We study capillary condensation in a bath consisting of active Brownian particles (ABPs) and the forces acting on the capillary close to the motility-induced phase separation (MIPS). The capillary is modelled as two parallel rods of high aspect ratio which are fixed in space. We consider a bath of ABPs having a self-propulsion speed much larger than the critical speed necessary for MIPS to occur. For a given particle speed, we gradually increase the packing fraction of ABPs, starting from a homogeneous dilute phase of ABPs and going towards the binodal of MIPS. Depending on the packing fraction of ABPs and capillary width, we find that the effective force between the capillary rods can be either attractive or repulsive. In fact, with increasing width it shows damped oscillations as long as capillary condensation occurs. We analyze them in detail by studying the distribution of particle distances from the inner and outer wall of the capillary, respectively. In addition, we examine the capillary in the active bath prepared under conditions close to the critical point. We do not observe signs of the presence of long-range Casimir interactions.
The capillary condensation for fluids into spherical nano-cavities is analyzed within the frame of two theoretical approaches. One description is based on a widely used simplified version of the droplet model formulated for studying atomic nuclei. The other, is a more elaborated calculation performed by applying a density functional theory. The agreement between both models is examined and it is shown that a small correction to the simple fluid model improves the predictions. A connection to results previously obtained for planar slits and cylindrical pores is done.
We report a new first-order phase transition preceding capillary condensation and corresponding to the discontinuous formation of a curved liquid meniscus. Using a mean-field microscopic approach based on the density functional theory we compute the complete phase diagram of a prototypical two-dimensional system exhibiting capillary condensation, namely that of a fluid with long-ranged dispersion intermolecular forces which is spatially confined by a substrate forming a semi-infinite rectangular pore exerting long-ranged dispersion forces on the fluid. In the T-mu plane the phase line of the n…
When two solid surfaces are brought in contact, water vapor present in the ambient air may condense in the region of the contact to form a liquid bridge connecting the two surfaces : this is the so-called capillary condensation. This phenomenon has drastic consequences on the contact between solids, modifying the macroscopic adhesion and friction properties. In this paper, we present a survey of the work we have performed both experimentally and theoretically to understand the microscopic foundations of the kinetics of capillary condensation. From the theoretical point of view, we have compute…
We study the spatio-temporal dynamics of water uptake by capillary condensation from unsaturated vapor in mesoporous silicon layers (pore radius $r_\mathrm{p} \simeq 2$ nm), taking advantage of the local changes in optical reflectance as a function of water saturation. Our experiments elucidate two qualitatively different regimes as a function of the imposed external vapor pressure: for low saturations, equilibration occurs via a diffusion-like process; for high saturations, an imbibition-like wetting front results in fast equilibration towards a fully saturated sample. We show that the imbibi…
This paper is devoted to the thermally activated dynamics of the capillary condensation. We present a simple model which enables us to identify the critical nucleus involved in the transition mechanism. This simple model is then applied to calculate the nucleation barrier from which we can obtain informations on the nucleation time. We present a simple estimation of the nucleation barrier in slab geometry both in the two dimensional case and in the three dimensional case. We extend the model in the case of rough surfaces which is closer to the experimental case and allows comparison with exper…
It is shown that a bare simple fluid model (SFM) proposed some years ago for studying adsorption between two semi-infinite solid walls can be improved by modifying the surface term in the grand potential for the film phase. Such a correction substantially improves the agreement between the predictions for phase transitions provided by that SFM and results obtained from calculations carried out for $^4$He with the density-functional method at zero temperature. The corrective term depends on the strength of the adsorption potential and observables of bulk helium.
The dynamics of saturated vapor between two intersecting walls is examined. It is shown that, if the angle $ϕ$ between the walls is sufficiently small, the vapor becomes unstable, and spontaneous condensation occurs in the corner, similar to the so-called capillary condensation of vapor into a porous medium. As a result, an ever-growing liquid meniscus develops near the corner. The diffuse-interface model and the lubrication approximation are used to demonstrate that the meniscus grows if and only if $ϕ+2θ<π$, where $θ$ is the contact angle corresponding to the fluid/solid combination under co…
We consider the Asakura-Oosawa model of hard sphere colloids and ideal polymers in contact with a porous matrix modeled by immobilized configurations of hard spheres. For this ternary mixture a fundamental measure density functional theory is employed, where the matrix particles are quenched and the colloids and polymers are annealed, i.e. allowed to equilibrate. We study capillary condensation of the mixture in a tiny sample of matrix as well as demixing and the fluid-fluid interface inside a bulk matrix. Density profiles normal to the interface and surface tensions are calculated and compare…
This paper is devoted to the thermally activated dynamics of the capillary condensation. We present a simple model which enables us to identify the critical nucleus involved in the transition mechanism. This simple model is then applied to calculate the nucleation barrier from which we can obtain informations on the nucleation time. These results are compared to the numerical simulation of a Landau-Ginzburg model for the liquid-vapor interface combined with a Langevin dynamics.
