Avoided critical behavior in dynamically forced wetting

A solid object can be coated by a nonwetting liquid since a receding contact line cannot exceed a critical speed. In this Letter we study the dynamical wetting transition at which a liquid film gets deposited by withdrawing a vertical plate out of a liquid reservoir. It has recently been predicted that this wetting transition is critical with diverging time scales and coincides with the disappearance of stationary menisci. We demonstrate experimentally and theoretically that the transition is due to the formation of a solitary wave, well below the critical point. As a consequence, relaxation times remain finite at threshold. The structure of the liquid deposited on the plate involves a capillary ridge that does not trivially match the Landau-Levich film.     

Wetting of Alkanes on Water from a Cahn-Type Theory: Effects of Long-Range Forces

We apply the phenomenological wetting theory of Cahn to fluids with van der Waals forces, and in particular to the wetting of pentane on water. Taking into account explicitly the long-range substrate–adsorbate interaction allows us to reproduce the experimentally observed critical wetting transition, which arises from the vanishing of the Hamaker constant at T53°C. This transition is preceded by a first-order transition between a thin and a thick film at a (much) lower temperature. If long-range forces are neglected, this thin–thick transition is the only wetting transition and critical wetting is missed. Our study focuses on the development of useful theoretical tools, such as phase portraits and interface potentials adapted to systems with van der Waals forces.     

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.     

三维倾斜平板液氧降膜润湿数值模拟研究

建立三维倾斜平板降膜模型,利用VOF两相流模型计算了液氧降膜的润湿情况,研究了工质物性、倾斜角、液膜入口高度对润湿面积的影响。结果表明:Weber数(We)相同时,液氧和水的润湿比均随Kapitza数(Ka)增大而减小;相同Ka下,液氧和水的润湿比均随We增大而增大,而液氧润湿比一直小于水润湿比,两者的差值也随We增大而增大。拟合得到液氧在液膜入口高度0.4 mm、接触角70°时的界面润湿比经验关联式,拟合值和模拟值相对误差≤±20%;在We=0.76时,液氧的润湿比随倾斜角增大而减小,但降低速率随Ka增大而减小;在倾斜角为90°时,易出现液膜脱离壁面的现象;当We固定时,液氧的润湿比随液膜入口高度增大而增大。     

Excess Volume of the Solid/Liquid Interface in Fe-6 at.%Si Bicrystals Wetted by Liquid Zinc

The pressure effect on grain boundary wetting in Fe-6 at.%Si bicrystals of different misorientation angles but constant misorientation axis has been studied. The wetting agent was liquid zinc. It was found that the pressure for the dewetting transition is higher for the near 5 boundary than for the other general boundaries, where is the inverse density of the coincidence sites in the two misoriented crystal lattices. This result was explained assuming a thinner liquid film wetting the near 5 boundary than in the case of nonperiodic grain boundaries. Furthermore, the wetting angle increased with increasing pressure. The wetting angle dependence on pressure could be understood assuming a excess surface volume of the solid/liquid (S/L) interface higher than 0.2 nm. This is considerably higher than the estimated excess volumes of grain boundaries based on computer simulations. To explain this result, it was postulated that in the system studied, where diffusion of Zn, Fe and Si perpendicular to the S/L interface takes place, the S/L interface is relatively thick and the interaction between the two crystals separated by the melt extends over more than 2 nm distance. This long-range interaction was rationalized in terms of clusters of several atoms, detaching from the solid and dissolving in the melt at some distance from the bulk.     

A mesoscopic model for (de)wetting

We present a mesoscopic model for simulating the dynamics of a non-volatile liquid on a solid substrate. The wetting properties of the solid can be tuned from complete wetting to total non-wetting. This model opens the way to study the dynamics of drops and liquid thin films at mesoscopic length scales of the order of the nanometer. As particular applications, we analyze the kinetics of spreading of a liquid drop wetting a solid substrate and the dewetting of a liquid film on a hydrophobic substrate. In all these cases, very good agreement is found between simulations and theoretical predictions.     

