Surface aided replica exchange algorithm applied to the prewetting transition

A novel algorithm, termed surface aided replica exchange (SARE), was introduced in which the fluid–surface interaction was varied in order to generate different replicas in a particular ensemble. Exchange between replicas was allowed with a probability of acceptance obtained by imposing detailed balance. The method was implemented in a modified isothermal-isobaric ensemble that permitted precise characterization of the prewetting line of a simple adsorbed fluid. The prewetting line for each surface was characterized by computing the adsorption of the fluid as a function of pressure, and the wetting temperature estimated for each surface.     

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.     

Extraordinary wetting phase diagram for mixtures of Bose-Einstein condensates

The possibility of wetting phase transitions in Bose-Einstein condensed gases is predicted on the basis of Gross-Pitaevskii theory. The surface of a binary mixture of Bose-Einstein condensates can undergo a first-order wetting phase transition upon varying the interparticle interactions, using, e.g., Feshbach resonances. Interesting ultra-low-temperature effects shape the wetting phase diagram. The prewetting transition is, contrary to general expectations, not of first order but critical, and the prewetting line does not meet the bulk phase coexistence line tangentially. Experimental verification of these extraordinary results is called for, especially now that it has become possible, using optical methods, to realize a planar "hard wall" boundary for the condensates.     

Hydrogen and helium films as model systems of wetting

Optical experiments on the wetting properties of liquid ⁴He and molecular hydrogen are reviewed. Hydrogen films on noble metal surfaces serve as model systems for studying triple point wetting, a continuous transition between wetting and non-wetting. By means of optically excited surface plasmons, the adsorbed film thickness for temperatures around, and far below, the bulk melting temperature is measured, and the physical mechanisms responsible for the transition are elucidated. Possible applications for other experiments in pure and applied research are discussed. Thin films and droplets of liquid helium are studied on cesium surfaces, on which there is a first order wetting transition. Our studies concentrate on dynamical observations via surface plasmon microscopy, which provide insight into the morphology of liquid helium droplets spreading at different temperatures. Features corresponding to pinning forces, the prewetting line, and the Kosterlitz-Thouless transition are clearly observed.     

Phase transitions of adsorbed fluids computed from multiple-histogram reweighting

This paper demonstrates the effectiveness of using multiple-histogram reweighting (MHR) to study phase transitions in confined fluids by examining capillary condensation, prewetting, and layering transitions for different systems. A comparison is made with previously published simulations, where available, to establish the accuracy of MHR as applied to inhomogeneous systems. Overlap between adjacent state points is assessed through single-histogram reweighting. Capillary condensation for methane adsorption in slit-like graphite pores exhibits 2D behaviour. Crossover of the effective exponent for the width of the coexistence curve from 2D Ising-like (1/8) further away from the critical point to mean-field (1/2) near the critical point is observed. The reduced critical temperature, the density and the effective value of the exponent for the model system are 0.77, 0.482, and 0.119, respectively, based on a fit to the simulation data. Prewetting transitions are observed for adsorption of Ar on solid CO₂ using model potentials. The wetting temperature is estimated based on the intersection of the pre-wetting and bulk vapour-liquid lines, and also by extrapolation to zero of the difference between the saturation and prewetting chemical potentials. The reduced wetting temperature is estimated to be around 0.69. The reduced prewetting critical temperature, calculated from the disappearance of the two peaks in the density probability distribution, is estimated to be 0.92. The monolayer to bilayer (1-2) transition for propane on graphite is computed over a range of temperatures. Results for the 1–2 layering transition computed from MHR from a small system are in good agreement with grand canonical Monte Carlo simulations for a much larger system.     

