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 around a single particle for various shapes and configurations of the surface patches. The formalism encompasses several interesting configurations, including Janus particles of circular and needle shapes with dipolar symmetry and a circular particle with quadrupolar symmetry. From these single-particle properties we construct the so-called small particle operator expansion (SPOE), which enables us to obtain asymptotically exact expressions for the position- and orientation-dependent critical Casimir interactions of the particles with distant objects, such as another particle or the confining walls of a half plane, strip, or wedge, with various boundary conditions for the order parameter. In several cases we compare the interactions at large distances with the ones at close distance (but still large on the molecular scale). We also compare our analytical results for two Janus particles with recent simulation data.
We report an entropy-driven orientational hopping transition in a magnetically confined colloidal Janus rod. In a magnetic field, the sedimented rod randomly hops between horizontal and vertical states: the latter state comes at a substantial gravitational cost at no reduction of magnetic potential energy. The probability distribution over the angles of the rod shows that the presence of an external magnetic field leads to the emergence of a metastable vertical state separated from the ground state by an effective barrier. This barrier does not come from the potential energy but rather from th…
Most available theoretical predictions for the self-diffusiophoretic motion of colloidal particles are based on the hydrodynamic thin boundary layer approximation in combination with a solvent body force due to a self-generated local solute gradient. This gradient is enforced through specifying boundary conditions, typically without accounting for the thermodynamic cost to maintain the gradient. Here we present an alternative thermodynamic approach that exploits a direct link between dynamics and entropy production: the local detailed balance condition. We study two cases: First, we revisit se…
We investigate the influence of geometric confinement on the free energy of an idealized model for charge-stabilized colloidal suspensions. The mean-field Poisson-Boltzmann formulation for this system predicts pure repulsion among macroionic colloidal spheres. Fluctuations in the simple ions' distribution provide a mechanism for the macroions to attract each other at large separations. Although this Casimir interaction is long-ranged, it is too weak to influence colloidal crystals' dynamics.
Colloidal Janus spheres in water (one hemisphere attractive and the other repulsive) assemble into two-dimensional hexagonal crystals with orientational order controlled by anisotropic interactions. We exploit the decoupled translational and rotational order to quantify the orientational dynamics. Via imaging experiments and Monte Carlo simulations we demonstrate that the correlations in the orientation of individual Janus spheres exhibit glasslike dynamics that can be controlled via the ionic strength. Thus, these colloidal building blocks provide a particularly suitable model glass system fo…
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…
Critical Casimir forces can play an important role for applications in nano-science and nanotechnology, owing to their piconewton strength, nanometric action range, fine tunability as a function of temperature, and exquisite dependence on the surface properties of the involved objects. Here, we investigate the effects of critical Casimir forces on the free dynamics of a pair of colloidal particles dispersed in the bulk of a near-critical binary liquid solvent, using blinking optical tweezers. In particular we measure the time evolution of the distance between the two colloids to determine thei…
By using the critical Casimir force, we study the attractive strength dependent aggregation of colloids with and without gravity by means of Near Field scattering. Significant differences were seen between microgravity and ground experiments, both in the structure of the formed fractal aggregates as well as the kinetics of growth. Ground measurements are severely affected by sedimentation resulting in reaction limited behavior. In microgravity, a purely diffusive behavior is seen reflected both in the measured fractal dimensions for the aggregates as well as the power law behavior in the rate …
We study the fluctuation-induced Casimir interactions in colloidal suspensions, especially between colloids immersed in a binary liquid close to its critical demixing point. To simulate these systems, we present a highly efficient cluster Monte Carlo algorithm based on geometric symmetries of the Hamiltonian. Utilizing the principle of universality, the medium is represented by an Ising system while the colloids are areas of spins with fixed orientation. Our results for the Casimir interaction potential between two particles at the critical point in two dimensions perfectly agree with the exac…
Some time ago, Fisher and de Gennes pointed out that long-ranged correlations in a fluid close to its critical point Tc cause distinct forces between immersed colloidal particles which can even lead to flocculation [C. R. Acad. Sc. Paris B 287, 207 (1978)]. Here we calculate such forces between pairs of spherical particles as function of both relevant thermodynamic variables, i.e., the reduced temperature t = (T-Tc)/Tc and the field h conjugate to the order parameter. This provides the basis for specific predictions concerning the phase behavior of a suspension of colloidal particles in a near…
