We study the behavior of fluids, confined by geometrically structured substrates, upon approaching a critical point at T = Tc in their bulk phase diagram. As generic substrate structures periodic arrays of wedges and ridges are considered. Based on general renormalization group arguments we calculate, within mean field approximation, the universal scaling functions for order parameter profiles of a fluid close to a single structured substrate and discuss the decay of its spatial variation into the bulk. We compare the excess adsorption at corrugated substrates with the one at planar walls. The confinement of a critical fluid by two walls generates effective critical Casimir forces between them. We calculate corresponding universal scaling functions for the normal critical Casimir force between a flat and a geometrically structured substrate as well as the lateral critical Casimir force between two identically patterned substrates.
We study the critical Casimir force for a film geometry in the Ising universality class. We employ a homogeneous adsorption preference on one of the confining surfaces, while the opposing surface exhibits quenched random disorder, leading to a random local adsorption preference. Disorder is characterized by a parameter p, which measures, on average, the portion of the surface that prefers one component, so that p=0, 1 correspond to homogeneous adsorption preference. By means of Monte Carlo simulations of an improved Hamiltonian and finite-size scaling analysis, we determine the critical Casimi…
Motivated by recent experiments with confined binary liquid mixtures near demixing, we study the universal critical properties of a system, which belongs to the Ising universality class, in the film geometry. We employ periodic boundary conditions in the two lateral directions and fixed boundary conditions on the two confining surfaces, such that one of them has a spatially homogeneous adsorption preference while the other one exhibits a laterally alternating adsorption preference, resembling locally a single chemical step. By means of Monte Carlo simulations of an improved Hamiltonian, so tha…
We show that hydrophilic ions present in a confined, near-critical aqueous mixture can lead to an attraction between like charge surfaces with opposing preferential adsorption of the two species of the mixture, even though the corresponding Casimir potential in uncharged systems is repulsive. This prediction agrees with recent experiment [Nellen {\it{et al.}}, Soft Matter{\bf{80}}, 061143 (2011)]. We also show that oppositely charged hydrophobic surfaces can repel each other, although the Casimir potential between uncharged surfaces with like preferential adsorption (selectivity) is attractive…
We study the normal and lateral effective critical Casimir forces acting on a spherical colloid immersed in a critical binary solvent and close to a chemically structured substrate with alternating adsorption preference. We calculate the universal scaling function for the corresponding potential and compare our results with recent experimental data [Soyka F., Zvyagolskaya O., Hertlein C., Helden L., and Bechinger C., Phys. Rev. Lett., 101, 208301 (2008)]. The experimental potentials are properly captured by our predictions only by accounting for geometrical details of the substrate pattern for…
We experimentally demonstrate that critical Casimir forces in colloidal systems can be continuously tuned by the choice of boundary conditions. The interaction potential of a colloidal particle in a mixture of water and 2,6-lutidine has been measured above a substrate with a gradient in its preferential adsorption properties for the mixture's components. We find that the interaction potentials at constant temperature but different positions relative to the gradient continuously change from attraction to repulsion. This demonstrates that critical Casimir forces respond not only to minute temper…
Critical properties of a liquid film between two planar walls are investigated in the canonical ensemble, within which the total number of particles, rather than their chemical potential, is kept constant. The effect of this constraint is analyzed within mean field theory (MFT) based on a Ginzburg-Landau free energy functional as well as via Monte Carlo simulations of the 3D Ising model with fixed total magnetization. Within MFT and for finite adsorption strengths at the walls, the thermodynamic properties of the film in the canonical ensemble can be mapped exactly onto a grand canonical ensem…
We study the adsorption of simple fluids at smoothly structured, completely wet, walls and show that a meniscus osculation transition occurs when the Laplace and geometrical radii of curvature of locally parabolic regions coincide. Macroscopically, the osculation transition is of fractional, $7/2$, order and separates regimes in which the adsorption is microscopic, containing only a thin wetting layer, and mesoscopic, in which a meniscus exists. We develop a scaling theory for the rounding of the transition due to thin wetting layers and derive critical exponent relations that determine how th…
We consider binary liquid mixtures near their critical consolute points and exposed to geometrically flat but chemically structured substrates. The chemical contrast between the various substrate structures amounts to opposite local preferences for the two species of the binary liquid mixtures. Order parameters profiles are calculated for a chemical step, for a single chemical stripe, and for a periodic stripe pattern. The order parameter distributions exhibit frustration across the chemical steps which heals upon approaching the bulk. The corresponding spatial variation of the order parameter…
We study theoretically and experimentally the solvent-mediated critical Casimir force acting on colloidal particles immersed in a binary liquid mixture of water and 2,6-lutidine and close to substrates which are chemically patterned with periodically alternating stripes of antagonistic adsorption preferences. These patterns are experimentally realized via microcontact printing. Upon approaching the critical demixing point of the solvent, normal and lateral critical Casimir forces generate laterally confining effective potentials for the colloids. We analyze in detail the rich behavior of the s…
We study critical Casimir forces between planar walls and geometrically structured substrates within mean-field theory. As substrate structures, crenellated surfaces consisting of periodic arrays of rectangular crenels and merlons are considered. Within the widely used proximity force approximation, both the top surfaces of the merlons and the bottom surfaces of the crenels contribute to the critical Casimir force. However, for such systems the full, numerically determined critical Casimir forces deviate significantly fromthe pairwise addition formalismunderlying the proximity force approximat…
Recent experiments have demonstrated a fluctuation-induced lateral trapping of spherical colloidal particles immersed in a binary liquid mixture near its critical demixing point and exposed to chemically patterned substrates. Inspired by these experiments, we study this kind of effective interaction, known as the critical Casimir effect, for elongated colloids of cylindrical shape. This adds orientational degrees of freedom. When the colloidal particles are close to a chemically structured substrate, a critical Casimir torque acting on the colloids emerges. We calculate this torque on the basi…
