Critical effects at 3D wedge wetting

We show that continuous filling transitions are possible in 3D wedge geometries made from substrates exhibiting first-order wetting transitions, and develop a fluctuation theory yielding a complete classification of the critical behavior. Our fluctuation theory is based on the derivation of a Ginzburg criterion for filling and also on an exact transfer-matrix analysis of a novel effective Hamiltonian that we propose as a model for wedge fluctuation effects. The influence of interfacial fluctuations is very strong and, in particular, leads to a remarkable universal divergence of the interfacial roughness xi( perpendicular) approximately (T(F)-T)(-1/4) on approaching the filling temperature T(F), valid for all possible types of intermolecular forces.     

Depinning and wetting in two-dimensional Potts and chiral clock models

The interplay of depinning and interfacial adsorption or wetting phenomena is studied for two-dimensional three-state Potts and chiral clock models where the variables on opposite boundaries are fixed in different states and the interactions near one of the surfaces are weakened compared to the ones in the bulk. Using a transfer matrix approach and Monte Carlo techniques a new interfacial multicritical point is found at which both interfacial properties become critical simultaneously. However, in general the two types of transitions are decoupled.     

Nonlocality and short-range wetting phenomena

We propose a nonlocal interfacial model for 3D short-range wetting at planar and nonplanar walls. The model is characterized by a binding-potential functional depending only on the bulk Ornstein-Zernike correlation function, which arises from different classes of tubelike fluctuations that connect the interface and the substrate. The theory provides a physical explanation for the origin of the effective position-dependent stiffness and binding potential in approximate local theories and also obeys the necessary classical wedge covariance relationship between wetting and wedge filling. Renormalization group and computer simulation studies reveal the strong nonperturbative influence of nonlocality at critical wetting, throwing light on long-standing theoretical problems regarding the order of the phase transition.     

First-order and critical wetting of alkanes on water

Ellipsometry measurements of the wetting behavior of different alkanes on water show a sequence of two wetting transitions: a first-order (discontinuous) transition followed by a critical (continuous) one. We report temperature-induced wetting transitions for different alkanes and a novel pressure-induced wetting transition for an alkane mixture. The experiments enable us to determine the global wetting phase diagram as a function of chain length and temperature which we subsequently calculate theoretically. The two transition lines are found to be approximately parallel, in accordance with basic theoretical arguments.     

Theory of interfacial phase transitions in surfactant systems

The spin-1 Ising model, which is equivalent to the three-component lattice gas model, is used to study wetting transitions in three-component surfactant systems consisting of an oil, water, and a nonionic surfactant. Phase equilibria, interfacial profiles, and interfacial tensions for three-phase equilibrium are determined in mean field approximation, for a wide range of temperature and interaction parameters. Surfactant interaction parameters are found to strongly influence interfacial tensions, reducing them in some cases to ultralow values. Interfacial tensions are used to determine whether the middle phase, rich in surfactant, wets or does not wet the interface between the oil-rich and water-rich phases. By varying temperature and interaction parameters, a wetting transition is located and found to be of the first order. Comparison is made with recent experimental results on wetting transitions in ternary surfactant systems.This paper is dedicated to J. K. Percus in honor of his 65th birthday.     

Fluid adsorption near an apex: covariance between complete and critical wetting

Critical wetting is an elusive phenomenon for solid-fluid interfaces. Using interfacial models we show that the diverging length scales, which characterize complete wetting at an apex, precisely mimic critical wetting with the apex angle behaving as the contact angle. Transfer matrix, renormalization group, and mean-field analysis show that this covariance is obeyed in 2D and 3D and for long- and short-ranged forces. This connection should be experimentally accessible and provides a means of checking theoretical predictions for critical wetting.     

Wetting transitions in polydisperse fluids

The properties of the coexisting bulk gas and liquid phases of a polydisperse fluid depend not only on the prevailing temperature but also on the overall parent density. As a result, a polydisperse fluid near a wall will exhibit density-driven wetting transitions inside the coexistence region. We propose a likely topology for the wetting phase diagram, which we test using Monte Carlo simulations of a model polydisperse fluid at an attractive wall, tracing the wetting line inside the cloud curve and identifying the relationship to prewetting.     

3D short-range wetting and nonlocality

Analysis of a microscopic Landau-Ginzburg-Wilson model of 3D short-ranged wetting shows that correlation functions are characterized by two length scales, not one, as previously thought. This has a simple diagrammatic explanation using a nonlocal interfacial Hamiltonian and yields a thermodynamically consistent theory of wetting in keeping with exact sum rules. For critical wetting the second length serves to lower the cutoff in the spectrum of interfacial fluctuations determining the repulsion from the wall. We show how this corrects previous renormalization group predictions for fluctuation effects, based on local interfacial Hamiltonians. In particular, lowering the cutoff leads to a substantial reduction in the effective value of the wetting parameter and prevents the transition being driven first order. Quantitative comparison with Ising model simulation studies due to Binder, Landau, and co-workers is also made.     