Grain Boundary Phase Transitions and their Influence on Properties of Polycrystals

Grain boundary (GB) phase transitions can change drastically the properties of polycrystals. The GB wetting phase transition can occur in the two-phase area of the bulk phase diagram where the liquid (L) and solid (S) phases are in equlibrium. Above the temperature of the GB wetting phase transition a GB cannot exist in equlibrium contact with the liquid phase. The experimental data on GB wetting phase transitions in numerous systems are analysed. The GB wetting tie-line can continue in the one-phase area of the bulk phase diagram as a GB solidus line. This line represents the GB premelting or prewetting phase transitions. The GB properties change drastically when GB solidus line is crossed by a change in the temperature or concentration. The experimental data on GB segregation, energy, mobility and diffusivity obtained in various systems both in polycrystals and bicrystals are analysed. In case if two solid phases are in equilibrium, the GB “solid state wetting” can occur. In this case the layer of the solid phase 2 has to substitute GBs in the solid phase 1. Such GB phase transition occurs if the energy of two interphase boundaries is lower than the GB energy in the phase 1.     

Random anisotropy nematic model: Connection with experimental systems

We study theoretically the phase behavior of the continuum Random Anisotropy Nematic model. A domain-type pattern is assumed to appear in a distorted nematic liquid crystal (LC) phase. We map the model parameters to physical quantities characterizing LCs confined to Controlled-Pore Glasses and LC-aerosil dispersions. The domain size dependence on the disorder strength is obtained in accordance with the Imry-Ma prediction. The model estimates for temperature shifts of the paranematic-nematic phase transition and for the critical point, where this transition ceases to exist, are compared to the available experimental results.Received: 28 March 2004, Published online: 29 June 2004PACS: 61.30.-v Liquid crystals - 61.30.Dk Continuum models and theories of liquid crystal structure - 61.30.Gd Orientational order of liquid crystals; electric and magnetic field effects on order - 61.30.Hn Surface phenomena: alignment, anchoring, anchoring transitions, surface-induced layering, surface-induced ordering, wetting, prewetting transitions, and wetting transitions     

Stability of thin nematic films

We discuss the peculiarity of thin nematic films on solid substrates with a free surface, underlining the differences with what is usually seen in dewetting. We review the thermodynamic basis of the coupled phase/thickness separation that has previously been shown experimentally. We give new experimental evidences for the origin of the coupling force chosen in our previous theoretical model. This additional information contributes to the discussion raised by the article of Ziherl and Zumer in this issue [19].Received: 3 December 2003PACS: 68.15. + e Liquid thin films - 64.70.Md Transitions in liquid crystals - 61.30 Surface phenomena in liquid crystals including anchoring, anchoring transitions, surface-induced layering, surface-induced ordering, wetting, prewetting transitions and wetting transitions     

Stabilization of Nanoscale Quasi-Liquid Interfacial Films in Inorganic Materials: A Review and Critical Assessment

Recent observations of three classes of nanometer-thick, disordered, interfacial films in multicomponent inorganic materials are reviewed and critically assessed. The three classes of films are equilibrium-thickness intergranular films (IGFs) in ceramics, their free-surface counterparts, that is, surficial amorphous films (SAFs), and their metallic counterparts. Also briefly reviewed are several related wetting and adsorption phenomena in simpler systems, including premelting in unary systems, prewetting in binary liquids or vapor adsorption on inert walls, and frustrated-complete wetting. Analogous diffuse-interface and force-balance models are discussed with the goal of exploring a unifying thermodynamic framework. In general, the stability of these nanometer-thick interfacial films does not follow bulk phase diagrams. Stabilization of quasi-liquid interfacial films at subeutectic or undersaturation conditions in multicomponent materials can be understood from coupled interfacial premelting and prewetting transitions. More realistic models should include additional interfacial interactions, for example, dispersion and electrostatic forces, and consider the possibility for metastable equilibration. It is suggested that quasi-liquid grain boundary films in binary metallic systems can be used to validate a basic thermodynamic model. These nanoscale interfacial films are technologically important. For example, the short-circuit diffusion that occurs in interface-stabilized, subeutectic, quasi-liquid films explains the long-standing mystery of the solid-state activated sintering mechanism in ceramics, refractory metals, and ice.     

