The non-equilibrium distribution of colloids in a polymer solution under a temperature gradient is studied experimentally. A slight increase of local temperature by a focused laser drives the colloids towards the hot region, resulting in the trapping of the colloids irrespective of their own thermophoretic properties. An amplification of the trapped colloid density with the polymer concentration is measured, and is quantitatively explained by hydrodynamic theory. The origin of the attraction is a migration of colloids driven by a non-uniform polymer distribution sustained by the polymer's thermophoresis. These results show how to control thermophoretic properties of colloids.
Depletion-induced interactions between colloids in colloid-polymer mixtures depend in range and strength on size, shape, and concentration of depletants. Crowding by colloids in turn affects shapes of polymer coils, such as biopolymers in biological cells. By simulating hard-sphere colloids and random-walk polymers, modeled as fluctuating ellipsoids, we compute depletion-induced potentials and polymer shape distributions. Comparing results with exact density-functional theory calculations, molecular simulations, and experiments, we show that polymer shape fluctuations play an important role in…
Depletion interactions arise from entropic forces, and their ability to induce aggregation and even ordering of colloidal particles through self-assembly is well established, especially for spherical colloids. We vary the size and concentration of penetrable hard sphere depletants in a system of cuboctahedra, and we show how depletion changes the preferential facet alignment of the colloids and thereby selects different crystal structures. Moreover, we explain the cuboctahedra phase behavior using perturbative free energy calculations. We find that cuboctahedra can form a stable simple cubic p…
The common rules of classical nonequilibrium thermodynamics do not allow an Onsager coefficient like the viscosity to depend on the shear rate. Such a dependence is experimentally well documented, however. In this paper it is shown, using nonequilibrium thermodynamics alone, how it is possible that the effective viscosity coefficient of an isotropic colloidal system depends on both the shear rate and the frequency.
We investigate binary mixtures of large colloids interacting through soft potentials with small, ideal depletants. We show that softness has a dramatic effect on the resulting colloid-colloid effective potential when the depletant-to-colloid size ratio $q$ is small, with significant consequences on the colloidal phase behaviour. We also provide an exact relation that allows us to obtain the effective pair potential for {\it any} type of colloid-depletant interactions in the case of ideal depletants, without having to rely on complicated and expensive full-mixture simulations. We also show that…
Depletion interactions between colloidal particles dispersed in a fluid medium are effective interactions induced by the presence of other types of colloid. They are not instantaneous but build up in time. We show by means Brownian dynamics simulations that the fluctuations in the depletion force between two guest particles in a host dispersion of differently sized colloids do not decay exponentially with time, but show a power-law dependence. A simple scaling theory accurately describes the dependence of the magnitude of these fluctuations on time, on the inter-particle distance and on the si…
We show that two-dimensional bidisperse assemblies of colloids with strictly repulsive interactions exhibit stripe, cluster, and partially crystallized states when driven over a quenched random substrate. The nonequilibrium states on a substrate are significantly more ordered than equilibrium states both with and without substrates. A minimum substrate strength is necessary to induce the nonequilibrium pattern formation. Our results suggest that a combination of driving and quenched disorder offers a new approach to controlling pattern formation in colloid mixtures.
We consider depletion effects of a pear-shaped colloidal particle in a hard-sphere solvent, for two different model realisations of the pear-shaped colloidal particle. The two models are the pear hard Gaussian overlap (PHGO) particles and the hard pears of revolution (HPR). The motivation for this study is to provide a microscopic understanding for the substantially different mesoscopic self-assembly properties of these pear-shaped colloids, in dense suspensions, that have been reported in the first part of this series. This is done by determining the differing depletion attraction via MC simu…
We study the irreversible adsorption of spherical $2AnB$ patchy colloids (with two $A$-patches on the poles and $n$ $B$-patches along the equator) on a substrate. In particular, we consider dissimilar $AA$, $AB$, and $BB$ binding probabilities. We characterize the patch-colloid network and its dependence on $n$ and on the binding probabilities. Two growth regimes are identified with different density profiles and we calculate a growth mode diagram as a function of the colloid parameters. We also find that, close to the substrate, the density of the network, which depends on the colloid paramet…
When non-adsorbing polymers are added to an isotropic suspension of rod-like colloids, the colloids effectively attract each other via depletion forces. We performed Monte Carlo simulations to study the phase diagram of such rod-polymer mixture. The colloidal rods were modelled as hard spherocylinders; the polymers were described as spheres of the same diameter as the rods. The polymers may overlap with no energy cost, while overlap of polymers and rods is forbidden. Large amounts of depletant cause phase separation of the mixture. We estimated the phase boundaries of isotropic-isotropic coexi…
The surface tension, the adsorption, and the depletion thickness of polymers close to a single nonadsorbing colloidal sphere are computed by means of Monte Carlo simulations. We consider polymers under good-solvent conditions and in the thermal crossover region between good-solvent and $θ$ behavior. In the dilute regime we consider a wide range of values of $q$, from $q = 0$ (planar surface) up to $q\approx 30$-50, while in the semidilute regime, for $ρ_p/ρ_p^*\le 4$ ($ρ_p$ is the polymer concentration and $ρ_p^*$ is its value at overlap), we only consider $q = 0,0.5,1$ and 2. The results are …
The binodals and the non-ergodicity lines of a binary mixture of hard sphere-like particles with large size ratio are computed for studying the interplay between dynamic arrest and phase separation in depletion-driven colloidal mixtures. Contrarily to the case of hard core plus short range effective attraction, physical gellation without competition with the fluid-phase separation can occur in such mixtures. This behavior due to the oscillations in the depletion potential should concern all simple mixtures with non-ideal depletant, justifying further studies of their dynamic properties.
