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. Unlike the latter work, inequivalent walls are used here: while the left wall has a hard-core repulsion for both polymers and colloids, at the right wall an additional square-well repulsion of variable strength acting only on the colloids is present. We study how the phase separation into colloid-rich and colloid-poor phases occurring already in the bulk is modified by such a confinement. When the asymmetry of the wall-colloid interaction increases, the character of the transition smoothly changes from capillary condensation-type to interface localization-type. The critical behavior of these transitions is discussed, as well as the colloid and polymer density profiles across the film in the various phases, and the correlation of interfacial fluctuations in the direction parallel to the confining walls. The experimental observability of these phenomena also is briefly discussed.
Within a general framework we study the effective, deformation-induced interaction between two colloids trapped at a fluid interface. As an application, we consider the interface deformation owing to the electrostatic field of charged colloids. The effective interaction is attractive and overcomes the direct electrostatic repulsion at large separations if the system is not mechanically isolated. Otherwise, a net attraction seems possible only for large enough colloidal charges.
We calculate the effective force mediated by thermally excited capillary waves between spherical or disklike colloids trapped at a fluid interface. This Casimir type interaction is shown to depend sensitively on the boundary conditions imposed at the three-phase contact line. For large distances between the colloids an unexpected cancellation of attractive and repulsive contributions is observed leading to a fluctuation force which decays algebraically very rapidly. For small separations the resulting force is rather strong and it may play an important role in two-dimensional colloid aggregati…
In directed assembly, small building clocks are assembled into an organized structures under the influence of guiding fields. Capillary interactions provide a versatile route for structure formation. Colloids adsorbed on fluid interfaces distort the interface, which creates an associated energy field. When neighboring distortions overlap, colloids interact to minimize interfacial area. Contact line pinning, particle shape and surface chemistry play important roles in structure formation. Interface curvature acts like an external field; particles migrate and assemble in patterns dictated by cur…
We determine the capillary attraction and equilibrium configurations of particles trapped at a liquid-fluid interface due to the pinning of their contact-line. We calculate analytically the asymptotic interaction energy between two particles and, numerically, the multi-body energy landscape for up to four contacting particles. Our results are consistent with recent experiments. We show that a system composed of a large number of such particles behaves as a jammed system.
We image the flow of a nearly random close packed, hard-sphere colloidal suspension (a `paste') in a square capillary using confocal microscopy. The flow consists of a `plug' in the center while shear occurs localized adjacent to the channel walls, reminiscent of yield-stress fluid behavior. However, the observed scaling of the velocity profiles with the flow rate strongly contrasts yield-stress fluid predictions. Instead, the velocity profiles can be captured by a theory of stress fluctuations originally developed for chute flow of dry granular media. We verified this behavior both for smooth…
We investigate the evolution of a system of colloidal particles, trapped at a fluid interface and interacting via capillary attraction, as function of the range of the capillary interaction and temperature. We address the collapse of an initially homogeneous particle distribution and of a radially symmetric (disk--shaped) distribution of finite size, both theoretically by using a perturbative approach inspired by cosmological models and numerically by means of Brownian dynamics (BD) and dynamical density functional theory (DDFT). The results are summarized in a "dynamical phase diagram", descr…
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.…
The structure and the statistical fluctuations of interfaces between coexisting phases in the Asakura-Oosawa (AO) model for a colloid--polymer mixture are analyzed by extensive Monte Carlo simulations. We make use of a recently developed grand canonical cluster move with an additional constraint stabilizing the existence of two interfaces in the (rectangular) box that is simulated. Choosing very large systems, of size LxLxD with L=60 and D=120, measured in units of the colloid radius, the spectrum of capillary wave-type interfacial excitations is analyzed in detail. The local position of the i…
Capillary bridges can form between colloids immersed in a two phase fluid, e.g., in a binary liquid mixture, if the surface of the colloids prefers the species other than the one favored in the bulk liquid. Here, we study the formation of liquid bridges induced by confining colloids to a slit, with the slit walls having a preference opposite to the one of the colloid surface. Using mean field theory, we show that there is a line of first-order phase transitions between the bridge and the no-bridge states, which ends at a critical point. By decreasing the slit width, this critical point is shif…
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…
We investigate the dynamics of colloids at a fluid interface driven by attractive capillary interactions. At submillimeter length scales, the capillary attraction is formally analogous to two-dimensional gravity. In particular it is a non-integrable interaction and it can be actually relevant for collective phenomena in spite of its weakness at the level of the pair potential. We introduce a mean-field model for the dynamical evolution of the particle number density at the interface. For generic values of the physical parameters the homogeneous distribution is found to be unstable against larg…
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 fractio…
Using Brownian dynamics simulations, density functional theory, and analytical perturbation theory we study the collapse of a patch of interfacially trapped, micrometer-sized colloidal particles, driven by long-ranged capillary attraction. This attraction {is formally analogous} to two--dimensional (2D) screened Newtonian gravity with the capillary length \hatλ as the screening length. Whereas the limit \hatλ \to \infty corresponds to the global collapse of a self--gravitating fluid, for finite \hatλ we predict theoretically and observe in simulations a ringlike density peak at the outer rim o…
