Demixing of a binary mixture in slit-like pores at high temperatures

We investigate the fluid—fluid demixing transitions in the case of adsorption of so-called symmetric binary mixtures in slit-like pores at temperatures higher than the bulk gas—liquid critical temperature. The aim of the study is to determine how the demixing of such mixtures in the pores depends on the bulk phase composition and on the parameters characterizing the pore. The calculations have been carried out by means of a density functional theory. In the case of an equimolar bulk mixture, the demixing transition inside the pore occurs only when the adsorption potentials of both species are identical. The occurrence of this transition is manifested by a cusp in the adsorption isotherm. For nonequimolar bulk phase compositions, the transition can also take place if the adsorption energies of both components are different. However, the difference in the adsorption energies should be small enough, otherwise a continuous demixing takes place. For non-equimolar compositions two branches of the grand canonical potential intersect, whereas for equimolar bulk composition they meet tangentially. We have determined phase behaviour for several model systems.     

Entropic wetting and many-body induced layering in a model colloid-polymer mixture

We develop an efficient simulation scheme to study a model suspension of equally sized colloidal hard spheres and nonadsorbing ideal polymer coils, both in bulk and adsorbed against a planar hard wall. The many-body character of the polymer-mediated effective interactions between the colloids yields a bulk phase diagram and adsorption phenomena that differ substantially from those found for pairwise simple fluids; e.g., we find an anomalously large bulk liquid regime and, far from the bulk triple point, three layering transitions in the partial wetting regime prior to a transition to complete wetting by colloidal liquid.     

The mean-field adsorption on a sinusoidally corrugated substrate revised

The fluid system at the bulk liquid–gas coexistence in a presence of a sinusoidally corrugated substrate exhibits not only the wetting transition, but additionally a first-order, thin–thick transition. The mean-field analysis of this transition based on a simple effective Hamiltonian is valid only in long wavelength limit. In this case the filling transition occurs so close to the wetting temperature, that the behavior of the interface is dominated by fluctuations, therefore the mean-field approach breaks down. We analyze the filling transition with the help of Hamiltonian evaluated from Landau theory. The applicability of our Hamiltonian is not restricted only to the vicinity of the wetting point. We obtain the phase diagram valid beyond the temperature range corresponding to the strong fluctuations regime. It displays more complex dependence on different length scales of the system and includes the old one as a particular case.     

Pairwise correlations and wetting transitions at a solid-gas interface

We summarize the main results of our study of the density-density correlation function for Sullivan's model of a gas adsorbed on a solid substrate. In the approach to complete wetting, when a thick film of liquid density is adsorbed at the substrate, long-ranged transverse (parallel to the surface) correlations develop at the edge of the film where the density profile is similar to that of a liquid-gas interface. For a class I wetting situation the range of the transverse correlations increases and ultimately diverges as the bulk gas pressure approaches the saturated vapour pressure. We comment on other situations where long-ranged correlations arise and mention the possibility of observing these in diffraction experiments and in computer simulations. Sullivan's model always predicts a second-order phase transition between class II and class I wetting. By extending his model and allowing the attractive part of the solid-fluid potential to be longer-ranged than the attractive fluid-fluid potential we find that this wetting transition can become a first-order (Cahn) transition.     

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.     

Long ranged correlations at a solid-fluid interface A signature of the approach to complete wetting

We have investigated the behaviour of the pairwise distribution function for Sullivan's model of a gas adsorbed on a solid substrate. We show that in the approach to complete wetting, when a thick film of liquid density is adsorbed on the substrate, long ranged transverse correlations (parallel to the surface) develop at the edge of the film where the density profile of the fluid resembles that of a liquid-gas interface. The long ranged correlations can be attributed to damped capillary-wave-like fluctuations; for a class I wetting situation the damping decreases and the range of the correlations increases and ultimately diverges as the bulk gas pressure approaches the saturated vapour pressure.

Our analysis provides a physical explanation of the long ranged transverse correlations calculated by Foiles and Ashcroft in their recent study of a model of argon at a carbon dioxide substrate. We also predict that long range transverse correlations will occur for the case of adsorption from a dense liquid provided the solid-fluid potential is such that a thick film of gas forms between the substrate and the bulk liquid.     