The depletion interactions between two colloidal plates or between two colloidal spheres, induced by interacting polymers in a good solvent, are calculated theoretically and by computer simulations. A simple analytical theory is shown to be quantitatively accurate for case of two plates. A related depletion potential is derived for two spheres; it also agrees very well with direct computer simulations. Theories based on ideal polymers show important deviations with increasing polymer concentration: They overestimate the range of the depletion potential between two plates or two spheres at all …
We combine experiments, theory, and simulations to investigate the coexistence of nonequilibrium phases emerging from interacting colloidal particles that are electrokinetically propelled in a nematic liquid crystal solvent. We directly determine the mechanical pressure within the radial assemblies and measure a non-equilibrium equation of state for this athermal driven system. A generic model combines phoretic propulsion with the interplay between electrostatic effects and liquid-crystal-mediated hydrodynamics, which are effectively cast into a long-range interparticle repulsion, while elasti…
Active colloids constitute a novel class of materials composed of colloidal-scale particles locally converting chemical energy into motility, mimicking micro-organisms. Evolving far from equilibrium, these systems display structural organizations and dynamical properties distinct from thermalized colloidal assemblies. Harvesting the potential of this new class of systems requires the development of a conceptual framework to describe these intrinsically nonequilibrium systems. We use sedimentation experiments to probe the nonequilibrium equation of state of a bidimensional assembly of active Ja…
Entropic forces in colloidal suspensions and in polymer-colloid systems are of long-standing and continuing interest. Experiments show how entropic forces can be used to control the self-assembly of colloidal particles. Significant advances in colloidal synthesis made in the past two decades have enabled the preparation of high quality nano-particles with well-controlled sizes, shapes, and compositions, indicating that such particles can be utilized as "artificial atoms" to build new materials. To elucidate the effects of the shape of particles upon the magnitude of entropic interaction, we an…
We consider anisotropic colloidal particles immersed in a solution of long, flexible, and nonadsorbing polymers. For the dumbbell shapes of recently synthesized particles consisting of two intersecting spheres and for lens-shaped particles with spherical surfaces we calculate the isotropic and anisotropic interaction parameters that determine the immersion free energy and the orientation-dependent depletion interaction between particles that are induced by the polymers. Exact results are obtained for random-walk like (ideal) polymer chains.
The possibility to induce demixing in a colloidal mixture by adding small polymers, or other equivalent depletant agents, is theoretically investigated. By use of Mean Field Theory, suitably generalized to deal with short range effective interactions, the phase diagram of a binary mixture ofcolloidal particles (modelled as hard spheres) in a solvent is determined as a function of the polymer concentration on the basis of the Asakura-Oosawa model.The topology of the phase diagram changes when the relative size of the colloidal particles is reduced: the critical line connecting the liquid-vapour…
In a mixed suspension of rods and small polymer coils, the rods adsorb onto a hard wall in contact with the suspension. This adsorption is studied in the low density of rods limit. It is driven by depletion forces and is much stronger for long rods than for spheres. This is shown by means of exact, numerical, calculations and an approximate theory.
