Critical Casimir interactions around the consolute point of a binary solvent

Spatial confinement of a near-critical medium changes its fluctuation spectrum and modifies the corresponding order parameter distribution. These effects result in effective, so-called critical Casimir forces (CCFs) acting on the confining surfaces. These forces are attractive for like boundary conditions of the order parameter at the opposing surfaces of the confinement. For colloidal particles dissolved in a binary liquid mixture acting as a solvent close to its critical point of demixing, one thus expects the emergence of phase segregation into equilibrium colloidal liquid and gas phases. We analyze how such phenomena occur asymmetrically in the whole thermodynamic neighborhood of the consolute point of the binary solvent. By applying field-theoretical methods within mean-field approximation and the semi-empirical de Gennes-Fisher functional, we study the CCFs acting between planar parallel walls as well as between two spherical colloids and their dependence on temperature and on the composition of the near-critical binary mixture. We find that for compositions slightly poor in the molecules preferentially adsorbed at the surfaces, the CCFs are significantly stronger than at the critical composition, thus leading to pronounced colloidal segregation. The segregation phase diagram of the colloid solution following from the calculated effective pair potential between the colloids agrees surprisingly well with experiments and simulations

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

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

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 debat

Tunability of Critical Casimir Interactions by Boundary Conditions

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 temperature changes but also to small changes in the surface properties.Comment: 4 figures; http://www.iop.org/EJ/article/0295-5075/88/2/26001/epl_88_2_26001.htm

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

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 that the leading scaling corrections are suppressed, numerical integration, and finite-size scaling analysis we determine the critical Casimir force and its 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 system reduces 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 to equal and opposite values, respectively. We show that the universal scaling function of the critical Casimir force for small but finite aspect ratios displays a linear dependence on the aspect ratio which is solely due to the presence of the lateral inhomogeneity. We also analyze the order-parameter profiles at criticality and their universal scaling function which allows us to probe theoretical predictions and to compare with experimental data.Comment: revised version, section 5.2 expanded; 53 pages, 12 figures, iopart clas