In a recent Letter [Phys. Rev. Lett. 103, 156101 (2009)], we presented experiments on critical Casimir induced colloidal aggregation in a system with negligibly small van der Waals forces. We presented a simple model based on a competition between repulsive electrostatic and attractive critical Casimir forces to account for the observed aggregation. A recent comment [A. Gambassi, S. Dietrich, arXiv:1006.5897v1] proposed that the simple model should be regarded with caution as to its domain of application, and that it can be refined in a number of different ways. Here, we revisit our experimental finding and give a reply to the comment.
An arxiv paper, ref. [1] by Cao et al., claimed that the tunable attraction reported in our ref. [2] could not be detected. Ref. [1] was submitted to Nature in Apr. 2016 as a Comment on our ref. [2]. Our reply in May 2016 responded to ref. [1] and was reviewed by the editor of Nature and an external referee. Ref. [1] was rejected by Nature in Aug. 2016. We provide our reply, which answers all of the criticisms in ref. [1], in Appendix I. The main text contains a brief reply to the main criticisms.
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.
The critical Casimir effect provides a thermodynamic analogue of the well-known quantum mechanical Casimir effect. It acts between two surfaces immersed in a critical binary liquid mixture, and results from the confinement of concentration fluctuations of the solvent. Unlike the quantum mechanical effect, the magnitude and range of this attraction can be adjusted with temperature via the solvent correlation length, thus offering new opportunities for the assembly of nano and micron-scale structures. Here, we demonstrate the active assembly control of equilibrium phases using critical Casimir f…
G. Brambilla et al. Reply to a Comment by J. Reinhardt et al. questioning the existence of equilibrium dynamics above the critical volume fraction of colloidal hard spheres predicted by mode coupling theory.
We present a numerical study of the effective potential $V_\mathrm{eff}$ between two hard-sphere colloids dispersed in a solvent of interacting particles, for several values of temperature and solvent density, approaching the solvent gas-liquid critical point. We investigate the stability of a system of particles interacting via $V_\mathrm{eff}$ to evaluate the locus of colloidal aggregation in the solvent phase-diagram, and its dependence on the colloid size. We assess how the excluded volume depletion forces are modified by solvent attraction and discuss under which conditions solvent critic…
This is a reply to the recent comment from Ikeda, Berthier, and Sollich (arXiv:1602.04796) on "Constant stress and pressure rheology of colloidal suspensions", Phys. Rev. Lett. 115, 158301 (2015).
Composite colloidal assembly by critical Casimir forces
University of Amsterdam（阿姆斯特丹大学）；Wageningen University and Research（瓦赫宁根大学和研究机构）；Polish Academy of Sciences（波兰科学院）；Max-Planck-Institut für Intelligente Systeme（马克斯·普朗克智能系统研究所）
From experimental studies it is well-known that colloidal particles suspended in a near-critical binary solvent exhibit interesting aggregation phenomena, often associated with colloidal phase transitions, and assumed to be driven by long-ranged solvent mediated (SM) interactions (critical Casimir forces), set by the (diverging) correlation length of the solvent. We present the first simulation and theoretical study of an explicit model of a ternary mixture that mimics this situation. Both the effective SM pair interactions and the full ternary phase diagram are determined for Brownian discs s…
Using the critical Casimir force, we study the attractive-strength dependence of diffusion-limited colloidal aggregation in microgravity. By means of near field scattering we measure both the static and dynamic structure factor of the aggregates as the aggregation process evolves. The simultaneous measurement of both the static and dynamic structure factor under ideal microgravity conditions allows us to uniquely determine the ratio of the hydrodynamic and gyration radius as a function of the fractal dimension of the aggregate, enabling us to elucidate the internal structure of the aggregates …
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.
Percolation and critical phenomena show common features such as scaling and universality. Colloidal particles, immersed in a solvent close to criticality, experience long-range effective forces, named critical Casimir forces. %These originate from the confinement of the solvent critical fluctuations between the colloids. Building on the analogy between critical phenomena and percolation, we explore the possibility of observing long-range forces near a percolation threshold. To this aim we numerically evaluate the effective potential between two colloidal particles dispersed in a chemical sol a…
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 temper…
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 …
Recent experiments have demonstrated a fluctuation-induced lateral trapping of spherical colloidal particles immersed in a binary liquid mixture near its critical demixing point and exposed to chemically patterned substrates. Inspired by these experiments, we study this kind of effective interaction, known as the critical Casimir effect, for elongated colloids of cylindrical shape. This adds orientational degrees of freedom. When the colloidal particles are close to a chemically structured substrate, a critical Casimir torque acting on the colloids emerges. We calculate this torque on the basi…
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…
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. W…
Limited-valency colloidal particles can self-assemble into polymeric structures analogous to molecules. While their structural equilibrium properties have attracted wide attention, insight into their dynamics has proven challenging. Here, we investigate the polymerization dynamics of semiflexible polymers in two dimensions (2D) by direct observation of assembling divalent particles, bonded by critical Casimir forces. The reversible critical Casimir force creates living polymerization conditions with tunable chain dissociation, association and bending rigidity. We find that unlike dilute polyme…
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…
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 pos…
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 …
Using field-theoretical methods and exploiting conformal invariance, we study Casimir forces at tricritical points exerted by long-range fluctuations of the order-parameter field. Special attention is paid to the situation where the symmetry is broken by the boundary conditions (extraordinary transition). Besides the parallel-plate configuration, we also discuss the geometries of two separate spheres and a single sphere near a planar wall, which may serve as a model for colloidal particles immersed in a fluid. In the concrete case of ternary mixtures a quantitative comparison with critical Cas…
