Critical Casimir Forces Research Articles

Critical Casimir forces steered by patterned substrates

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 colloidal dispersions or the spatial distribution of colloids in the presence of chemically or topographically patterned substrates. The spatial direction of the effective force acting on a solute particle depends only on the surface properties of the immersed particles and can be spatially modulated by suitably patterned surfaces. These critical Casimir forces are largely independent of the specific materials properties of both the solvent and the confining surfaces. This characteristic universality of critical phenomena allows systematic and quantitative theoretical studies of the critical Casimir forces in terms of suitable representative and simplified models. Here we highlight recent theoretical and experimental advances concerning critical Casimir forces with a particular emphasis on the numerous possibilities of controlling these forces by substrate patterns.

Salt-induced changes of colloidal interactions in critical mixtures

We report on salt-dependent interaction potentials of a single charged particle suspended in a binary liquid mixture above a charged wall. For symmetric boundary conditions (BC) we observe attractive particle-wall interaction forces which are similar to critical Casimir forces previously observed in salt-free mixtures. However, in case of antisymmetric BC we find a temperature-dependent crossover from attractive to repulsive forces which is in strong contrast to salt-free conditions. Additionally performed small-angle x-ray scattering experiments demonstrate that the bulk critical fluctuations are not affected by the addition of salt. This suggests that the observed crossover can not be attributed alone to critical Casimir forces. Instead our experiments point towards a possible coupling between the ionic distributions and the concentration profiles in the binary mixture which then affects the interaction potentials in such systems.

Critical Casimir forces and adsorption profiles in the presence of a chemically structuredsubstrate

Motivated by recent experiments with confined binary liquid mixtures near demixing, westudy the universal critical properties of a system, which belongs to the Ising universalityclass, in the film geometry. We employ periodic boundary conditions in the twolateral directions and fixed boundary conditions on the two confining surfaces, suchthat one of them has a spatially homogeneous adsorption preference while theother one exhibits a laterally alternating adsorption preference, resembling locallya single chemical step. By means of Monte Carlo simulations of an improvedHamiltonian, so that the leading scaling corrections are suppressed, numericalintegration and finite-size scaling analysis we determine the critical Casimir force andits universal scaling function for various values of the aspect ratio of the film.In the limit of a vanishing aspect ratio the critical Casimir force of this systemreduces to the mean value of the critical Casimir force for laterally homogeneous + + and + − boundary conditions, corresponding to the surface spins on the two surfaces being fixed toequal and opposite values, respectively. We show that the universal scaling function of thecritical Casimir force for small but finite aspect ratios displays a linear dependence on theaspect ratio which is solely due to the presence of the lateral inhomogeneity. We alsoanalyse the order-parameter profiles at criticality and their universal scaling function,which allows us to probe theoretical predictions and to compare with experimentaldata.

Boundary conditions and the critical Casimir force on an Ising model film: Exact results in one and two dimensions

Finite-size effects in certain critical systems can be understood as universal Casimir forces. Here, we compare the Casimir force for free, fixed, periodic, and antiperiodic boundary conditions in the exactly calculable case of the ferromagnetic Ising model in one and two dimensions. We employ a procedure which allows us to calculate the Casimir force with the aforementioned boundary conditions analytically in a transparent manner. Among other results, we find an attractive Casimir force for the case of periodic boundary conditions and a repulsive Casimir force in the antiperiodic case.

Critical Casimir effect for colloids close to chemically patterned substrates

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 it fails only for surface structures which are very small compared to the geometric mean of the size of the colloid and its distance from the substrate. For certain chemical structures of the substrate, the critical Casimir force acting on the colloid can change sign as a function of the distance between the particle and the substrate; this provides a mechanism for stable levitation at a certain distance which can be strongly tuned by temperature, i.e., with a sensitivity of more than 200 nm/K.

Colloidal Aggregation and Critical Casimir Forces

A recent Letter [Phys. Rev. Lett. 103, 156101 (2009)] reports the experimental observation of aggregation of colloidal particles dispersed in a liquid mixture of heavy water and 3-methylpyridine. The experimental data are interpreted in terms of a model which accounts solely for the competing effects of the interparticle electrostatic repulsion and of the attractive critical Casimir force. Here we show, however, that the reported aggregation actually occurs within ranges of values of the correlation length and of the Debye screening length ruled out by the proposed model and that a significant part of the experimental data presented in the Letter cannot be consistently interpreted in terms of such a model.