Wetting-Induced Aggregation of Colloids

More than two decades ago, in a seminal paper John Cahn proposed scaling arguments for the possibility of a wetting transition in two coexisting fluid phases near the critical point. Since then, Cahn's model has been tested in many fluid systems and further refined by including the real interactions between the fluid and the solid wall. A fascinating consequence of the existence of a wetting transition is the possibility for a transition from weak to strong adsorption in the homogeneous phase. The situation is further enriched in nonstandard geometries having special geometrical constraints. The subject of this review concerns one such situation, where charge-stabilized colloidal particles are suspended in the homogeneous region of a binary liquid mixture. In this case, the preferential adsorption of one of the liquid components on to the colloid surface completely modifies the stability of the particles leading to an aggregation process. Although the exact mechanism underlying the adsorption phenomenon is still debated, it is closely related to the wetting transition. Recent experimental developments concerning the static and dynamic aspects of this phenomenon are reviewed. In addition, the main findings of a theoretical model based on the adsorption-modified electrostatic interactions between the colloidal particles are discussed.     

Demixing transitions in a binary Gaussian-core fluid confined in narrow slit-like pores

Using a mean-field density functional approach we investigate phase separation transition in a binary mixture of Gaussian-core molecules confined in narrow slit-like pores. We consider pores with repulsive and attractive walls. In the case of fluid confinement in pores with repulsive and non-selective attracting walls, no phase separation in the confined fluid, prior to the bulk separation transition, was observed. However, in the case of pores with the walls selectively attracting fluid particles, we reveal that the separation transition may take place as a two-step process. During the first step the composition change occurs within a few layers adjacent to the pore walls, whereas in the second step, it takes place in the pore interior.     

Wetting Transition of Nonpolar Neutral Molecule System on a Neutral and Atomic Length Scale Roughness Substrate

One recently proposed new method for accurately determining wetting temperature is applied to the wetting transition occurring in a single component nonpolar neutral molecule system near a neutral planar substrate with roughness produced by cosinusoidal modulation(s). New observations are summarized into five points: (i) for a planar substrate superimposed with one cosinusoidal modulation, with increasing of the periodicity length or the surface attraction force field, or decreasing of the amplitude, wetting temperature \(T_W\) drops accordingly and the three parameters show multiplication effect; moreover, both the periodicity length and amplitude effect curves display pole phenomena and saturation phenomena, and the \(T_W\) saturation occurs at small (for case of large amplitude) or large (for case of small amplitude) periodicity length side, respectively. (ii) In the case of the planar substrate superimposed with two cosinusoidal modulations with equal periodicity length, the initial phase difference is critical issue that influences the \(T_W\), which decreases with the initial phase difference. (iii) In the case of the planar substrate superimposed with two cosinusoidal modulations with zero phase difference, change of the \(T_W\) with one periodicity length under the condition of another periodicity length unchanged is non-monotonous. (iv) When the parameters are chosen such that the \(T_W\) draws ever closer to the bulk critical temperature, wetting transition on the roughness substrate eventually does not occur. (v) The present microscopic calculation challenges traditional macroscopic theory by confirming that the atomic length scale roughness always renders the surface less hydrophilic and whereas the mesoscopical roughness renders the surface more hydrophilic. All of these observations summarized can be reasonably explained by the relative strength of the attraction actually enjoyed by the surface gas molecules to the attraction the gas molecules can get when in bulk.     

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.     

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.     

Wetting, drying, and layering of colloid-polymer mixtures at porous interfaces

The influence of interface porosity on the wetting properties of colloid-polymer mixtures is studied within density functional theory for the Asakura-Oosawa-Vrij model at the surface of a quenched hard-sphere matrix. While the porosity hardly changes the location of the transition from partial to complete wetting at colloidal bulk gas-liquid coexistence, the onset of wetting, as signaled by the first discontinuous layering transition, can be efficiently controlled by tailoring the porosity. We furthermore find that the penetrability of the porous interface induces complete drying into the matrix upon approaching capillary coexistence.     

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.     

