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.
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…
We investigate the behavior of colloidal particles immersed in a binary liquid mixture of water and 2,6-lutidine in the presence of a chemically patterned substrate. Close to the critical point of the mixture, the particles are subjected to critical Casimir interactions with force components normal and parallel to the surface. Because the strength and sign of these interactions can be tuned by variations in the surface properties and the mixtures temperature, critical Casimir forces allow the formation of highly ordered monolayers but also extend the use of colloids as model systems.
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…
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…
Using an interface displacement model we calculate the shapes of thin liquidlike films adsorbed on flat substrates containing a chemical stripe. We determine the entire phase diagram of morphological phase transitions in these films as function of temperature, undersaturation, and stripe width
Based on a microscopic density functional theory we investigate the morphology of thin liquidlike wetting films adsorbed on substrates endowed with well-defined chemical heterogeneities. As paradigmatic cases we focus on a single chemical step and on a single stripe. In view of applications in microfluidics the accuracy of guiding liquids by chemical microchannels is discussed. Finally we give a general prescription of how to investigate theoretically the wetting properties of substrates with arbitrary chemical structures.
Colloids immersed in a critical or near-critical binary liquid mixture and close to a chemically patterned substrate are subject to normal and lateral critical Casimir forces of dominating strength. For a single colloid we calculate these attractive or repulsive forces and the corresponding critical Casimir potentials within mean-field theory. Within this approach we also discuss the quality of the Derjaguin approximation and apply it to Monte Carlo simulation data available for the system under study. We find that the range of validity of the Derjaguin approximation is rather large and that i…
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…
Using an interface displacement model derived from a microscopic density functional theory we investigate thin liquidlike wetting layers adsorbed on flat substrates with an embedded chemical heterogeneity forming a stripe. For a wide range of effective interface potentials we find first-order phase transitions as well as continuous changes between lateral interfacial configurations bound to and repelled from the stripe area. We determine phase diagrams and discuss the conditions under which these morphological changes arise.
{\it Surface-directed spinodal decomposition} (SDSD) is the kinetic interplay of phase separation and wetting at a surface. This process is of great scientific and technological importance. In this paper, we report results from a numerical study of SDSD on a chemically patterned substrate. We consider simple surface patterns for our simulations, but most of the results apply for arbitrary patterns. In layers near the surface, we observe a dynamical crossover from a {\it surface-registry regime} to a {\it phase-separation regime}. We study this crossover using layer-wise correlation functions a…
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.
Nematic liquid crystals confined to geometrically as well as chemically patterned substrate on one end and a flat substrate with strong anchoring on the other is studied using non-Boltzmann Monte Carlo methods. We observe significant deviations from the continuum-based predictions of the phase diagram which was studied as a function of tilt angle at the top substrate and thickness of the cell. Onset of biaxiality at larger tilt angles at the top substrate is observed. A phase shift introduced between the geometrical and chemical pattern has significant effect on the director structures in the …
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 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 consider a nematic liquid crystal confined by two parallel planar interfaces, one being laterally homogeneous and the other provided by a substrate endowed with a periodic chemical stripe pattern. Based on continuum theory we analyze the influence of the lateral pattern on the liquid-crystalline Casimir force acting on the interfaces of the nematic cell at distance d due to the thermal fluctuations of the nematic director. For d much larger than the pattern periodicity, the influence of the patterned substrate can be described by a homogeneous, effective anchoring energy. By tuning this par…
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…
We compute the Casimir force for a system composed of two layers as substrates within three different homogenous layers. We use the scattering approach along with the Matsubara formalism in order to calculate the Casimir force at finite temperature. We impose the appropriate boundary condition on the tangential components of the electric and magnetic fields to construct the reflection matrices. Our calculation is simple such that one can extend it to systems containing inhomogeneous layers as good candidates for designing nanomachines. We find that the Casimir force is proportional to L^(-5) w…
We report on the first measurement of a temperature dependence of the Casimir-Polder force. This measurement was obtained by positioning a nearly pure 87-Rb Bose-Einstein condensate a few microns from a dielectric substrate and exciting its dipole oscillation. Changes in the collective oscillation frequency of the magnetically trapped atoms result from spatial variations in the surface-atom force. In our experiment, the dielectric substrate is heated up to 605 K, while the surrounding environment is kept near room temperature (310 K). The effect of the Casimir-Polder force is measured to be ne…