Casimir Interactions in Ising Strips with Boundary Fields: Exact Results

An exact statistical mechanical derivation is given of the critical Casimir forces for Ising strips with arbitrary surface fields applied to edges. Our results show that the strength as well as the sign of the force can be controlled by varying the temperature or the fields. An interpretation of the results is given in terms of a linked cluster expansion. This suggests a systematic approach for deriving the critical Casimir force which can be used in more general models.

Crossover of critical Casimir forces between different surface universality classes

In confined systems near a continuous phase transition the long-ranged fluctuations of the corresponding order parameter are subject to boundary conditions. These constraints result in so-called critical Casimir forces acting as effective forces on the confining surfaces. For systems belonging to the Ising bulk universality class corresponding to a scalar order parameter the critical Casimir force is studied for the film geometry in the crossover regime characterized by different surface fields at the two surfaces. The scaling function of the critical Casimir force is calculated within mean-field theory. Within our approach, the scaling functions of the critical Casimir force and of the order parameter profile for finite surface fields can be mapped by rescaling, except for a narrow crossover regime, onto the corresponding scaling function of the so-called normal fixed point of strong surface fields. In the crossover regime, the critical Casimir force as function of temperature exhibits more than one extremum and for certain ranges of surface field strengths it changes sign twice upon varying temperature. Monte Carlo simulation data obtained for a three-dimensional Ising film show similar trends. The sign of the critical Casimir force can be inferred from the comparison of the order parameter profiles in the film and in the semi-infinite geometry.

The critical Casimir force in the superfluid phase: effect of fluctuations

We have considered the critical Casimir force on a 4He film below and above the bulk λ point. We have explored the role of fluctuations around the mean field theory in a perturbative manner, and have substantially improved the mean field result of Zandi et al (2007 Phys. Rev. E 76 030601(R)). The Casimir scaling function obtained by us approaches a universal constant () for T≲2.13 K.

Coupling of demixing and magnetic ordering phase transitions probed by turbidimetricmeasurements in a binary mixture doped with magnetic nanoparticles

We present a novel study on the effect of a magnetic field applied on a binary mixturedoped with magnetic nanoparticles close to its demixing transition. Turbiditymeasurements in the Faraday configuration show that the effect of applying an externalfield produces changes in the critical opalescence of the mixture that allow us to track anaggregation produced by critical Casimir forces and a reversible aggregation dueto the formation of chain-like flocks in response to the external magnetic field.The observation of a crossover of the aggregation curves through optical signalsis interpreted as the evolution from low to high power dispersion nuclei due toan increase in the radius of the condensation seed brought about by Casimir ormagnetic interactions. Finally, evidence of an enhanced magnetocaloric effect due tothe coupling between mixing and ordering phase transitions is presented whichopens up a nonsolid state approach of designing refrigerating cycles and devices.

Proposed fitting function for the critical Casimir force on 4He film below the [formula omitted] point

We have extended the mean field calculations [9] of Zandi et al. (2007) and have obtained an approximate mathematical expression for the Casimir scaling function ϑ ( y ) , which if extrapolated to the domain π 2 ≥ − y ≥ 0 , becomes surprisingly similar to that obtained experimentally [16] by Ganshin et al. (2006). The extrapolated ϑ ( y ) can be regarded as a proposed fitting function, that appears to agree better with the experiments [16] in D = 3 , than the exact mean field results of Zandi et al. (2007) [9].

Critical Casimir effect in classical binary liquid mixtures

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 of critical Casimir forces by total internal reflection microscopy with femtonewton resolution. The corresponding potentials are determined for individual colloidal particles floating above a substrate under the action of the critical thermal noise in the solvent medium, constituted by a binary liquid mixture of water and 2,6-lutidine near its lower consolute point. Depending on the relative adsorption preferences of the colloid and substrate surfaces with respect to the two components of the binary liquid mixture, we observe that, upon approaching the critical point of the solvent, attractive or repulsive forces emerge and supersede those prevailing away from it. Based on the knowledge of the critical Casimir forces acting in film geometries within the Ising universality class and with equal or opposing boundary conditions, we provide the corresponding theoretical predictions for the sphere-planar wall geometry of the experiment. The experimental data for the effective potential can be interpreted consistently in terms of these predictions and a remarkable quantitative agreement is observed.