Mean-field phenomenology of wetting in nanogrooves

ABSTRACT

In this special issue article, we bring together our recent research on wetting in confinement, in particular planar walls, wedges, capillary grooves and slit pores, with emphasis on phase transitions and competition between wetting, filling and condensation, and highlight their similarities and disparities. The results presented are obtained with the classical density functional theory (DFT) for fluids, which is a mean-field statistical mechanical framework for including the spatial variations of the fluid density into the thermodynamic equation of state. For wetting in sculpted substrates, we solve numerically the DFT equations to obtain the fluid density profiles, wetting isotherms and phase diagrams. This allows us to contrast the wetting phenomenology of grooves, planar walls, slit and wedge-shaped pores. Of particular interest are the transitions associated with capillary condensation, planar pre-wetting and mean-field wedge pre-filling lines.     

Fluctuation forces and wetting layers in colloid-polymer mixtures

We present confocal microscopy experiments on the wetting of phase-separated colloid-polymer mixtures. We observe that an unusually thick wetting layer of the colloid-rich phase forms at the walls of the glass container that holds the mixture. Because of the ultralow interfacial tension between the colloid-rich and the polymer-rich phases, the thermally activated roughness of the interfaces becomes very big and measurable. We observe that close to the critical point the roughness of the interface between the wetting layer and the polymer-rich phase decreases with decreasing layer thickness: large excursions of the interface are confined in the wetting layer. The measured relationship between the roughness and the thickness of the wetting layer is in qualitative agreement with the predictions of renormalization group theory for short-range forces and complete wetting.     

Wetting phase transitions and critical phenomena in condensed matter

Equilibrium wetting phase transitions and critical phenomena are discussed from a phenomenological point of view. The ubiquitous character of the wetting phase transition is illustrated through its occurrence in a variety of condensed matter systems, ranging from classical fluids to superconductors and Bose-Einstein condensates. The intriguing behaviour of the three-phase contact line and its line tension, at wetting, is an example of a fundamental problem in this field on which much progress has been made.     

Condensation in a capped capillary is a continuous critical phenomenon

We show that condensation in a capped capillary slit is a continuous interfacial critical phenomenon, related intimately to several other surface phase transitions. In three dimensions, the adsorption and desorption branches correspond to the unbinding of the meniscus from the cap and opening, respectively, and are equivalent to 2D-like complete-wetting transitions. For dispersion forces, the singularities on the two branches are distinct, owing to the different interplay of geometry and intermolecular forces. In two dimensions we establish precise connection, or covariance, with 2D critical-wetting and wedge-filling transitions: i.e., we establish that certain interfacial properties in very different geometries are identical. Our predictions of universal scaling and covariance in finite capillaries are supported by extensive Ising model simulation studies in two and three dimensions.     

Nonequilibrium wetting transition in a nonthermal 2D Ising model

Nonequilibrium wetting transitions are observed in Monte Carlo simulations of a kinetic spin system in the absence of a detailed balance condition with respect to an energy functional. A nonthermal model is proposed starting from a two-dimensional Ising spin lattice at zero temperature with two boundaries subject to opposing surface fields. Local spin excitations are only allowed by absorbing an energy quantum (photon) below a cutoff energy E _c . Local spin relaxation takes place by emitting a photon which leaves the lattice. Using Monte Carlo simulation nonequilibrium critical wetting transitions are observed as well as nonequilibrium first-order wetting phenomena, respectively in the absence or presence of absorbing states of the spin system. The transitions are identified from the behavior of the probability distribution of a suitably chosen order parameter that was proven useful for studying wetting in the (thermal) Ising model.     

Recent advances on “ordered water monolayer that does not completely wet water” at room temperature

The molecular scales behavior of interfacial water at the solid/liquid interfaces is of a fundamental significance in a diverse set of technical and scientific contexts,ranging from the efficiency of oil mining to the activity of biological molecules.Recently,it has become recognized that,both the physical interactions and the surface morphology have significant impact on the behavior of interfacial water,including the water structures as well as the wetting properties of the surface.In this review,we summarize some of recent advances in the atom-level pictures of the interfacial water,which exhibits the ordered character on various solid surfaces at room or cryogenic temperature.Special focus has been devoted to the wetting phenomenon of"ordered water monolayer that does not completely wet water"and the underlying mechanism on model and some real solid surfaces at room temperature.The possible applications of this phenomenon are also discussed.     