As first explained by the classic Asakura-Oosawa (AO) model, effective attractive forces between colloidal particles induced by depletion of nonadsorbing polymers can drive demixing of colloid-polymer mixtures into colloid-rich and colloid-poor phases, with practical relevance for purification of water, stability of foods and pharmaceuticals, and macromolecular crowding in biological cells. By idealizing polymer coils as effective penetrable spheres, the AO model qualitatively captures the influence of polymer depletion on thermodynamic phase behavior of colloidal suspensions. In previous work…
Performing light scattering experiments we show that introducing short-ranged attraction to a colloidal suspension of nearly hard spheres by addition of free polymer produces new glass transition phenomena. We observe a dramatic acceleration of the density fluctuations amounting to the melting of a colloidal glass. Increasing the strength of the attractions the system freezes into another nonergodic state sharing some qualitative features with gel states occurring at lower colloid packing fractions. This reentrant glass transition is in qualitative agreement with recent theoretical predictions…
We study the depletion-induced self-assembly of indented colloids. Using state-of-the-art Monte Carlo simulation techniques that treat the depletant particles explicitly, we demonstrate that colloids assemble by a lock-and-key mechanism, leading to colloidal polymerization. The morphology of the chains that are formed depends sensitively on the size of the colloidal indentation, with smaller values additionally permitting chain branching. In contrast to the case of spheres with attractive patches, Wertheim's thermodynamic perturbation theory fails to provide a fully quantitative description of…
We analyze the depletion interaction between two hard colloids in a hard--sphere solvent and pay special attention to the limit of large size ratio between colloids and solvent particles which is governed by the well--known Derjaguin approximation. For separations between the colloids of less than the diameter of the solvent particles (defining the depletion region), the solvent structure between the colloids can be analyzed in terms of an effective two--dimensional gas. Thereby we find that the Derjaguin limit is approached more slowly than previously thought. This analysis is in good agreeme…
In drying liquid films of polymer-colloid mixtures, the stratification in which polymers are placed on top of larger colloids is studied. It is often presumed that the formation of segregated polymer-colloid layers is solely due to the proportion in size at fast evaporation as in binary colloid mixtures. By comparing experiments with a theoretical model, we found that the transition in viscosity near the drying interface was another important parameter for controlling the formation of stratified layers in polymer-colloid mixtures. At high evaporation rates, increased polymer concentrations nea…
We investigate the response of a dense monodisperse quasi-two-dimensional (q2D) colloid suspension when a particle is dragged by a constant velocity optical trap. Consistent with microrheological studies of other geometries, the perturbation induces a leading density wave and trailing wake, and we use Stokesian Dynamics (SD) simulations to parse direct colloid-colloid and hydrodynamic interactions. We go on to analyze the underlying individual particle-particle collisions in the experimental images. The displacements of particles form chains reminiscent of stress propagation in sheared granula…
When a colloid is mixed with a depletant such as a non-adsorbing polymer, one observes attractive effective interactions between the colloidal particles. If these particles are anisotropic, analysis of these effective interactions is challenging in general. We present a method for inference of approximate (coarse-grained) effective interaction potentials between such anisotropic particles. Using the example of indented (lock-and-key) colloids, we show how numerical solutions can be used to integrate out the (hard sphere) depletant, leading to a depletion potential that accurately characterises…
We study indented spherical colloids, interacting via depletion forces. These systems exhibit liquid-vapor phase transitions whose properties are determined by a combination of strong "lock-and-key" bonds and weaker non-specific interactions. As the propensity for lock-and-key binding increases, the critical point moves to significantly lower density, and the coexisting phases change their structure. In particular, the liquid phase is "porous", exhibiting large percolating voids. The properties of this system depend strongly on the topological structure of an underlying bond network: we commen…
We use thermodynamic perturbation theory to calculate the free energies and resulting phase diagrams of binary systems of spherical colloidal particles and interacting polymer coils in good solvent within an effective one-component representation of such mixtures, whereby the colloidal particles interact via a polymer-induced depletion potential. MC simulations are used to test the convergence of the high temperature expansion of the free energy. The phase diagrams calculated for several polymer to colloid size ratios differ considerably from the results of similar calculations for mixtures of…
A binary mixture of particles interacting via long-ranged repulsive forces is studied in gravity by computer simulation and theory. The more repulsive A-particles create a depletion zone of less repulsive B-particles around them reminiscent to a bubble. Applying Archimedes' principle effectively to this bubble, an A-particle can be lifted in a fluid background of B-particles. This "depletion bubble" mechanism explains and predicts a brazil-nut effect where the heavier A-particles float on top of the lighter B-particles. It also implies an effective attraction of an A-particle towards a hard co…
Monodisperse rod-like colloidal particles are known for spontaneously forming both nematic and smectic liquid crystal phases, but their self-assembly was typically exploited from the fundamental soft condensed matter physics perspective. Here we demonstrate that depletion interactions, driven by non-adsorbing polymers like dextran and surfactants, can be used to enrich self-organization of photon-upconversion nanorods into orientationally ordered nematic and smectic-like membrane colloidal superstructures. We study thermodynamic phase diagrams and demonstrate polarization-dependent photon upco…