A nematic liquid crystal in contact with a grating surface possessing an alternating stripe pattern of locally homeotropic and planar anchoring is studied within the Frank--Oseen model. The combination of both chemical and geometrical surface pattern leads to rich phase diagrams, involving a homeotropic, a planar, and a tilted nematic texture. The effect of the groove depth and the anchoring strengths on the location and the order of phase transitions between different nematic textures is studied. A zenithally bistable nematic device is investigated by confining a nematic liquid crystal betwee…
Chemically patterned surfaces are of significant interest in the context of microfluidic applications. Miniaturization of such devices will eventually lead to structures on the nano-scale. Whereas on the micron scale purely macroscopic descriptions of liquid flow are valid, on the nanometer scale long-ranged inter-molecular interactions, thermal fluctuations such as capillary waves, and finally the molecular structure of the liquid become important. We discuss the most important conceptual differences between flow on chemically patterned substrates on the micron scale and on the nanometer scal…
Among the various kinds of effective forces in soft matter, the spatial range and the direction of the so-called critical Casimir force - which is generated by the enhanced thermal fluctuations close to a continuous phase transition - can be controlled and reversibly modified to an uncommonly large extent. In particular, minute temperature changes of the fluid solvent, which provides the near-critical thermal fluctuations, lead to a significant change of the range and strength of the effective interaction among the solute particles. This feature allows one to control, e.g., the aggregation of …
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…
Based on renormalization group concepts and explicit mean field calculations we study the universal contribution to the effective force and torque acting on an ellipsoidal colloidal particle which is dissolved in a critical fluid and is close to a homogeneous planar substrate. At the same closest distance between the substrate and the surface of the particle, the ellipsoidal particle prefers an orientation parallel to the substrate and the magnitude of the fluctuation induced force is larger than if the orientation of the particle is perpendicular to the substrate. The sign of the critical tor…
This paper is the second in a two-part exposition on {\it surface-directed spinodal decomposition} (SDSD), i.e., the interplay of kinetics of wetting and phase separation at a surface which is wetted by one of the components of a binary mixture. In our first paper [P. Das, P.K. Jaiswal and S. Puri, Phys. Rev. E {\bf 102}, 012803 (2020)], we studied SDSD on chemically heterogeneous and physically flat substrates. In this paper, we study SDSD on a chemically homogeneous but morphologically patterned substrate. Such substrates arise in a vast variety of technological applications. Our goal is to …
We investigate theoretically the morphology of a thin nematic film adsorbed at flat substrate patterned by stripes with alternating aligning properties, normal and tangential respectively. We construct a simple "exactly-solvable" effective interfacial model where the liquid crystal distortions are accounted for via an effective interface potential. We find that chemically patterned substrates can strongly deform the nematic-air interface. The amplitude of this substrate-induced undulations increases with decreasing average film thickness and with increasing surface pattern pitch. We find a reg…
We present a general linear response description of membrane adhesion at rough or chemically structured surfaces. Our method accounts for non-local Van der Waals effects and contains the more approximate (and local) Deryagin approach in a simple limit. Specializing to supported membranes we consider the effects of substrate structure on the membrane adhesion energy and configuration. Adhesion is usually less favorable for rough substrates and the membrane shape tends to follow that of the surface contours. Chemical patterning, however, favors adhesion with the membrane configuration being out …
Simulations show that when a phase-separated binary AB fluid is driven to flow past chemically patterned substrates in a microchannel, the fluid exhibits unique morphological instabilities. For the pattern studied, these instabilities give rise to the simultaneous, periodic formation of monodisperse droplets of A-in-B and B-in-A. The system bifurcates between time-independent behavior and different types of regular, non-decaying oscillations in the structural characteristics. The surprisingly complex behavior is observed even in the absence of hydrodynamic interactions and arises from the inte…
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…
A novel approach is proposed, where energy filtered electrons, carrying both chemical identity and electrical information, serve as fine and flexible electrodes in direct electrical measurements. The method, termed 'chemically resolved electrical measurements' (CREM), is simple and general, demonstrated here with a slightly modified X-ray photoelectron spectrometer. Selected sub-surface regions are electrically analyzed and I-V curves of self-assembled monolayers, free of substrate and top contact contributions, are derived with no need for improved metallic substrates. Unique electrical infor…
We consider dynamics of an isolated polymer chain with a chemically active end-bead on a 2D solid substrate containing immobile, randomly placed chemically active sites (traps). For a particular situation when the end-bead can be irreversibly trapped by any of these sites, which results in a complete anchoring of the whole chain, we calculate the time evolution of the probability $P_{ch}(t)$ that the initially non-anchored chain remains mobile until time $t$. We find that for relatively short chains $P_{ch}(t)$ follows at intermediate times a standard-form 2D Smoluchowski-type decay law $ln P_…
