Critical Casimir forces in soft matter.

We review recent advances in the theoretical, numerical, and experimental studies of critical Casimir forces in soft matter, with particular emphasis on their relevance for the structures of colloidal suspensions and on their dynamics. Distinct from other interactions which act in soft matter, such as electrostatic and van der Waals forces, critical Casimir forces are effective interactions characterised by the possibility to control reversibly their strength via minute temperature changes, while their attractive or repulsive character is conveniently determined via surface treatments or by structuring the involved surfaces. These features make critical Casimir forces excellent candidates for controlling the equilibrium and dynamical properties of individual colloids or colloidal dispersions as well as for possible applications in micro-mechanical systems. In the past 25 years a number of theoretical and experimental studies have been devoted to investigating these forces primarily under thermal equilibrium conditions, while their dynamical and non-equilibrium behaviour is a largely unexplored subject open for future investigations.

Modeling Active Non-Markovian Oscillations.

Modeling noisy oscillations of active systems is one of the current challenges in physics and biology. Because the physical mechanisms of such processes are often difficult to identify, we propose a linear stochastic model driven by a non-Markovian bistable noise that is capable of generating self-sustained periodic oscillation. We derive analytical predictions for most relevant dynamical and thermodynamic properties of the model. This minimal model turns out to describe accurately bistablelike oscillatory motion of hair bundles in bullfrog sacculus, extracted from experimental data. Based on and in agreement with these data, we estimate the power required to sustain such active oscillations to be of the order of 100 k_{B}T per oscillation cycle.

Direct measurement of critical Casimir forces.

When fluctuating fields are confined between two surfaces, long-range forces arise. A famous example is the quantum-electrodynamical Casimir force that results from zero-point vacuum fluctuations confined between two conducting metal plates. A thermodynamic analogue is the critical Casimir force: it acts between surfaces immersed in a binary liquid mixture close to its critical point and arises from the confinement of concentration fluctuations within the thin film of fluid separating the surfaces. So far, all experimental evidence for the existence of this effect has been indirect. Here we report the direct measurement of critical Casimir force between a single colloidal sphere and a flat silica surface immersed in a mixture of water and 2,6-lutidine near its critical point. We use total internal reflection microscopy to determine in situ the forces between the sphere and the surface, with femtonewton resolution. Depending on whether the adsorption preferences of the sphere and the surface for water and 2,6-lutidine are identical or opposite, we measure attractive and repulsive forces, respectively, that agree quantitatively with theoretical predictions and exhibit exquisite dependence on the temperature of the system. We expect that these features of critical Casimir forces may result in novel uses of colloids as model systems.

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.

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.

Critical Casimir effect in superfluid wetting films.

Recent experimental data for the complete wetting behavior of pure 4He and of 3He-4He mixtures exposed to solid substrates show that there is a change of the corresponding film thicknesses L upon approaching thermodynamically the lambda transition and the tricritical end point, respectively, which can be attributed to critical Casimir forces fC. We calculate the scaling functions theta of fC within models representing the corresponding universality classes. For the mixtures our analysis provides an understanding of the rich behavior of theta deduced from the experimental data and predicts the crossover behavior between the tricritical point and the lambda transition of pure 4He which are connected by a line of critical points. The formation of a "soft-mode" phase within the wetting films gives rise to a pronounced maximum of fC below the tricritical point as observed experimentally. Near the tricritical point we find logarithmic corrections approximately L(-3)(ln L)1/2 for the leading behavior of theta dominating the contributions from the background dispersion forces.

Spreading in narrow channels.

We study a lattice model for the spreading of fluid films, which are a few molecular layers thick, in narrow channels with inert lateral walls. We focus on systems connected to two particle reservoirs at different chemical potentials, considering an attractive substrate potential at the bottom, confining sidewalls, and hard-core repulsive fluid-fluid interactions. Using kinetic Monte Carlo simulations we find a diffusive behavior. The corresponding diffusion coefficient depends on the density and is bounded from below by the free one-dimensional diffusion coefficient, valid for an inert bottom wall. These numerical results are rationalized within the corresponding continuum limit.

Aging at criticality in model-C dynamics.

We study the off-equilibrium two-point critical response and correlation functions for the relaxational dynamics with a coupling to a conserved density (model C) of the O(N) vector model. They are determined in an epsilon=4-d expansion for vanishing momentum. We briefly discuss their scaling behaviors and the associated scaling forms are determined up to first order in epsilon. The corresponding fluctuation-dissipation ratio has a nontrivial large time limit in the aging regime and, up to one-loop order, it is the same as that of the model A for the physically relevant case N=1. The comparison with predictions of local scale invariance is also discussed.

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.