Near-critical fluid boiling: Overheating and wetting films

The heating of coexisting gas and liquid phases of pure fluid through its critical point makes the fluid extremely compressible, expandable, slows the diffusive transport, and decreases the contact angle to zero (perfect wetting by the liquid phase). We have performed experiments on near-critical fluids in a variable volume cell in the weightlessness of an orbiting space vehicle, to suppress buoyancy-driven flows and gravitational constraints on the liquid-gas interface. The high compressibility, high thermal expansion, and low thermal diffusivity lead to a pronounced adiabatic heating called the piston effect. We have directly visualized the near-critical fluid’s boundary layer response to a volume quench when the external temperature is held constant. We have found that when the system’s temperature T is increased at a constant rate past the critical temperature T _c , the interior of the fluid gains a higher temperature than the hot wall (overheating). This extends previous results in temperature quenching experiments in a similarly prepared system when the gas is clearly isolated from the wall. Large elliptical wetting film distortions are also seen during these ramps. By ray tracing through the elliptically shaped wetting film, we find very thick wetting film on the walls. This wetting film is at least one order of magnitude thicker than films that form in the Earth’s gravity. The thick wetting film isolates the gas bubble from the wall allowing gas overheating to occur due to the difference in the piston effect response between gas and liquid. Remarkably, this overheating continues and actually increases when the fluid is ramped into the single-phase supercritical phase.     

Dewetting on porous media with aspiration

We consider a porous solid covered with a water film (or with a drop) in situations where the liquid is pumped in, either spontaneously (if the porous medium is hydrophilic) or mechanically (by an external pump). The dynamics of dewetting is then strongly modified. We analyse a few major examples, a) horizontal films, which break at a certain critical thickness, b) the “modified Landau-Levich problem” where a porous plate moves up from a bath and carries a film: aspiration towards the plate limits the height H reached by the film, c) certain situation where the hysteresis of contact angles is important. Received 5 October 1999 and Received in final form 7 February 2000     

Dynamics of wetting layer formation

We study the formation and growth of wetting layers in the binary liquid mixture cyclohexane-methanol. By progressively deuterating the methanol we can tune the equilibrium wetting layer thickness. Hysteresis of the transition is observed for large thicknesses and is absent for thinner ones. This can be understood by calculating the activation energy for wetting layer nucleation as a function of the film thickness. We also show that the late-stage growth of the wetting layer after the nucleation process follows a power law in time, in agreement with a diffusion-limited growth mechanism proposed theoretically.     

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.     

Generation of acoustic waves by power microwave pulses with the use of thin metal films

We study the features of excitation of acoustic waves by high-power microwave pulses in thin metal films bordering on liquid. Aluminum films with thicknesses 1–10 nm deposited onto a quartz substrate were used in experiments. It is shown theoretically that the absorption coefficient of microwaves is maximum for film thickness from 2 to 3 nm and the value of this maximum is determined by the dielectric permittivity of the bordering liquid. Theoretical calculations and experiments are performed for water and ethyl alcohol. The sound generation in a layered system quartz-aluminum film-liquid is analyzed with the help of the step-by-step approach. At the first step, microwave energy is absorbed in the film and heat is released. Then heat almost instantly diffuses into a liquid whose thermal expansion creates an acoustic signal. Profiles of acoustic signals excited in aluminum films by microwave pulses with a 5-ns duration and an energy of up to 1 mJ are experimentally detected. The most efficient transduction was observed for an aluminum film 3.5 nm thick.     

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.     

Spectroscopic evidence of a wetting and prewetting transition in liquid K-KCl mixtures

Spectroscopic ellipsometry and simultaneous reflectivity measurements of liquid KxKCl1-x solutions clearly exhibit a first order wetting transition in metal-rich melts. At the sample/substrate interface, salt-rich wetting films of mesoscopic thickness ( approximately 100 nm) are observed at and off of coexistence. They are uniquely characterized by the liquid F-center absorption band. However, crossing the prewetting line towards metal-rich concentrations, the F bands disappear. From the observation of the liquid F-center band, it is concluded that a strong undercooling of the wetting films of about 200 K may occur in binary metallic fluids, which is demonstrated here for the first time.     