Direct Observation of Colloidal Aggregation by Critical Casimir Forces

We present a refractive-index-matched colloidal system that allows direct observation of critical Casimir induced aggregation with a confocal microscope. We show that in this system, in which van der Waals forces are negligible, a simple competition between repulsive screened Coulomb and attractive critical Casimir forces can account quantitatively for the reversible aggregation. Above the temperature T(a), the critical Casimir force drives aggregation of the particles into fractal clusters, while below T(a), the electrostatic repulsion between the particles breaks up the clusters, and the particles resuspend by thermal diffusion. The aggregation is observed in a remarkably wide temperature range of as much as 15 degrees. We derive a simple expression for the particle pair potential that accounts quantitatively for the temperature-dependent aggregation and aggregate breakup.

Erratum: Universal scaling functions of critical Casimir forces obtained by Monte Carlo simulations [Phys. Rev. E79, 041142 (2009)

Erratum: Universal scaling functions of critical Casimir forces obtained by Monte Carlo simulations [Phys. Rev. E<b>79</b>, 041142 (2009)

Universal scaling functions of critical Casimir forces obtained by Monte Carlo simulations

Effective Casimir forces induced by thermal fluctuations in the vicinity of bulk critical points are studied by means of Monte Carlo simulations in three-dimensional systems for film geometries and within the experimentally relevant Ising and XY universality classes. Several surface universality classes of the confining surfaces are considered, some of which are relevant for recent experiments. An approach introduced previously [O. Vasilyev, EPL 80, 60009 (2007)], based inter alia on an integration scheme of free-energy differences, is utilized to compute the universal scaling functions of the critical Casimir forces in the critical range of temperatures above and below the bulk critical temperature. The resulting predictions are compared with corresponding experimental data for wetting films of fluids and with available theoretical results.

The Casimir effect: From quantum to critical fluctuations

The Casimir effect in quantum electrodynamics (QED) is perhaps the best-known example of fluctuation-induced long-ranged force acting on objects (conducting plates) immersed in a fluctuating medium (quantum electromagnetic field in vacuum). A similar effect emerges in statistical physics, where the force acting, e.g., on colloidal particles immersed in a binary liquid mixture is affected by the classical thermal fluctuations occurring in the surrounding medium. The resulting Casimir-like force acquires universal features upon approaching a critical point of the medium and becomes long-ranged at criticality. In turn, this universality allows one to investigate theoretically the temperature dependence of the force via representative models and to stringently test the corresponding predictions in experiments. In contrast to QED, the Casimir force resulting from critical fluctuations can be easily tuned with respect to strength and sign by surface treatments and temperature control. We present some recent advances in the theoretical study of the universal properties of the critical Casimir force arising in thin films. The corresponding predictions compare very well with the experimental results obtained for wetting layers of various fluids. We discuss how the Casimir force between a colloidal particle and a planar wall immersed in a binary liquid mixture has been measured with femto-Newton accuracy, comparing these experimental results with the corresponding theoretical predictions.

Critical Casimir Forces in Colloidal Suspensions on Chemically Patterned Surfaces

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.

Kinetic Study of the Aggregation of Colloids Immersed in a Binary Mixture of Polymers

AbstractSummary: We consider an assembly of colloidal particles, which are immersed in a binary mixture of polymers. At temperatures close to the critical point of the free mixture, the fluctuations of the composition induce a critical Casimir force between colloids. This force naturally depends on their distance and it is responsible for the colloidal aggregation. In this paper, we propose to study the kinetics of such a transition leading colloids from a dispersed phase (gas) to a dense one (liquid). This kinetics is studied through the relaxation rate, which is a function of the transfer wave‐vector.

Critical adsorption and critical Casimir forces for geometrically structured confinements

We study the behavior of fluids, confined by geometrically structured substrates, upon approaching a critical point at T=T(c) 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 to 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.

Crossover from Attractive to Repulsive Casimir Forces and Vice Versa

Systems described by an O(n) symmetrical varphi;{4} Hamiltonian are considered in a d-dimensional film geometry at their bulk critical points. The critical Casimir forces between the film's boundary planes B_{j}, j=1,2, are investigated as functions of film thickness L for generic symmetry-preserving boundary conditions partial differential_{n}phi=c[over composite function]_{j}phi. The L-dependent part of the reduced excess free energy per cross-sectional area takes the scaling form f_{res} approximately D(c_{1}L;{Phi/nu},c_{2}L;{Phi/nu})/L;{d-1} when d<4, where c_{i} are scaling fields associated with the variables c[over composite function]_{i} and Phi is a surface crossover exponent. Explicit two-loop renormalization group results for the function D(c_{1},c_{2}) at d=4- dimensions are presented. These show that (i) the Casimir force can have either sign, depending on c_{1} and c_{2}, and (ii) for appropriate choices of the enhancements c[over composite function]_{j}, crossovers from attraction to repulsion and vice versa occur as L increases.