A mesoscopic continuum model is employed to analyse the transport mechanisms and structure formation during the redistribution stage of deposition experiments where organic molecules are deposited on a solid substrate with periodic stripe-like wettability patterns. Transversally invariant ridges located on the more wettable stripes are identified as very important transient states and their linear stability is analysed. It is found that there exist two different instability modes that result (i) at large ridge volume in the formation of bulges that spill from the more wettable stripes onto the…
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…
Controlling the spatial distribution of liquid droplets on surfaces via surface energy patterning can be used to control material delivery to specified regions via selective liquid/solid wetting. While studies of the equilibrium shape of liquid droplets on heterogenous substrates exist, much less is known about the corresponding wetting kinetics. We make significant progress towards elucidating details of this topic by studying, via large-scale atomistic simulations, liquid nanodroplets spreading on chemically patterned surfaces. A model is presented for lines of polymer liquid (droplets) on s…
We propose coupled evolution equations for the thickness of a liquid film and the density of an adsorbate layer on a partially wetting solid substrate. Therein, running droplets are studied assuming a chemical reaction underneath the droplets that induces a wettability gradient on the substrate and provides the driving force for droplet motion. Two different regimes for moving droplets -- reaction-limited and saturated regime -- are described. They correspond to increasing and decreasing velocities with increasing reaction rates and droplet sizes, respectively. The existence of the two regimes…
Random (disordered) components in the surface anchoring of the smectic-A liquid crystalline film in general modify the thermal pseudo-Casimir interaction. Anchoring disorder of the quenched type is in general decoupled from the thermal pseudo-Casimir force and gives rise to an additional disorder-generated interaction, in distinction to the annealed disorder, whose effect on the pseudo-Casimir force is non-additive. We consider the effects of the surface anchoring disorder by assuming that one of the substrates of the film is contaminated by a disorder source, resulting in a Gaussian-weighted …
Using general scaling arguments combined with mean-field theory we investigate the critical ($T \simeq T_c$) and off-critical ($T\ne 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 $μ$. We find that the total force is attractive both below and above $T_c$. If, however, the direct substrate-substrate contribution is subt…
Within mean-field theory we calculate the scaling functions associated with critical Casimir forces for a system consisting of two spherical colloids immersed in a binary liquid mixture near its consolute point and facing a planar, homogeneous substrate. For several geometrical arrangements and boundary conditions we analyze the normal and the lateral critical Casimir forces acting on one of the two colloids. We find interesting features such as a change of sign of these forces upon varying either the position of one of the colloids or the temperature. By subtracting the pairwise forces from t…
Investigations of the elastic behavior of bulk elastomers have traditionally proceeded on the basis of classical rubber elasticity, which regards chains as thermally fluctuating but disregards the thermal fluctuations of the cross-links. Here, we consider an incompressible and flat elastomer film of an axisymmetric shape confined between two large hard co-planar substrates, with the axis of the film perpendicular to the substrates. We address the impact that thermal fluctuations of the cross-links have on the free energy of elastic deformation of the system, subject to the requirement that the…
We use density functional theory to investigate adsorption of liquid mixtures on solid surfaces modified with end-grafted chains. The chains are modelled as freely joined spheres. The fluid molecules are spherical. All spherical species interact via the Lennard-Jones (12-6) potential. The Lennard-Jones (9-3) potential describes interactions of solvent molecules with the substrate. We study the relative excess adsorption isotherms, the structure of surface layer and its composition. The impact of the following parameters on adsorption is discussed: the grafting density, the grafted chain length…
Recently there is strong experimental and theoretical interest in studying the self-assembly and the phase behavior of patchy and of Janus particles, which form colloidal suspensions. Although in this quest a variety of effective interactions have been proposed and used in order to achieve directed assembly, the critical Casimir effect stands out as being particularly suitable in this respect because it provides both attractive and repulsive interactions as well as the potential of a sensitive temperature control of their strength. Specifically, we have calculated the critical Casimir force be…
We model an infinitely long liquid bridge confined between two plates chemically patterned by stripes of same width and different contact angle, where the three-phase contact line runs, on average, perpendicular to the stripes. This allows us to study the corrugation of a contact line in the absence of pinning. We find that, if the spacing between the plates is large compared to the length scale of the surface patterning, the cosine of the macroscopic contact angle corresponds to an average of cosines of the intrinsic angles of the stripes, as predicted by the Cassie equation. If, however, the…
We present a molecular dynamics study of the motion of cylindrical polymer droplets on striped surfaces. We first consider the equilibrium properties of droplets on different surfaces, we show that for small stripes the Cassie-Baxter equation gives a good approximation of the equilibrium contact angle. As the stripe width becomes non-negligible compared to the dimension of the droplets, the droplet has to deform significantly to minimize its free energy, this results in a smaller value of the contact angle than the continuum model predicts. We then evaluate the slip length, and thus the dampin…