Wetting transitions of simple liquid films adsorbed on self-assembled monolayer substrates: an ellipsometric study

We report on an ellipsometric experimental study designed to explore the relevance of the wetting phase diagram predicted by liquid state physics of basic models, to the wide class of simple organic liquid films that adsorb from saturated vapour onto planar substrates at room temperature. The wetting properties are explored by measuring adsorption isotherms in the approach to saturation, in particular, for adsorption of n-hexane on a variety of specially constructed substrates (self-assembled monolayers) spanning a wide range of surface energy, and by carrying out the microscopic equivalent of contact angle experiments at saturation. We locate a wetting transition, which in our case is continuous, and then study its properties in detail. The general prediction of the wetting phase diagram, that wetting transitions should be ubiquitous in nature and readily located via control over the substrate field, is supported by our data, but the quantitative nature of the thick film adsorption regime is not in agreement with Lifshitz theory. This conclusion supports the work of a variety of earlier related studies, but contrasts with recent results for adsorption onto the surface of water. In addition, the correlation length determined from our complete wetting adsorption isotherms is mesoscopic, suggesting that equilibrium statistical mechanics of simple models of inhomogeneous fluids cannot explain the data.     

Spreading of a drop on a contaminated substrate

Most wetting or spreading problems are treated with surface and interfacial free energies taken as constants for the system in question. We consider here the case where a two-dimensional drop (ribbon) is deposited on a solid substrate bearing a very fine layer of a contaminant which modifies the effective drop/solid interfacial free energy. As the contaminant diffuses into the drop, the interfacial free energy, and thus the capillary balance, evolve. This has strange effects on wetting behaviour, including causing a wetting `overshoot'. Possible applications are briefly discussed.     

Wetting properties of rare gases on weak substrates

Since the original prediction that liquid He does not wet Cs at low temperatures and the soon after experimental observation of a wetting transition on this system, noble gases on alkalis have become model systems for the study of wetting transitions and of their accompanying line of prewetting transitions off coexistence. Here we review very briefly the theory of wetting and prewetting and discuss some results on the properties of rare gases adsorbed on alkali surfaces obtained with the use of the density functional theory and of accurate adsorbate-substrate potentials.     

Spurious character of singularities associated with phase transitions in cylindrical pores

Phase transitions of simple fluids and binary fluid mixtures confined into long cylindrical pores are re-examined, such as capillary condensation/evaporation and wetting transitions. While a large part of the literature ignores the fact that due to the quasi-one-dimensional character of these systems a singular behavior associated with a sharp phase transition cannot occur, we pay attention to the extent in which these phase transitions are smoothed out (in relation to the magnitude of the pore cross-sectional area). We argue that the finiteness of the pore length is an important parameter which controls the physical phenomena that are observed in simulations (and presumably also experiments explaining the distinction between the apparent “pore critical temperature” and the “hysteresis critical temperature”). We illustrate our arguments with recent findings from simulations of a lattice gas/Ising system and of the Asakura-Oosawa model of colloid-polymer mixtures.     

Coupled Hamiltonians and three-dimensional short-range wetting transitions

We address three problems faced by effective interfacial Hamiltonian models of wetting based on a single collective coordinate

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(y) representing the position of the unbinding fluid interface. Problems (P1) and (P2) refer to the predictions of non-universality at the upper critical dimension d = 3 at critical and complete wetting, respectively, which are not borne out by Ising model simulation studies. (P3) relates to mean-field correlation function structure in the underlying continuum Landau model. Building on earlier work by Parry and Boulter we investigate the hypothesis that these concerns arise due to the coupling of order parameter fluctuations near the unbinding interface and wall. For quite general choices of collective coordinates X_i(y) we show that arbitrary two-field models H[X₁,X₂] can recover the required anomalous structure of mean-field correlation functions (P3). To go beyond mean-field theory we introduce a set

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of Hamiltonians based on proper collective coordinates s(y) near the wall which have both interfacial and spin-like components. We argue that an optimum model H[s,

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]

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, in which the degree of coupling is controlled by an angle like variable δ^*, best describes the non-universality of the Ising model and investigate its critical behaviour. For critical wetting the appropriate Ginzburg criterion shows that the true asymptotic critical regime for the local susceptibility χ₁ is dramatically reduced consistent with observations of mean-field behaviour in simulations (P1). For complete wetting the model yields a precise expression for the temperature dependence of the renormalised critical amplitude θ in good agreement with simulations (P2). We highlight the importance of a new wetting parameter which describes the physics that emerges due to the coupling effects.