Wetting, spreading, and adsorption on randomly rough surfaces

The wetting properties of solid substrates with customary (i.e., macroscopic) random roughness are considered as a function of the microscopic contact angle of the wetting liquid and its partial pressure in the surrounding gas phase. Analytic expressions are derived which allow for any given lateral correlation function and height distribution of the roughness to calculate the wetting phase diagram, the adsorption isotherms, and to locate the percolation transition in the adsorbed liquid film. Most features turn out to depend only on a few key parameters of the roughness, which can be clearly identified. It is shown that a first-order transition in the adsorbed film thickness, which we term "Wenzel prewetting", occurs generically on typical roughness topographies, but is absent on purely Gaussian roughness. It is thereby shown that even subtle deviations from Gaussian roughness characteristics may be essential for correctly predicting even qualitative aspects of wetting.     

Surface phase transitions of multiple-site associating fluids

Surface phase transitions of Lennard–Jones (LJ) based two- and four-site associating fluids have been studied for various associating strengths using grand-canonical transition matrix Monte Carlo simulations. Our results suggest that, in the case of a smooth surface, represented by a LJ 9-3-type potential, multiple-site associating fluids display a prewetting transition within a certain temperature range. However, the range of the prewetting transition decreases with increasing associating strength and increasing number of sites on the fluid molecules. With the addition of associating sites on the surface, a quasi-2D vapor–liquid transition may appear, which is observed at a higher surface site density for weaker associating fluids. The prewetting transition at lower associating strength is found to shift towards the quasi-2D vapor–liquid transition with increasing surface site density. However, for highly associating fluids, the prewetting transition is still intact, but shifts slightly towards the lower temperature range. Adsorption isotherms, chemical potentials and density profiles are used to characterize surface phase transitions.     

An exactly solved model with a wetting transition

A model of a binary mixture, showing a wetting transition, is examined. No prewetting phenomena are found. The scaling functions are obtained for the film thickness and for the correlation lengths.     

Cross-Over Between First-Order and Critical Wetting at the Liquid-Vapour Interface of n-Alkane/Methanol Mixtures: Tricritical Wetting and Critical Prewetting

A simple mean-field theory is presented which describes the basic observations of recent experiments revealing rich wetting behaviour of n-alkane/methanol mixtures at the liquid-vapour interface. The theory, qualitative and in part heuristic, is based on a microscopic lattice-gas model from which a Cahn–Landau approach is distilled. Besides the physics associated with the short-range components of the intermolecular interactions, effects of the long-range tails of the net van der Waals forces between interfaces are also taken into account. Further, gravitational thinning of the wetting phase is incorporated. The calculation of the spreading coefficient S is extended to the experimentally relevant situation in which the bulk adsorbate is slightly away from two-phase coexistence due to gravity. Analysis of this novel approximation to S for systems with short-range forces leads to the conclusion that the surface specific heat exponents _s =1,1/2, and 0, for first-order wetting, tricritical wetting and critical wetting, respectively, are robust with respect to (weak) gravitational thinning, consistently with experiment. For three different systems the adsorption is calculated as a function of temperature and compared with the experimentally measured ellipticity. Including weak long-range forces which favour wetting in the theory does not visibly alter the critical wetting transition for the nonane/methanol mixture, in contrast with the generic expectation of first-order wetting for such systems, but in good agreement with experiment. For decane/methanol weak long-range forces bring the transition very close to the prewetting critical point, leading to an adsorption behaviour closely reminiscent of short-range tricritical wetting, observed experimentally for alkane chain length between 9.6 and 10. Finally, for undecane/methanol the transition is clearly of first order. First-order wetting is also seen in the experiment.     