A binary colloidal mixture of unequal sizes, subjected to an external potential barrier, has been investigated using canonical ensemble molecular dynamics simulations. The attractive depletion interaction between the external barrier and larger species in the binary mixture causes the mixture to phase separate. At higher volume fractions, a pure phase of larger particles forms near the potential barrier, and the local density of this pure phase is high enough that a face centered cubic crystalline domain is formed at this region. This crystalline phase diffuses perpendicular to the external po…
The density distributions and Soret coefficient in a nonequilibrium colloidal system with nonuniform temperature are studied by the overdamped Langevin equation for Brownian motion in an inhomogeneous strong friction medium. Based on the relation between the temperature gradient, the interaction potential and the q-parameter in nonextensive statistics, We show that the colloidal particle density can be a function of the temperature and anomalously follows the noted alpha-distribution, or equivalently it can also be a function of the potential energy and follows Tsallis distribution. With the q…
Using numerical simulations, we study how a solution of small active disks, acting as depletants, induces effective interactions on large passive colloids. Specifically, we analyze how the range, strength, and sign of these interactions are crucially dependent on the shape of the colloids. Our findings indicate that while colloidal rods experience a long-ranged predominantly attractive interaction, colloidal disks feel a purely repulsive force that is short-ranged in nature and grows in strength with the size ratio between the colloids and active depletants. For colloidal rods, simple scaling …
We present a direct experimental measurement of an effective temperature in a colloidal glass of Laponite, using a micrometric bead as a thermometer. The nonequilibrium fluctuation-dissipation relation, in the particular form of a modified Einstein relation, is investigated with diffusion and mobility measurements of the bead embedded in the glass. We observe an unusual non-monotonic behavior of the effective temperature : starting from the bath temperature, it is found to increase up to a maximum value, and then decreases back, as the system ages. We show that the observed deviation from the …
We analyze theoretically the dynamics of a single colloidal particle in an externally applied electric field. The thermal motions of microions lead to an anisotropic, nonequilibrium source of noise, pro- portional to the field, in the effective Langevin equation for the colloid. The fluctuation-dissipation ratio depends strongly on frequency, and the colloid if displaced from its steady-state position relaxes with a velocity not proportional to the gradient of the logarithm of the steady-state probability.
We study a nonequilibrium Langevin many-body system containing two 'test' particles and many 'background' particles. The test particles are spatially confined by a harmonic potential, and the background particles are driven by an external driving force. Employing numerical simulations of the model, we formulate an effective description of the two test particles in a nonequilibrium steady state. In particular, we investigate several different definitions of the effective force acting between the test particles. We find that the law of action and reaction does not hold for the total mechanical f…
The depletion interaction mediated by non-adsorbing polymers promotes condensation and assembly of repulsive colloidal particles into diverse higher-order structures and materials. One example, with particularly rich emergent behaviors, is the formation of two-dimensional colloidal membranes from a suspension of filamentous $\it{fd}$ viruses, which act as rods with effective repulsive interactions, and dextran, which acts as a condensing, depletion-inducing agent. Colloidal membranes exhibit chiral twist even when the constituent virus mixture lacks macroscopic chirality, change from a circula…
We examine the structure and dynamics of small isolated $N$-particle clusters interacting via short-ranged Morse potentials. "Ideally preprared ensembles" obtained via exact enumeration studies of sticky hard sphere packings serve as reference states allowing us to identify key statistical-geometrical properties and to quantitatively characterize how nonequilibrium ensembles prepared by thermal quenches at different rates $\dot{T}$ differ from their equilibrium counterparts. Studies of equilibrium dynamics show nontrival temperature dependence: nonexponential relaxation indicates both glassy d…
In mixtures of colloids and nonadsorbing polyelectrolytes, a Donnan potential arises across the region between surfaces that are depleted of polyelectrolyte and the rest of the system. This Donnan potential tends to shift the polyelectrolyte density profile towards the colloidal surface and leads to local accumulation of polyelectrolytes. We derive a zero-field theory for the disjoining pressure between two parallel flat plates. Polyelectrolyte is allowed to enter the confined interplate region at the cost of a conformational free energy penalty. The resulting disjoining pressure shows a cross…
Patchy colloids with highly directional interactions are ideal building blocks to control the local arrangements resulting from their spontaneous self-organization. Here we propose their use, combined with substrates and nonequilibrium conditions, to obtain structures, different from those of equilibrium thermodynamic phases. Specifically, we investigate numerically the irreversible adhesion of three-patch colloids near attractive substrates, and analyze the fractal network of connected particles that is formed. The network density profile exhibits three distinct regimes, with different struct…
We demonstrate the effect of the depletion force in experiments and simulations of vertically vibrated mixtures of large and small steel spheres. The system exhibits size segregation and a large increase in the pair correlation function of the large spheres for short distances that can be accurately described using a combination of the depletion potential derived for equilibrium colloidal systems and a Boltzmann factor. The Boltzmann factor defines an effective temperature for the system, which we compare to other measures of the temperature.