The Casimir effect arises when long-ranged fluctuations are geometrically confined between two surfaces, leading to a macroscopic force. Traditionally, these forces have been observed in quantum systems and near critical points in classical systems. Here we show the existence of Casimir-like forces between two pinned particles immersed in two-dimensional systems near the jamming transition. We observe two components to the total force: a short-ranged, depletion force and a long-ranged, repulsive Casimir-like force. The Casimir-like force dominates as the jamming transition is approached, and w…
Recent experiments have measured the critical Casimir force acting on a colloid immersed in a binary liquid mixture near its continuous demixing phase transition and exposed to a chemically structured substrate. Motivated by these experiments, we study the critical behavior of a system, which belongs to the Ising universality class, for the film geometry with one planar wall chemically striped, such that there is a laterally alternating adsorption preference for the two species of the binary liquid mixture, which is implemented by surface fields. For the opposite wall we employ alternatively a…
Recent experimental realizations of the critical Casimir effect have been implemented by monitoring colloidal particles immersed in a binary liquid mixture near demixing and exposed to a chemically structured substrate. In particular, critical Casimir forces have been measured for surfaces consisting of stripes with periodically alternating adsorption preferences, forming chemical steps between them. Motivated by these experiments, we analyze the contribution of such chemical steps to the critical Casimir force for the film geometry and within the Ising universality class. By means of Monte Ca…
Motivated by recent experiments with confined binary liquid mixtures near their continous demixing phase transition we study the critical behavior of a system, which belongs to the Ising universality class, for the film geometry with one planar wall chemically structured such that there is a laterally alternating adsorption preference for the species of the binary liquid mixture. By means of Monte Carlo simulations and finite-size scaling analysis we determine the critical Casimir force and the corresponding universal scaling function.
Adsorption properties of chain fluids are of interest from both fundamental and industrial points of view. Density Functional Theory (DFT) based models are among the most appropriate techniques allowing to describe surface phenomena. At the same time Statistical Associating Fluid Theory (SAFT) successfully describes bulk PVT properties of chain-fluids. In this publication we have developed novel version of SAFT-DFT approach entitled RS-SAFT which is capable to describe adsorption of short hydrocarbons on geometrically rough surface. Major advantage of our theory is application to adsorption on…
In soft and condensed matter physics, effective interactions often emerge as a result of the spatial confinement of a fluctuating field. For instance, microscopic particles in a binary liquid mixture are subject to critical Casimir forces whenever their surfaces confine the thermal fluctuations of the order parameter of this kind of solvent, the range of which diverges upon approaching the critical demixing point. Critical Casimir forces are predicted to be nonadditive on a particular large scale. However, a direct experimental evidence of this fact is still lacking. Here, we fill in this gap …
In a recent study [Phys. Rev. E \textbf{94}, 022103 (2016)] it has been shown that, for a fluid film subject to critical adsorption, the resulting critical Casimir force (CCF) may significantly depend on the thermodynamic ensemble. Here, we extend that study by considering fluid films within the so-called ordinary surface universality class. We focus on mean-field theory, within which the OP profile satisfies Dirichlet boundary conditions and produces a nontrivial CCF in the presence of external bulk fields or, respectively, a nonzero total order parameter within the film. Our analytical resul…
We consider binary liquid mixtures close to their critical points confined by two parallel, geometrically flat but chemically structured, substrates. Universal order parameters profiles are calculated within mean field theory for periodic patterns of stripes with alternating preferences for the two species of the mixture and with different relative positions of the two substrates. From the order parameters profiles the effective forces between the two plates are derived. The tuning of Casimir amplitudes is discussed.
We study colloidal particles with chemically inhomogeneous surfaces suspended in a critical binary liquid mixture. The inhomogeneous particle surface is composed of patches with alternating adsorption preferences for the two components of the binary solvent. By describing the binary liquid mixture \emph{at} its consolute point in terms of the critical Ising model we exploit its conformal invariance in two spatial dimension. This allows us to determine exactly the universal profiles of the order parameter, the energy density, and the stress tensor as well as some of their correlation functions …
Density functional theory is used to study colloidal hard-rod fluids near an individual right-angled wedge or edge as well as near a hard wall which is periodically patterned with rectangular barriers. The Zwanzig model, in which the orientations of the rods are restricted to three orthogonal orientations but their positions can vary continuously, is analyzed by numerical minimization of the grand potential. Density and orientational order profiles, excess adsorptions, as well as surface and line tensions are determined. The calculations exhibit an enrichment [depletion] of rods lying parallel…
If a fluctuating medium is confined, the ensuing perturbation of its fluctuation spectrum generates Casimir-like effective forces acting on its confining surfaces. Near a continuous phase transition of such a medium the corresponding order parameter fluctuations occur on all length scales and therefore close to the critical point this effect acquires a universal character, i.e., to a large extent it is independent of the microscopic details of the actual system. Accordingly it can be calculated theoretically by studying suitable representative model systems. We report on the direct measurement…
We present an experimental and theoretical study of the phase behavior of a binary mixture of colloids with opposite adsorption preferences in a critical solvent. As a result of the attractive and repulsive critical Casimir forces, the critical fluctuations of the solvent lead to a further critical point in the colloidal system, i.e. to a critical colloidal-liquid--colloidal-liquid demixing phase transition which is controlled by the solvent temperature. Our experimental findings are in good agreement with calculations based on a simple approximation for the free energy of the system.