Morphology and structure of thin liquid-crystalline films at nematic-isotropic transition

We review the main features of very thin nematic liquid-crystalline films on solid substrates, focusing on 5CB on oxidized silicon wafers. By discussing the theoretical aspects of the observed structures, we show that the phenomena at work include isotropic capillary condensation and that the coexistence of isotropic and nematic terraces in thin films is a result of the interplay of several mechanisms. Further theoretical as well as experimental efforts are needed to completely understand the wetting behavior of these systems.Received: 1 August 2003PACS: 68.08.Bc Wetting - 68.15. + e Liquid thin films - 61.30.Hn Surface phenomena in liquid crystals including anchoring, anchoring transitions, surface-induced layering, surface-induced ordering, wetting, prewetting transitions, and wetting transitions     

Static and dynamic electro-optic properties of a SmC* phase in surface stabilized geometry and dispersed in the polymer matrix

Comparative electro-optical measurements have been made on a ferroelectric liquid crystal (FLC) in surface stabilized geometry and confined to an ellipsoidal cavity within a polymer matrix. The static and dynamic electro-optical characteristics were measured for both systems and show qualitatively similar behaviours. A fast switching and important bistability were observed and characterized as a function of the applied electric field strength. The switching time between the two stable states of the surface stabilized cell was found to be longer than that found for the composite films. We argue that the faster switching dynamic of the FLC in cavities is due to the enhance of the rotational mobility of the molecules, probably (and partly) because of the soft anchoring character of the molecules at the cavity walls. Using a collective switching model in the high field regime, which assume a linear coupling between the spontaneous polarization and the local cavity electric field, we give an estimate of the rotational viscosity of the FLC molecules in the droplets.Received: 5 October 2003, Published online: 5 February 2004PACS: 61.30.Pq Microconfined liquid crystals: droplets, cylinders, randomly confined liquid crystals, polymer dispersed liquid crystals, and porous systems - 61.30.Hn Surface phenomena: alignment, anchoring, anchoring transitions, surface-induced layering, surface-induced ordering, wetting, prewetting transitions, and wetting transitions - 77.80.Fm Switching phenomena     

Suspended penetration wetting state of droplets on microstructured surfaces

When a water droplet on a micropillar-structured hydrophobic surface is submitted to gradually increased pressure, the CassieBaxter wetting state transforms into the Wenzel wetting state once the pressure exceeds a critical value. It has been assumed that the reverse transition(Wenzel-to-Cassie-Baxter wetting state) cannot happen spontaneously after the pressure has been removed.In this paper, we report a new wetting-state transition. When external pressure is exerted on a droplet in the Cassie-Baxter wetting state on textured surfaces with high micropillars to trigger the breakdown of this wetting state, the droplet penetrates the micropillars but does not touch the base of the surface to trigger the occurrence of the Wenzel wetting state. We have named this state the suspended penetration wetting state. Spontaneous recovery from the suspended penetration wetting state to the initial Cassie-Baxter wetting state is achieved when the pressure is removed. Based on the experimental results, we built models to establish the penetration depth that the suspended penetration wetting state could achieve and to understand the energy barrier that influences the equilibrium position of the liquid surface. These results deepen our understanding of wetting states on rough surfaces subjected to external disturbances and shed new light on the design of superhydrophobic materials with a robust wetting stability.     

Prewetting boundary tensions from Monte Carlo simulation

We examine the boundary tension of a model system along the prewetting saturation line. Boundary tensions are evaluated through a combination of finite-size scaling and grand canonical Monte Carlo simulation. The model system consists of Lennard-Jones particles interacting with a single structureless surface. After scaling our dimensionless results with a characteristic force, we obtain a value of 2 x 10(-11) N for the boundary tension at the system's wetting temperature. This estimate is consistent with theoretical and recent experimental values.     

Helium wetting: Theme and variations on inhomogeneous helium

The surprising discovery, in 1991, that liquid helium does not wet a cesium surface at low temperature has triggered an important activity both theoretical and experimental: helium has become a model system for the study of wetting transitions. After summarizing the main theme of helium wetting, I will focus on more recent studies, such as the structure and excitations of helium interfaces, experiments on the capillary rise, the “surfactant effect” of helium-3 impurities on liquid helium-4 and the “quantum prewetting transition” of pure helium-3. Unexpected consequences on the phase separation of³He?⁴He mixtures in restricted geometry will be drawn.     

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.