, symmetry-broken configurations do occur in a metastable part of the phase diagram which lies very close to the equilibrium-bridging phase boundary. Implications for phase transitions on other types of patterned surface are considered.