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Register a new userInterplay of complete wetting, critical adsorption, and capillary condensation
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The excess adsorption $Gamma $ in two-dimensional Ising strips $(infty times L)$ subject to identical boundary fields, at both one-dimensional surfaces decaying in the orthogonal direction $j$ as $-h_1j^{-p}$, is studied for various values of $p$ and along various thermodynamic paths below the critical point by means of the density-matrix renormalization-group method. The crossover behavior between the complete wetting and critical adsorption regimes, occurring in semi-infinite systems, are strongly influenced by confinement effects. Along isotherms $T=const$ the asymptotic power law dependences on the external bulk field, which characterize these two regimes, are undercut by capillary condensation. Along the pseudo first-order phase coexistence line of the strips, which varies with temperature, we find a broad crossover regime where both the thickness of the wetting film and $Gamma$ increase as function of the reduced temperature $tau$ but do not follow any power law. Above the wetting temperature the order parameter profiles are not slab-like but exhibit wide interfacial variations and pronounced tails. Inter alia, our explicit calculations demonstrate that, contrary to opposite claims by Kroll and Lipowsky [Phys. Rev. B {bf 28}, 5273 (1983)], for $p=2$ critical wetting transitions do exist and we determine the corresponding wetting phase diagram in the $(h_1,T)$ plane.
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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 (3d), 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 2d 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 2d and 3d.
Using general scaling arguments combined with mean-field theory we investigate the critical ($T simeq T_c$) and off-critical ($T e T_c$) behavior of the Casimir forces in fluid films of thickness $L$ governed by dispersion forces and exposed to long-ranged substrate potentials which are taken to be equal on both sides of the film. We study the resulting effective force acting on the confining substrates as a function of $T$ and of the chemical potential $mu$. We find that the total force is attractive both below and above $T_c$. If, however, the direct substrate-substrate contribution is subtracted, the force is repulsive everywhere except near the bulk critical point $(T_c,mu_c)$, where critical density fluctuations arise, or except at low temperatures and $(L/a) (betaDelta mu) =O(1)$, with $Delta mu=mu-mu_c <0$ and $a$ the characteristic distance between the molecules of the fluid, i.e., in the capillary condensation regime. While near the critical point the maximal amplitude of the attractive force if of order of $L^{-d}$ in the capillary condensation regime the force is much stronger with maximal amplitude decaying as $L^{-1}$. Essential deviations from the standard finite-size scaling behavior are observed within the finite-size critical region $L/xi=O(1)$ for films with thicknesses $L lesssim L_{rm crit}$, where $L_{rm crit}=xi_0^pm (16 |s|)^{ u/beta}$, with $ u$ and $beta$ as the standard bulk critical exponents and with $s=O(1)$ as the dimensionless parameter that characterizes the relative strength of the long-ranged tail of the substrate-fluid over the fluid-fluid interaction. We present the modified finite-size scaling pertinent for such a case and analyze in detail the finite-size behavior in this region.
Using grand canonical Monte Carlo simulations, we have explored the phenomenon of capillary condensation (CC) of Ar at the triple temperature inside infinitely long, cylindrical pores. Pores of radius R= 1 nm, 1.7 nm and 2.5 nm have been investigated, using a gas-surface interaction potential parameterized by the well-depth D of the gas on a planar surface made of the same material as that comprising the porous host. For strongly attractive situations, i.e., large D, one or more (depending on R) Ar layers adsorb successively before liquid fills the pore. For very small values of D, in contrast, negligible adsorption occurs at any pressure P below saturated vapor pressure P0; above saturation, there eventually occurs a threshold value of P at which the coverage jumps from empty to full, nearly discontinuously. Hysteresis is found to occur in the simulation data whenever abrupt CC occurs, i.e. for R>= 1.7 nm, and for small D when R=1nm. Then, the pore-emptying branch of the adsorption isotherm exhibits larger N than the pore-filling branch, as is known from many experiments and simulation studies. The relation between CC and wetting on planar surfaces is discussed in terms of a threshold value of D, which is about one-half of the value found for the wetting threshold on a planar surface. This finding is consistent with a simple thermodynamic model of the wetting transition developed previously.
An ultralow-temperature binary mixture of Bose-Einstein condensates adsorbed at an optical wall can undergo a wetting phase transition in which one of the species excludes the other from contact with the wall. Interestingly, while hard-wall boundary conditions entail the wetting transition to be of first order, using Gross-Pitaevskii theory we show that first-order wetting as well as critical wetting can occur when a realistic exponential optical wall potential (evanescent wave) with a finite turn-on length $lambda$ is assumed. The relevant surface excess energies are computed in an expansion in $lambda/xi_i$, where $xi_i$ is the healing length of condensate $i$. Experimentally, the wetting transition may best be approached by varying the interspecies scattering length $a_{12}$ using Feshbach resonances. In the hard-wall limit, $lambda rightarrow 0$, exact results are derived for the prewetting and first-order wetting phase boundaries.
Capillary condensation of water is ubiquitous in nature and technology. It routinely occurs in granular and porous media, can strongly alter such properties as adhesion, lubrication, friction and corrosion, and is important in many processes employed by microelectronics, pharmaceutical, food and other industries. The century-old Kelvin equation is commonly used to describe condensation phenomena and shown to hold well for liquid menisci with diameters as small as several nm. For even smaller capillaries that are involved in condensation under ambient humidity and, hence, of particular practical interest, the Kelvin equation is expected to break down, because the required confinement becomes comparable to the size of water molecules. Here we take advantage of van der Waals assembly of two-dimensional crystals to create atomic-scale capillaries and study condensation inside. Our smallest capillaries are less than 4 angstroms in height and can accommodate just a monolayer of water. Surprisingly, even at this scale, the macroscopic Kelvin equation using the characteristics of bulk water is found to describe accurately the condensation transition in strongly hydrophilic (mica) capillaries and remains qualitatively valid for weakly hydrophilic (graphene) ones. We show that this agreement is somewhat fortuitous and can be attributed to elastic deformation of capillary walls, which suppresses giant oscillatory behavior expected due to commensurability between atomic-scale confinement and water molecules. Our work provides a much-needed basis for understanding of capillary effects at the smallest possible scale important in many realistic situations.
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