Hydrodynamic-flow-driven wetting in thin film polymer blends: growth kinetics and morphology

A thin film of deuterated poly(methyl methacrylate) (A) and poly(styrene-ran-acrylonitrile) at the critical composition is annealed in the two phase region to induce simultaneous phase separation and wetting of the A-rich phase at the surface. Using forward recoil spectrometry, the wetting layer thickness is found to grow linearly with time at 185 degrees C and 190 degrees C. After selective etching of A, atomic force microscopy reveals a depletion layer having a bicontinuous, phase separated morphology. The A-rich tubes in this layer provide a pathway for rapid transport of the wetting phase from the bulk to the surface via hydrodynamic flow. Taken together, fast wetting layer growth t(1) and connectivity between the wetting layer and bulk provide unambiguous support for hydrodynamic-flow-driven wetting in thin film polymer blends.     

Statistical-thermodynamic theory of ordering in a binary film deposited on the surface of a monocrystal

The ordering of a binary monolayer deposited on the surface of a monocrystal is studied. In the case when the structure of the film is equivalent to that of the crystal surface, the ordering in the film is qualitatively similar to that in the bulk of the sample: When the ordering energy is positive there exists an order-disorder phase transition at a certain temperature and for a certain concentration interval. If the structure of the film is different from the structure of the surface, then the film is ordered at all temperatures, independently of the sign of the ordering energy. In this case, in addition to the equilibrium ordered state in the region T < T_* (T_* is a certain temperature which is determined by the composition of the alloy and by the magnitude of the energy shift of the atoms of the film in the field of the substrate), there exists a metastable ordered state in which there is a jump-like change in the ordering at the point T_*, analogous to a first-order phase transition. Possible methods of experimental study of the ordering in films are discussed.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 5, pp. 53–57, May, 1987.     

Demixing transition in a quasi-two-dimensional surface-frozen layer

A thin/thick transition was observed by x-ray reflectivity in a surface-frozen crystalline bilayer on the surface of a molten binary mixture of long alcohols. This rare example of a solid-solid phase transition in a quasi-2D system is shown to result from an abrupt temperature-driven change in the layer's composition, kinetically enabled by the layer's ability to exchange molecules with the underlying 3D liquid bulk. Mean-field thermodynamics yields a Gibbs-adsorption-like expression which accounts very well for the transition.     

Surface freezing and a two-step pathway of the isotropic-smectic phase transition in colloidal rods

We study the kinetics of the isotropic-smectic phase transition in a colloidal rod/polymer mixture by visualizing individual smectic layers. First, we show that the bulk isotropic-smectic phase transition is preceded by a surface freezing transition in which a quasi-two-dimensional smectic phase wets the isotropic-nematic interface. Next, we identify a two-step kinetic pathway for the formation of a bulk smectic phase. In the first step a metastable isotropic-nematic interface is formed. This interface is wetted by the surface-induced smectic phase. In the subsequent step, smectic layers nucleate at this surface phase and grow into the isotropic bulk phase.     

Kinetic wetting of a moving planar defect by a new phase

Close to a bulk phase transition, a moving planar defect can be covered by a layer of the ordered phase. This, in fact, happens above the transition point in some finite region of the temperature-velocity diagram. In the case of a first-order transition this region is furnished with a net of nonequilibrium phase-transition lines. The topology of this net resembles that of the phase diagram of a first-order wetting transition in thermal equilibrium. In particular, there appears a kinetic complete-wetting line where a significant change of the drag coefficient of the defect is predicted.     

Reversible sphere-to-lamellar wetting transition at the interface of a diblock copolymer system

We use ellipsometry to investigate a transition in the morphology of a sphere-forming diblock copolymer thin-film system. At an interface the diblock morphology may differ from the bulk when the interfacial tension favours wetting of the minority domain, thereby inducing a sphere-to-lamella transition. In a small, favourable window in energetics, one may observe this transition simply by adjusting the temperature. Ellipsometry is ideally suited to the study of the transition because the additional interface created by the wetting layer affects the polarisation of light reflected from the sample. Here we study thin films of poly(butadiene-ethylene oxide) (PB-PEO), which order to form PEO minority spheres in a PB matrix. As temperature is varied, the reversible transition from a partially wetting layer of PEO spheres to a full wetting layer at the substrate is investigated.