Paramagnetic colloidal particles that are optically trapped in a linear array can form a zigzag pattern when an external magnetic field induces repulsive interparticle interactions. When the traps are abruptly turned off, the particles form a nonequilibrium expanding pattern with a zigzag symmetry, even when the strength of the magnetic interaction is weaker than that required to break the linear symmetry of the equilibrium state. We show that the transition to the equilibrium zigzag state is always potentially possible for purely harmonic traps. For anharmonic traps that have a finite height,…
We determine the depletion-induced phase-behavior of hard sphere colloids and interacting polymers by large-scale Monte Carlo simulations using very accurate coarse-graining techniques. A comparison with standard Asakura-Oosawa model theories and simulations shows that including excluded volume interactions between polymers leads to qualitative differences in the phase diagrams. These effects become increasingly important for larger relative polymer size. Our simulations results agree quantitatively with recent experiments.
Interfacial properties of colloid--polymer mixtures are examined within an effective one--component representation, where the polymer degrees of freedom are traced out, leaving a fluid of colloidal particles interacting via polymer--induced depletion forces. Restriction is made to zero, one and two--body effective potentials, and a free energy functional is used which treats colloid excluded volume correlations within Rosenfeld's Fundamental Measure Theory, and depletion--induced attraction within first--order perturbation theory. This functional allows a consistent treatment of both ideal and…
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…
The change of the structure of concentrated colloidal suspensions upon addition of non-adsorbing polymer is studied within a two-component, Ornstein-Zernicke based liquid state approach. The polymers' conformational degrees of freedom are considered and excluded volume is enforced at the segment level. The polymer correlation hole, depletion layer, and excess chemical potentials are described in agreement with polymer physics theory in contrast to models treating the macromolecules as effective spheres. Known depletion attraction effects are recovered for low particle density, while at higher …
The density profile and surface tension for the interface of phase-separated colloid-polymer mixtures have been studied in the framework of the square gradient approximation for both ideal and interacting polymers in good solvent. The calculations show that in the presence of polymer-polymer excluded volume interactions the interfaces have lower widths and surface tensions compared to the case of ideal polymers. These results are a direct consequence of the shorter range and smaller depth of the depletion potential between colloidal particles induced by interacting polymers.
We propose a model for the nonequilibrium enhancement of colloidal self-diffusion in an externally imposed shear flow in charged systems. The enhancement of diffusion is calculated in terms of the electrostatic, two--body interactions between the particles in the shear flow. In the high shear rate, low volume fraction limit in which our model is valid, we compare these calculations to the experiments of Qiu et al. [Phys. Rev. Lett. 61, 2554 (1988)].
Computer simulations and theory are used to systematically investigate how the effective force between two big colloidal spheres in a sea of small spheres depends on the basic (big-small and small-small) interactions. The latter are modeled as hard-core pair potentials with a Yukawa tail which can be both repulsive or attractive. For a repulsive small-small interaction, the effective force follows the trends as predicted by a mapping onto an effective non-additive hard-core mixture: both a depletion attraction and an accumulation repulsion caused by small spheres adsorbing onto the big ones ca…
A general class of nonadditive sticky-hard-sphere binary mixtures, where small and large spheres represent the solvent and the solute, respectively, is introduced. The solute-solute and solvent-solvent interactions are of hard-sphere type, while the solute-solvent interactions are of sticky-hard-sphere type with tunable degrees of size nonadditivity and stickiness. Two particular and complementary limits are studied using analytical and semi-analytical tools. The first case is characterized by zero nonadditivity, lending itself to a Percus-Yevick approximate solution from which the impact of s…
We investigate excluded-volume effects in a bidisperse colloidal suspension near a flexible interface. Inspired by a recent experiment by Dinsmore et al. (Phys. Rev, Lett. 80, 409 (1998)), we study the adsorption of a mesoscopic bead on the surface and show that depletion forces could in principle lead to particle encapsulation. We then consider the effect of surface fluctuations on the depletion potential itself and construct the density profile of a polymer solution near a soft interface. Surprisingly we find that the chains accumulate at the wall, whereas the density displays a deficit of p…