Drying of colloidal droplets on solid, rigid substrates is associated with a capillary pressure developing within the droplet. In due course of time, the capillary pressure builds up due to droplet evaporation resulting in the formation of a colloidal thin film that is prone to crack formation. In this study, we show that introducing a minimal amount of nematic liquid crystal (NLC) can completely suppress the crack formation. The mechanism behind the curbing of the crack formation may be attributed to the capillary stress-absorbing cushion provided by the elastic arrangements of the liquid cry…
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…
We study numerically the hydrodynamics of dip coating from a suspension and report a mechanism for colloidal assembly and pattern formation on smooth and uniform substrates. Below a critical withdrawal speed of the substrate, capillary forces required to deform the meniscus prevent colloidal particles from entering the coating film. Capillary forces are overcome by hydrodynamic drag only after a minimum number of particles organize in a close-packed formation within the meniscus. Once within the film, the formed assembly moves at nearly the withdrawal speed and rapidly separates from the next …
The elastic and capillary interactions between a pair of colloidal particles trapped on top of a nematic film are studied theoretically for large separations $d$. The elastic interaction is repulsive and of quadrupolar type, varying as $d^{-5}$. For macroscopically thick films, the capillary interaction is likewise repulsive and proportional to $d^{-5}$ as a consequence of mechanical isolation of the system comprised of the colloids and the interface. A finite film thickness introduces a nonvanishing force on the system (exerted by the substrate supporting the film) leading to logarithmically …
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.
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…
The effective potential between charged colloids trapped at water interfaces is analyzed. It consists of a repulsive electrostatic and an attractive capillary part which asymptotically both show dipole--like behavior. For sufficiently large colloid charges, the capillary attraction dominates at large separations. The total effective potential exhibits a minimum at intermediate separations if the Debye screening length of water and the colloid radius are of comparable size.
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…
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 $a<2/π$,…
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…
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.
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 analyze the effective potential for nanoparticles trapped at a fluid interface within a simple model which incorporates surface and line tensions as well as a thermal average over interface fluctuations (capillary waves). For a single colloid, a reduced steepness of the potential well hindering movements out of the interface plane compared to rigid interface models is observed, and an instability of the capillary wave partition sum in case of negative line tensions is pointed out. For two colloids, averaging over the capillary waves leads to an effective Casimir--type interaction which is l…
The adsorption of single colloidal microparticles (0.5--1 $μ$m radius) at a water-oil interface has been recently studied experimentally using digital holographic microscopy [Kaz \textit{et al., Nat. Mater.}, 2012, \textbf{11}, 138--142]. An initially fast adsorption dynamics driven by capillary forces is followed by an unexpectedly slow relaxation to equilibrium that is logarithmic in time and can span hours or days. The slow relaxation kinetics has been attributed to the presence of surface "defects" with nanoscale dimensions (1--5\,nm) that induce multiple metastable configurations of the c…
Extreme deformation of soft matter is central to our understanding of the effects of shock, fracture, and phase change in a variety of systems. Yet, despite, the increasing interest in this area, far-from-equilibrium behaviours of soft matter remain challenging to probe. Colloidal suspensions are often used to visualise emergent behaviours in soft matter, as they offer precise control of interparticle interactions, and ease of visualisation by optical microscopy. However, previous studies have been limited to deformations that are orders of magnitude too slow to be representative of extreme de…
Using Gibbs ensemble Monte Carlo simulations and density functional theory we investigate the fluid-fluid demixing transition in inhomogeneous colloid-polymer mixtures confined between two parallel plates with separation distances between one and ten colloid diameters covering the complete range from quasi two-dimensional to bulk-like behavior. We use the Asakura-Oosawa-Vrij model in which colloid-colloid and colloid-polymer interactions are hard-sphere like, whilst the pair potential between polymers vanishes. Two different types of confinement induced by a pair of parallel walls are consider…
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 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…
Within a general theoretical framework we study the effective, deformation-induced interaction between two colloidal particles trapped at a fluid interface in the regime of small deformations. In many studies, this interaction has been computed with the ansatz that the actual interface configuration for the pair is given by the linear superposition of the interface deformations around the single particles. Here we assess the validity of this approach and compute the leading term of the effective interaction for large interparticle separation beyond this so-called superposition approximation. A…
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…
We calculate the effective fluctuation induced force between spherical or disk-like colloids trapped at a flat, fluid interface mediated by thermally excited capillary waves. This Casimir type force is determined by the partition function of the system which in turn is calculated in a functional integral approach, where the restrictions on the capillary waves imposed by the colloids are incorporated by auxiliary fields. In the long-range regime the fluctuation induced force is shown to depend sensitively on the boundary conditions imposed at the three-phase contact line between the colloids an…
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…
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…
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 discuss the phase diagram of fluid confined in AFM-like geometry. It combines the properties of capillary condensation and complete filling of a wedge.