The influence of a chemically or electrically heterogeneous distribution of interaction sites at a planar substrate on the number density of an adjacent fluid is studied by means of classical density functional theory (DFT). In the case of electrolyte solutions the effect of this heterogeneity is particularly long ranged, because the corresponding relevant length scale is set by the Debye length which is large compared to molecular sizes. The DFT used here takes the solvent particles explicitly into account and thus captures phenomena, inter alia, due to ion-solvent coupling. The present appro…
Using a coarse-grained bead-spring model of flexible polymer chains, the structure of a polymeric nanodroplet adsorbed on a chemically decorated flat wall is investigated by means of Molecular Dynamics simulation. We consider sessile drops on a lyophilic (attractive for the monomers) region of circular shape with radius R_D while the remaining part of the substrate is lyophobic. The variation of the droplet shape, including its contact angle, with R_D is studied, and the density profiles across these droplets also are obtained. In addition, the interaction of droplets adsorbed on two walls for…
The Casimir-Polder-Lifshitz force felt by an atom near the surface of a substrate is calculated out of thermal equilibrium in terms of the dielectric function of the material and of the atomic polarizability. The new force decays like $1/z^3$ at large distances (i.e. slower than at equilibrium), exhibits a sizable temperature dependence and is attractive or repulsive depending on whether the temperature of the substrate is higher or smaller than the one of the environment. Our predictions can be relevant for experiments with ultracold atomic gases. Both dielectric and metal substrates are cons…
We investigate morphologies of semiflexible polymer rings, such as circular DNA, which are adsorbed onto topographically or chemically structured substrate surfaces. We classify all equilibrium morphologies for two striped surface structures, (i) topographical surface grooves and (ii) chemically structured surface domains. For both types of stripes, we find four equilibrium shapes: a round toroidal and a confined elongated shape as well as two shapes containing bulges. We determine the complete bifurcation diagram of these morphologies as a function of their contour length and the ratio of adh…
We analyze the transverse intersubstrate pseudo-Casimir force, arising as a result of thermal fluctuations of the liquid crystalline layers of a smectic-A film confined between two planar substrates in a bookshelf geometry, in which the equidistant smectic layers are placed perpendicular to the bounding surfaces. We discuss the variation of the interaction force as a function of the intersubstrate separation in the presence of surface anchoring to the substrates, showing that the force induced by confined fluctuations is attractive and depends on the penetration length as well as the layer spa…
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…
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 …
We consider a nematic liquid crystal confined by two parallel flat substrates whose anchoring conditions vary periodically in one lateral direction. Within the Gaussian approximation, we study the effective forces between the patterned substrates induced by the thermal fluctuations of the nematic director. The shear force oscillates as function of the lateral shift between the patterns on the lower and the upper substrates. We compare the strength of this fluctuation-induced lateral force with the lateral van der Waals force arising from chemically structured adsorbed monolayers. The fluctuati…
We present new capacitance measurements of critical Casimir force-induced thinning of $^4$He films near the superfluid/normal transition, focused on the region below $T_λ$ where the effect is the greatest. $^4$He films of 238, 285, and 340 Åthickness are adsorbed on N-doped silicon substrates with roughness $\approx 8 Å$. The Casimir force scaling function $\vartheta $, deduced from the thinning of these three films, collapses onto a single universal curve, attaining a minimum $\vartheta = -1.30 \pm 0.03$ at $x=td^{1/ν}=-9.7\pm 0.8 Å^{1/ν}$. The collapse confirms the finite-size scaling origin…
We examine fluctuation-induced (pseudo-Casimir) interactions in nematic liquid-crystalline films confined between two surfaces, where one of the surfaces imposes a strong homeotropic anchoring (ensuring a uniform mean director profile), while the other one is assumed to be a chemically disordered substrate exhibiting an annealed, random distribution of anchoring energies. We employ a saddle-point approximation to evaluate the free energy of interaction mediated between the two surfaces and investigate how the interaction force is influenced by the presence of disordered surface anchoring energ…
Casimir forces in quantum electrodynamics emerge between microscopic metallic objects because of the confinement of the vacuum electromagnetic fluctuations occurring even at zero temperature. Their generalization at finite temperature and in material media are referred to as Casimir--Lifshitz forces. These forces are typically attractive, leading to the widespread problem of stiction between the metallic parts of micro- and nanodevices. Recently, repulsive Casimir forces have been experimentally realized but their reliance on specialized materials prevents their dynamic control and thus limits…
Nanodroplets on chemically structured substrates move under the action of disjoining pressure induced forces. A detailed analysis of them shows that even in the absence of long-ranged lateral variations of the effective interface potential, already the fact, that due their small size nano-droplets do not sample the disjoining pressure at all distances from the substrate, can lead to droplet motion towards the less wettable part of the substrate, i.e., in the direction opposite to the one expected on the basis of macroscopic wettability considerations.