We study the polar collective dynamics of Janus colloidal particles fueled by an AC electric field. When the density is high enough, the polar interactions between the particles induce a polar orientationally ordered state which exhibits features reminiscent of the Vicsek model such as true long-range order and giant number fluctuations. Independent measurements of the polarity and velocity at the single particle level allowed us to investigate the single particle dynamics within the ordered state. We discovered theoretically-unaddressed statistical properties of the ordered state such as the …
A class of binary mixtures of Janus fluids formed by colloidal spheres with the hydrophobic hemispheres constrained to point either up or down are studied by means of Gibbs ensemble Monte Carlo simulations and simple analytical approximations. These fluids can be experimentally realized by the application of an external static electrical field. The gas-liquid and demixing phase transitions in five specific models with different patch-patch affinities are analyzed. It is found that a gas-liquid transition is present in all the models, even if only one of the four possible patch-patch interactio…
We present an experimental and theoretical study of the phase behavior of a binary mixture of colloids with opposite adsorption preferences in a critical solvent. As a result of the attractive and repulsive critical Casimir forces, the critical fluctuations of the solvent lead to a further critical point in the colloidal system, i.e. to a critical colloidal-liquid--colloidal-liquid demixing phase transition which is controlled by the solvent temperature. Our experimental findings are in good agreement with calculations based on a simple approximation for the free energy of the system.
To elucidate mechanisms of mesoscopic turbulence exhibited by active particles, we experimentally study turbulent states of non-living self-propelled particles. We realize an experimental system with dense suspensions of asymmetrical colloidal particles (Janus particles) self-propelling on a two-dimensional surface under an AC electric field. Velocity fields of the Janus particles in the crowded situation can be regarded as a sort of turbulence because it contains many vortices and their velocities change abruptly. Correlation functions of their velocity field reveal the coexistence of polar a…
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 a…
We present a detailed study of the kinetic cluster growth process during gelation of weakly attractive colloidal particles by means of experiments on critical Casimir attractive colloidal systems, simulations and analytical theory. In the experiments and simulations, we follow the mean coordination number of the particles during the growth of clusters to identify an attractive-strength independent cluster evolution as a function of mean coordination number. We relate this cluster evolution to the kinetic attachment and detachment rates of particles and particle clusters. We find that single-pa…
We study the active dynamics of self-propelled asymmetrical colloidal particles (Janus particles) fueled by an AC electric field. Both the speed and the direction of the self-propulsion and the strength of attractive interaction between the particles can be controlled by tuning the frequency of the applied electric field and the ion concentration of the solution. The strong attractive force at high ion concentration give rise to chain formation of the Janus particles, which can be explained by the quadrupolar charge distribution on the particles. The chain formation is observed irrespective of…
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…
In soft and condensed matter physics, effective interactions often emerge as a result of the spatial confinement of a fluctuating field. For instance, microscopic particles in a binary liquid mixture are subject to critical Casimir forces whenever their surfaces confine the thermal fluctuations of the order parameter of this kind of solvent, the range of which diverges upon approaching the critical demixing point. Critical Casimir forces are predicted to be nonadditive on a particular large scale. However, a direct experimental evidence of this fact is still lacking. Here, we fill in this gap …
We present a new Monte Carlo method to calculate Casimir forces acting on objects in a near-critical fluid, considering the two basic cases of a wall and a sphere embedded in a two-dimensional Ising medium. During the simulation, the objects are moved through the system with appropriate statistical weights, and consequently are attracted or repelled from the system boundaries depending on the boundary conditions. The distribution function of the object position is utilized to obtain the residual free energy, or Casimir potential, of the configuration as well as the corresponding Casimir force.…
The spatial suppression of order parameter fluctuations in a critical media produces Critical Casimir forces acting on confining surfaces. This scenario is realized in a critical binary mixture near the demixing transition point that corresponds to the second order phase transition of the Ising universality class. Due to these critical interactions similar colloids, immersed in a critical binary mixture near the consolute point, exhibit attraction. The numerical method for computation of the interaction potential between two spherical particles using Monte Carlo simulations for the Ising model…