We study the influence of wetting on the capillary condensation for a simple fluid in a pore-like geometry, where the reference system is an infinitely long slit. The Corner Transfer Matrix Renormalization Group method has been extended to study a two-dimensional Ising model confined in an L x L geometry with equal surface fields. Our results have confirmed that in both geometries the coexistence line shift is governed by the same scaling powers, but their prefactors are different.
We investigate with Monte Carlo computer simulations the capillary phase behaviour of model colloid-polymer mixtures confined between a flat wall and a corrugated wall. The corrugation is modelled via a sine wave as a function of one of the in-plane coordinates leading to a depletion attraction between colloids and the corrugated wall that is curvature dependent. We find that for increased amplitude of corrugation the region of the phase diagram where capillary condensation occurs becomes larger. We derive a Kelvin equation for this system and compare its predictions to the simulation results.…
We investigate phase separation of near-critical binary mixtures between parallel symmetric walls in the strong adsorption regime. We take into account the renormalization effect due to the critical fluctuations using the recent local functional theory [J. Chem. Phys. 136, 114704 (2012)]. In statics, a van der Waals loop is obtained in the relation between the average order parameter $<psi>$ in the film and the chemical potential when the temperature $T$ is lower than the film critical temperature $T_c^{ca}$ (in the case of an upper critical solution temperature). In dynamics, we lower $T$ bel…
We study the phase equilibria of a fluid confined in an open capillary slit formed when a wall of finite length $H$ is brought a distance $L$ away from a second macroscopic surface. This system shows rich phase equilibria arising from the competition between two different types of capillary condensation, corner filling and meniscus depinning transitions depending on the value of the aspect ratio $a=L/H$. For long capillaries, with $a<2/π$, the condensation is of type I involving menisci which are pinned at the top edges at the ends of the capillary characterized by an edge contact angle. For i…
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 a…
This work reports an innovative humidity driven actuation concept based on Bangham effect using simple nanoporous sol-gel silica thin films as humidity responsive materials. Bilayer shaped actuators, consisting on a humidity-sensitive active nanostructured silica film deposited on a polymeric substrate (Kapton) were demonstrated as an original mean to convert water molecule adsorption and capillary condensation in useable mechanical work. Reversible silica surface energy modifications by water adsorption and the energy produced by the rigid silica film contraction, induced by water capillary c…
An object withdrawn from a liquid bath is coated with a thin layer of liquid. Along with the liquid, impurities such as particles present in the bath can be transferred to the withdrawn substrate. Entrained particles locally modify the thickness of the film, hence altering the quality and properties of the coating. In this study, we show that it is possible to entrain the liquid alone and avoid contamination of the substrate, at sufficiently low withdrawal velocity in diluted suspensions. Using a model system consisting of a plate exiting a liquid bath, we observe that particles can remain tra…
Using molecular simulation, we analyze the capillary condensation and evaporation processes for Argon confined in a cylindrical nanopore. For this purpose, we define the entropy of the adsorbed fluid as a reaction coordinate and determine the free energy associated with both processes along entropic pathways. For capillary condensation, we identify a complex free energy profile resulting from the multi-stage nature of this phenomenon. We find capillary condensation to proceed through the nucleation of a liquid bridge across the nanopore, followed by its expansion throughout the pore to give ri…
Within self-consistent field theory we study the phase behaviour of a symmetric binary AB polymer blend confined into a thin film. The film surfaces interact with the monomers via short range potentials. One surface attracts the A component and the corresponding semi-infinite system exhibits a first order wetting transition. The surface interaction of the opposite surface is varied as to study the crossover from capillary condensation for symmetric surface fields to the interface localisation/delocalisation transition for antisymmetric surface fields. In the former case the phase diagram has a…
We study the low temperature phase equilibria of a fluid confined in an open capillary slit formed by two parallel walls separated by a distance $L$ which are in contact with a reservoir of gas. The top wall of the capillary is of finite length $H$ while the bottom wall is considered of macroscopic extent. This system shows rich phase equilibria arising from the competition between two different types of capillary condensation, corner filling and meniscus depinning transitions depending on the value of the aspect ratio $a=L/H$ and divides into three regimes: For long capillaries, with $a<2/π$,…
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 practica…