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 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…
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）
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…
In colloidal suspensions, self-organization processes can be easily fueled by external fields. One particularly interesting class of phenomena occurs in monolayers of dipolar particles that are driven by rotating external fields. Here we report results from a computer simulation study of such systems focusing on the clustering behavior also observed in recent experiments. The key result of this paper is a novel interpretation of this pattern formation phenomenon: We show the clustering to be a by-product of a vapor-liquid first order phase transition. In fact, the observed dynamic coarsening p…
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 …
We revisit the problem of semi-flexible chain condensation by neutral depleting agents (e.g. colloidal spheres or flexible polymers) by using a simple formalism that allows us to address its main features without specifying the kind of depleting agents. Correlations between depleting agents are shown to produce a reswelling of the chain at high enough volume fraction, consistent with an earlier analysis by Grosberg et al. (Biopolymers, 21:2413, 1982) in the context of DNA condensation induced by neutral polymers. It is also shown that the conditions under which spherical colloids can condense …
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…
The evolution of an initially prepared distribution of micron sized colloidal particles, trapped at a fluid interface and under the action of their mutual capillary attraction, is analyzed by using Brownian dynamics simulations. At a separation λ given by the capillary length of typically 1 mm, the distance dependence of this attraction exhibits a crossover from a logarithmic decay, formally analogous to two-dimensional gravity, to an exponential decay. We discuss in detail the adaption of a particle-mesh algorithm, as used in cosmological simulations to study structure formation due to gravit…
The liquid-liquid phase separation of a binary solvent can be arrested by colloidal particles trapped at the interface [K. Stratford et al., Science 309, 5744 (2005)]. We show experimentally that the colloidal network so formed can remain stable after fully remixing the liquids, creating a new type of gel in which colloids in a single-phase solvent have locally planar coordination. We argue that this structure is likely maintained by primary-minimum DLVO bonding of our charged colloids, created under strong compression by capillary forces. We present simulation evidence that the combination of…
Large-scale Monte Carlo simulations of a phase-separating colloid-polymer mixture are performed and compared to recent experiments. The approach is based on effective interaction potentials in which the central monomers of self-avoiding polymer chains are used as effective coordinates. By incorporating polymer nonideality together with soft colloid-polymer repulsion, the predicted binodal is in excellent agreement with recent experiments. In addition, the interfacial tension as well as the capillary length are in quantitative agreement with experimental results obtained at a number of points i…
To describe the full spectrum of surface fluctuations of the interface between phase-separated colloid-polymer mixtures from low scattering vector q (classical capillary wave theory) to high q (bulk-like fluctuations), one must take account of the interface's bending rigidity. We find that the bending rigidity is negative and that on approach to the critical point it vanishes proportionally to the interfacial tension. Both features are in agreement with Monte Carlo simulations.
We present a detailed analysis of the effective force between two smooth spherical colloids floating at a fluid interface due to deformations of the interface. The results hold in general and are applicable independently of the source of the deformation provided the capillary deformations are small so that a superposition approximation for the deformations is valid. We conclude that an effective long--ranged attraction is possible if the net force on the system does not vanish. Otherwise, the interaction is short--ranged and cannot be computed reliably based on the superposition approximation.…
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 …
Phase separation of colloid-polymer mixtures, described by the Asakura-Oosawa (AO) model, confined in a thin slit pore is studied by grand-canonical Monte Carlo simulation. While one wall is a hard wall for both particles, at the other wall there acts an additional repulsive potential on the colloids only. Varying the strength of this potential, a crossover from capillary condensation to an interface localization transition is found. The latter occurs under conditions where in the bulk almost complete phase separation has occurred.
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…
We use confocal microscopy to study an equilibrated crystal-liquid interface in a colloidal suspension. Capillary waves roughen the surface, but locally the intrinsic interface is sharply defined. We use local measurements of the structure and dynamics to characterize the intrinsic interface, and different measurements find slightly different widths of this interface. In terms of the particle diameter $d$, this width is either $1.5d$ (based on structural information) or $2.4d$ (based on dynamics), both not much larger than the particle size. This work is the first direct experimental visualiza…