Colloids immersed in a critical binary liquid mixture are subject to critical Casimir forces (CCFs) because they confine its concentration fluctuations and influence the latter via effective surface fields. To date, CCFs have only been studied in thermodynamic equilibrium. However, due to the critical slowing down, the order parameter around a particle can easily be perturbed by any motion of the colloid or by solvent flow. This leads to significant but largely unexplored changes in the CCF. Here we study the drag force on a single colloidal particle moving in a near-critical fluid mixture and…
The critical Casimir force (CCF) arises from confining fluctuations in a critical fluid and thus it is a fluctuating quantity itself. While the mean CCF is universal, its (static) variance has previously been found to depend on the microscopic details of the system which effectively set a large-momentum cutoff in the underlying field theory, rendering it potentially large. This raises the question how the properties of the force variance are reflected in experimentally observable quantities, such as the thickness of a wetting film or the position of a suspended colloidal particle. Here, based …
The dynamical arrest of attractive colloidal particles into out-of-equilibrium structures, known as gelation, is central to biophysics, materials science, nanotechnology, and food and cosmetic applications, but a complete understanding is lacking. In particular, for intermediate particle density and attraction, the structure formation process remains unclear. Here, we show that the gelation of short-range attractive particles is governed by a nonequilibrium percolation process. We combine experiments on critical Casimir colloidal suspensions, numerical simulations, and analytical modeling with…
Colloidal motors without moving parts can be propelled by self-diffusiophoresis, coupling molecular concentration gradients generated by surface chemical reactions to the velocity slip between solid Janus particles and the surrounding fluid solution. The interfacial properties involved in this propulsion mechanism can be described by nonequilibrium thermodynamics and statistical mechanics, disclosing the fundamental role of microreversibility in the coupling between motion and reaction. Among other phenomena, the approach predicts that propulsion by fuel consumption has the reciprocal effect o…
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…
Experimental realizations of self-propelled colloidal Janus particles exploit the conversion of free energy into directed motion. One route are phoretic mechanisms that can be modeled schematically as the interconversion of two chemical species. Here we consider the situation when the difference of chemical potential between the two species (the driving affinity) can be assumed to be constant, and we derive the thermodynamically consistent equations of motion. In contrast to the standard model of active Brownian particles parametrized by a constant self-propulsion speed, this yields a non-cons…
Colloidal patchy particles with divalent attractive interaction can self-assemble into linear polymer chains. Their equilibrium properties in 2D and 3D are well described by Wertheim's thermodynamic perturbation theory which predicts a well-defined exponentially decaying equilibrium chain length distribution. In experimental realizations, due to gravity, particles sediment to the bottom of the suspension forming a monolayer of particles with a gravitational height smaller than the particle diameter. In accordance with experiments, an anomalously high monomer concentration is observed in simula…
We study systems in which both long-ranged van der Waals and critical Casimir interactions are present. We study the interplay between these forces, as well as the {\it total} force (TF) between a spherical colloid particle and a thick planar slab, and between two spherical colloid particles. We do that using general scaling arguments and mean-field type calculations utilizing the Derjaguin and the surface integration approaches. They both are based on data of the forces between two parallel slabs separated at a distance $L$ from each other, confining the fluctuating fluid medium characterized…
We develop the scattering formalism to calculate the interaction between colloidal particles trapped at a fluid interface. Since, in addition to the interface, the colloids may also fluctuate in this system, we implement the fluctuation of the boundaries into the scattering formalism and investigate how the interaction between colloids is modified by their fluctuations. This general method can be applied to any number of colloids with various geometries at an interface. We apply the formalism derived in this work to a system of spherical colloids at the interface between two fluid phases. For …
The effective interaction between two planar walls immersed in a fluid is investigated by use of Density Functional Theory in the super-critical region of the phase diagram. A hard core Yukawa model of fluid is studied with special attention to the critical region. To achieve this goal a new formulation of the Weighted Density Approximation coupled with the Hierarchical Reference Theory, able to deal with critical long wavelength fluctuations, is put forward and compared with other approaches. The effective interaction between the walls is seen to change character on lowering the temperature: …
The dynamics and the steady states of a point-like tracer particle immersed in a confined critical fluid are studied. The fluid is modeled field-theoretically in terms of an order parameter (concentration or density field) obeying dissipative or conservative equilibrium dynamics and (non-)symmetry-breaking boundary conditions. The tracer, which represents, e.g., a colloidal particle, interacts with the fluid by locally modifying its chemical potential or its correlations. The coupling between tracer and fluid gives rise to a nonlinear and non-Markovian tracer dynamics, which is investigated he…