We investigate the critical behavior of a near-critical fluid confined between two parallel plates in contact with a reservoir by calculating the order parameter profile and the Casimir amplitudes (for the force density and for the grand potential). Our results are applicable to one-component fluids and binary mixtures. We assume that the walls absorb one of the fluid components selectively for binary mixtures. We propose a renormalized local functional theory accounting for the fluctuation effects. Analysis is performed in the plane of the temperature T and the order parameter in the reservoi…
The kinetics of droplet and bridge formation within striped nano-capillaries is studied when the wetting film grows via interface-limited growth. The phenomenological time-dependent Ginzburg-Landau (TDGL)-type model with thermal noise is used and numerically solved using the cell dynamics method. The model is two-dimensional and consists of undersaturated vapor confined within a nano-capillary made of two infinitely wide flat substrates. The surface of the substrate is chemically heterogeneous with a single stripe of lyophilic domain that exerts long-range attractive potential to the vapor mol…
Monte Carlo simulations of the Asakura-Oosawa (AO) model for colloid-polymer mixtures confined between two parallel repulsive structureless walls are presented and analyzed in the light of current theories on capillary condensation and interface localization transitions. Choosing a polymer to colloid size ratio of q=0.8 and studying ultrathin films in the range of D=3 to D=10 colloid diameters thickness, grand canonical Monte Carlo methods are used; phase transitions are analyzed via finite size scaling, as in previous work on bulk systems and under confinement between identical types of walls…
Beyond capillary condensation: Shear-induced bridging transitions in patterned slits
The Czech Academy of Sciences, Institute of Chemical Process Fundamentals（捷克科学院化学过程基础研究所）；University of Chemistry and Technology Prague（布拉格化工大学）；Imperial College London（伦敦帝国理工学院）
The excess adsorption $Γ$ 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 …
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…
We present a quantitative comparison between extensive Monte Carlo simulations and self-consistent field calculations on the phase diagram and wetting behavior of a symmetric, binary (AB) polymer blend confined into a film. The flat walls attract one component via a short range interaction. The critical point of the confined blend is shifted to lower temperatures and higher concentrations of the component with the lower surface free energy. The binodals close the the critical point are flattened compared to the bulk and exhibit a convex curvature at intermediate temperatures -- a signature of …
We report a numerical study of equilibrium phase-diagrams and interfacial properties of bulk and confined colloid-polymer mixtures using grand canonical Monte Carlo simulations. Colloidal particles are treated as hard spheres, while the polymer chains are described as soft repulsive spheres. The polymer-polymer, colloid-polymer, and wall-polymer interactions are described by density-dependent potentials derived by Bolhuis and Louis [Macromolecules, 35 (2002), p.1860]. We compared our results with those of the Asakura-Oosawa-Vrij model, that treats the polymers as ideal particles. We find that …
We study the phase transitions of a fluid confined in a capillary slit made from two adjacent walls each of which are a periodic composite of stripes of two different materials. For wide slits the capillary condensation occurs at a pressure which is described accurately by a combination of the Kelvin equation and the Cassie law for an averaged contact angle. However, for narrow slits the condensation occurs in two steps involving an intermediate bridging phase, with the corresponding pressures described by two new Kelvin equations. These are characterised by different contact angles due to int…
In this letter, we describe the capillary sorting of particles by size based on dip coating. A substrate withdrawn from a liquid bath entrains a coating whose thickness depends on the withdrawal speed and the liquid properties. If the coating material contains particles, they will only be entrained when the viscous force pulling them with the substrate overcomes the opposing capillary force at the deformable meniscus. This force threshold occurs at different liquid thicknesses for particles of different sizes. Here, we show that this difference can be used to separate small particles from a mi…
A simple theoretical approach is used to investigate active colloids at the free interface and near repulsive substrates. We employ dynamical density functional theory to determine the steady-state density profiles in an effective equilibrium system [Farage et al., Phys. Rev. E, 91 (2015) 042310]. In addition to the known accumulation at surfaces, we predict wetting and drying transitions at a flat repulsive wall and capillary condensation and evaporation in a slit pore. These new phenomena are closely related to the motility-induced phase separation (MIPS) in the bulk.
Capillary condensation, which takes place in confined geometries, is the first-order vapor-to-liquid phase transition and is explained by the Kelvin equation, but the equations applicability for arbitrarily curved surface has been long debated and is a sever problem. Recently, we have proposed generic dynamic equations for moving surfaces. Application of the equations to static shapes and modelling the pressure at the interface nearly trivially solves the generalization problem for the Kelvin equation. The equations are universally true for any surfaces: atomic, molecular, micro or macro scale…