If colloidal solute particles are suspended in a solvent close to its critical point, they act as cavities in a fluctuating medium and thereby restrict and modify the fluctuation spectrum in a way which depends on their relative configuration. As a result effective, so-called critical Casimir forces (CCFs) emerge between the colloids. The range and the amplitude of CCFs depend sensitively on the temperature and the composition of the solvent as well as on the boundary conditions of the order parameter of the solvent at the particle surfaces. These remarkable, moreover universal features of the…
We study theoretically and experimentally the solvent-mediated critical Casimir force acting on colloidal particles immersed in a binary liquid mixture of water and 2,6-lutidine and close to substrates which are chemically patterned with periodically alternating stripes of antagonistic adsorption preferences. These patterns are experimentally realized via microcontact printing. Upon approaching the critical demixing point of the solvent, normal and lateral critical Casimir forces generate laterally confining effective potentials for the colloids. We analyze in detail the rich behavior of the s…
Based on renormalization group concepts and explicit mean field calculations we study the universal contribution to the effective force and torque acting on an ellipsoidal colloidal particle which is dissolved in a critical fluid and is close to a homogeneous planar substrate. At the same closest distance between the substrate and the surface of the particle, the ellipsoidal particle prefers an orientation parallel to the substrate and the magnitude of the fluctuation induced force is larger than if the orientation of the particle is perpendicular to the substrate. The sign of the critical tor…
Recently there is strong experimental and theoretical interest in studying the self-assembly and the phase behavior of patchy and of Janus particles, which form colloidal suspensions. Although in this quest a variety of effective interactions have been proposed and used in order to achieve directed assembly, the critical Casimir effect stands out as being particularly suitable in this respect because it provides both attractive and repulsive interactions as well as the potential of a sensitive temperature control of their strength. Specifically, we have calculated the critical Casimir force be…
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) a…
We report a numerical investigation of two colloids immersed in a critical solvent, with the aim of quantifying the effective colloid-colloid interaction potential. By turning on an attraction between the colloid and the solvent particles we follow the evolution from the case in which the solvent density close to the colloids changes from values smaller than the bulk to values larger than the bulk. We thus effectively implement the so-called $(+,+)$ and $(-,-)$ boundary conditions defined in field theoretical approaches focused on the description of critical Casimir forces. We find that the ef…
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.
Within mean-field theory we calculate universal scaling functions associated with critical Casimir forces for a system consisting of three parallel cylindrical colloids immersed in a near-critical binary liquid mixture. For several geometrical arrangements and boundary conditions at the surfaces of the colloids we study the force between two colloidal particles along their center-to-center axis, analyzing the influence of the presence of a third particle on that force. Upon changing temperature or the relative positions of the particles we observe interesting features such as a change of sign …
The Casimir and electromagnetic interactions between objects at short separations are strongly influenced by the local geometry near the point of closest approach. In this paper we demonstrate that the assumptions underlying common statistical analysis of roughness may not hold in experiments using micro-spheres as interacting objects. Based on an extensive experimental and numerical analysis of the surface topology of the widely used colloidal particle types 4310A and 4320A, we show that the actual variation in the local surface curvature may give rise to large uncertainties in the comparison…
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 …
Critical Casimir forces emerge between objects, such as colloidal particles, whenever their surfaces spatially confine the fluctuations of the order parameter of a critical liquid used as a solvent. These forces act at short but microscopically large distances between these objects, reaching often hundreds of nanometers. Keeping colloids at such distances is a major experimental challenge, which can be addressed by the means of optical tweezers. Here, we review how optical tweezers have been successfully used to quantitatively study critical Casimir forces acting on particles in suspensions. 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…
Within mean field theory, we investigate the bridging transition between a pair of parallel cylindrical colloids immersed in a binary liquid mixture as a solvent which is close to its critical consolute point $T_c$. We determine the universal scaling functions of the effective potential and of the force between the colloids. For a solvent which is at the critical concentration and close to $T_c$, we find that the critical Casimir force is the dominant interaction at close separations. This agrees very well with the corresponding Derjaguin approximation for the effective interaction between the…
We investigate the universal orientation-dependent interactions between non-spherical colloidal particles immersed in a critical solvent by studying the instructive paradigm of a needle embedded in bounded two-dimensional Ising models at bulk criticality. For a needle in an Ising strip the interaction on mesoscopic scales depends on the width of the strip and the length, position, and orientation of the needle. By lattice Monte Carlo simulations we evaluate the free energy difference between needle configurations being parallel and perpendicular to the strip. We concentrate on small but noneth…
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…
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 …
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…
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…
Recently, Huang, Wu and Florin posted a Comment (0806.4632v1) on our preprint (0804.0730v1) describing nonequilibrium circulation of a colloidal sphere trapped in a optical tweezer. The Comment suggests that evidence for toroidal probability currents obtained from experiments and simulations in the original posting should be considered inconclusive. The authors' concerns are based on two claims: (1) that Brownian dynamics simulations of the trapped particle's motions reveal no statistically significant circulation, and (2) that a realistic description of the radiation pressure acting on the tr…
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 …
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…
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: …