Dissipative evolution of quantum statistical ensembles and nonlinear response to a time-periodic perturbation

We present a detailed discussion of the evolution of a statistical ensemble of quantum mechanical systems coupled weakly to a bath. The Hilbert space of the full system is given by the tensor product between the Hilbert spaces associated with the bath and the bathed system. The statistical states of the ensemble are described in terms of density matrices. Supposing the bath to be held at some - not necessarily thermal - statistical equilibrium and tracing over the bath degrees of freedom, we obtain reduced density matrices defining the statistical states of the bathed system. The master equations describing the evolution of these reduced density matrices are derived under the most general conditions. On time scales that are large with respect to the bath correlation time and with respect to the reciprocal transition frequencies of the bathed system, the resulting evolution of the reduced density matrix of the bathed system is of Markovian type. The detailed balance relations valid for a thermal equilibrium of the bath are derived and the conditions for the validity of the fluctuation-dissipation theorem are given. Based on the general approach, we investigate the non-linear response of the bathed subsystem to a time-periodic perturbation. Summing the perturbation series we obtain the coherences and the populations for arbitrary strengths of the perturbation.Received: 26 November 2003, Published online: 30 January 2004PACS: 05.30.-d Quantum statistical mechanics - 33.35. + r Electron resonance and relaxation - 33.25. + k Nuclear resonance and relaxation     

Thickening of a smectic membrane in an evanescent X-ray beam

We report an unusual thickening of smectic membranes under the influence of X-ray irradiation below the critical angle. In the case of a four-layer film the thickness was found to grow at the footprint of the beam, reaching within minutes tens of layers. The effect is attributed to the localized energy dissipation of the evanescent wave. The island thus created is not connected to the meniscus and after the beam is switched off the film returns to its original state. A possible explanation is given in terms of a local disrupture of the tension of the smectic membrane.Received: 22 July 2004, Published online: 1 October 2004PACS: 61.30.-v Liquid crystals - 61.30.Hn Surface phenomena: alignment, anchoring, anchoring transitions, surface-induced layering, surface-induced ordering, wetting, prewetting transitions, and wetting transitions - 52.25.Os Emission, absorption, and scattering of electromagnetic radiation     

Thin film dynamics in coating problems using Onsager principle

A new variational method is proposed to investigate the dynamics of the thin film in a coating flow where a liquid is delivered through a fixed slot gap onto a moving substrate. A simplified ODE system has also been derived for the evolution of the thin film whose thickness h_f is asymptotically constant behind the coating front. We calculate the phase diagram as well as the film profiles and approximate the film thickness theoretically, and agreement with the well-known scaling law as Ca~(2/3) is found.     

X-ray study of the wetting behaviour of CCl4 on Si/SiO2 surfaces

The complete wetting of an uncoated silicon wafer covered with a native oxide layer by saturated vapour of carbon tetrachloride was studied by using the x-ray reflectivity-technique. Differential heating of the substrate relative to a liquid reservoir was used to examine the disjoining pressure as a function of film thickness. The measurements were done at the temperaturesT=308K andT=318K of the reservoir. The observed film thicknesses varied between 26Å and 345Å depending on the temperature difference. A model for explaining the measured film thickness as a function of the temperature difference in terms of van der Waals forces is presented. It is based on the non-retarded interaction and includes terms of higher order in the film thickness. Microscopic constants like the Hamaker constant were determined and compared with reported values.     

Wetting by solid helium,a model system

This is a review of the wetting properties of solid helium on various solid substrates. Due to its extreme purity and to its very fast growth dynamics, solid helium 4 is often considered as a model system in materials science. Several wetting phenomena have been studied with helium 4 crystals, namely contact angles on solid substrates with variable roughness, wetting on graphite where epitaxial growth takes place, the roughening transition as a function of film thickness, the wetting of grain boundaries by the liquid phase.     

Quantum transport in mesoscopic 3He films: experimental study of the interference of bulk and boundary scattering

We discuss the mass transport of a degenerate Fermi liquid ^{3}He film over a rough surface, and the film momentum relaxation time, in the framework of theoretical predictions. In the mesoscopic regime, the anomalous temperature dependence of the relaxation time is explained in terms of the interference between elastic boundary scattering and inelastic quasiparticle-quasiparticle scattering within the film. We exploit a quasiclassical treatment of quantum size effects in the film in which the surface roughness, whose power spectrum is experimentally determined, is mapped into an effective disorder potential within a film of uniform thickness. Confirmation is provided by the introduction of elastic scattering centers within the film. The improved understanding of surface roughness scattering may impact on enhancing the conductivity in thin metallic films.