A. Maciolek

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.

Monte Carlo simulation results for critical Casimir forces

The confinement of critical fluctuations in soft media induces critical Casimir forces acting on the confining surfaces. The temperature and geometry dependences of such forces are characterized by universal scaling functions. A novel approach is presented to determine them for films via Monte Carlo simulations of lattice models. The method is based on an integration scheme of free energy differences. Our results for the Ising and the XY universality class agree well with corresponding experimental results for wetting layers of classical binary liquid mixtures and of 4He, respectively.

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.

Phase behavior of colloidal suspensions with critical solvents in terms of effective interactions

We study the phase behavior of colloidal suspensions the solvents of which are considered to be binary liquid mixtures undergoing phase segregation. We focus on the thermodynamic region close to the critical point of the accompanying miscibility gap. There, due to the colloidal particles acting as cavities in the critical medium, the spatial confinements of the critical fluctuations of the corresponding order parameter result in the effective, so-called critical Casimir forces between the colloids. Employing an approach in terms of effective, one-component colloidal systems, we explore the possibility of phase coexistence between two phases of colloidal suspensions, one being rich and the other being poor in colloidal particles. The reliability of this effective approach is discussed.

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.

Structure and aggregation of colloids immersed in critical solvents

We consider an ensemble of spherical colloidal particles immersed in a near-critical solvent such as a binary liquid mixture close to its critical demixing point. The emerging long-ranged fluctuations of the corresponding order parameter of the solvent drive the divergence of the correlation length. Spatial confinements of these critical fluctuations by colloidal solute particles, acting as cavities in the fluctuating medium, restrict and modify the fluctuation spectrum in a way which depends on their relative configuration. This results in effective, so-called critical Casimir forces (CCFs) acting on the confining surfaces. Using the available knowledge about CCFs we study the structure and stability of such colloidal suspensions by employing an approach in terms of effective, one-component colloidal systems. Applying the approximation of pairwise additive CCFs we calculate the radial distribution function of the colloids, which is experimentally accessible. We analyze colloidal aggregation due to CCFs and thus allude to previous experimental studies which are still under debate.

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.

Critical Casimir forces for Ising films with variable boundary fields

Monte Carlo simulations based on an integration scheme for free energy differences is used to compute critical Casimir forces for three-dimensional Ising films with various boundary fields. We study the scaling behavior of the critical Casimir force, including the scaling variable related to the boundary fields. Finite size corrections to scaling are taken into account. We pay special attention to that range of surface field strengths within which the force changes from repulsive to attractive upon increasing the temperature. Our data are compared with other results available in the literature.

Effects of weak surface fields on the density profiles and adsorption of a confined fluid near bulk criticality

The density profile ρ(z) and Gibbs adsorption Γ of a near-critical fluid confined between two identical planar walls is studied by means of Monte Carlo simulation and by density functional theory for a Lennard-Jones fluid. By reducing the strength of wall–fluid interactions relative to fluid–fluid interactions we observe a crossover from behavior characteristic of the normal surface universality class, strong critical adsorption, to behavior characteristic of a “neutral” wall. The crossover is reminiscent of that which occurs near the ordinary surface transition in Ising films subject to vanishing surface fields. For the “neutral” wall ρ(z), away from the walls, is almost constant throughout the slit capillary and gives rise to a Γ that is constant along the critical isochore. The same “neutral” wall yields a line of capillary coexistence that is almost identical to the bulk coexistence line. In the crossover regime we observe features in ρ(z) similar to those found in the magnetization profile of the cri...

Distribution of ions near a charged selective surface in critical binary solvents.

Near-critical binary mixtures containing ionic solutes near a charged wall preferentially adsorbing one component of the solvent are studied. Within the Landau-Ginzburg approach extended to include electrostatic interactions and the chemical preference of ions for one component of the solvent, we obtain a simple form for the leading-order correction to the Debye-Hückel theory result for the charge density profile. Our result shows that critical adsorption influences significantly distribution of ions near the wall. This effect may have important implications for the screening of electrostatic interactions between charged surfaces immersed in binary near-critical solvents.