Coexistence diameter in two-dimensional colloid-polymer mixtures

We demonstrate that the law of the rectilinear coexistence diameter in two-dimensional (2D) mixtures of non-spherical colloids and non-adsorbing polymers is violated. Upon approach of the critical point, the diameter shows logarithmic singular behavior governed by a term t ln(t), with t the relative distance from the critical point. No sign of a term t^2b could be detected, with b the critical exponent of the order parameter, indicating a very weak or absent Yang-Yang anomaly. Our analysis thus reveals that non-spherical particle shape alone is not sufficient for the formation of a pronounced Yang-Yang anomaly in the critical behavior of fluids.Comment: 4 pages, 4 figures, to appear in Phys. Rev. E (R

Equilibrium properties of highly asymmetric star-polymer mixtures

We employ effective interaction potentials to study the equilibrium structure and phase behavior of highly asymmetric mixtures of star polymers. We consider in particular the influence of the addition of a component with a small number of arms and a small size on a concentrated solution of large stars with a high functionality. By employing liquid integral equation theories we examine the evolution of the correlation functions of the big stars upon addition of the small ones, finding a loss of structure that can be attributed to a weakening of the repulsions between the large stars due to the presence of the small ones. We analyze this phenomenon be means of a generalized depletion mechanism which is supported by computer simulations. By applying thermodynamic perturbation theory we draw the phase diagram of the asymmetric mixture, finding that the addition of small stars melts the crystal formed by the big ones. A systematic comparison between the two- and effective one-component descriptions of the mixture that corroborates the reliability of the generalized depletion picture is also carried out.Comment: 26 pages, 9 figures, submitted to Phys. Rev.

Systematic characterization of thermodynamic and dynamical phase behavior in systems with short-ranged attraction

In this paper we demonstrate the feasibility and utility of an augmented version of the Gibbs ensemble Monte Carlo method for computing the phase behavior of systems with strong, extremely short-ranged attractions. For generic potential shapes, this approach allows for the investigation of narrower attractive widths than those previously reported. Direct comparison to previous self-consistent Ornstein-Zernike approximation calculations are made. A preliminary investigation of out-of-equilibrium behavior is also performed. Our results suggest that the recent observations of stable cluster phases in systems without long-ranged repulsions are intimately related to gas-crystal and metastable gas-liquid phase separation.Comment: 10 pages, 8 figure

Stabilization of colloidal suspensions by means of highly-charged nanoparticles

We employ a novel Monte Carlo simulation scheme to elucidate the stabilization of neutral colloidal microspheres by means of highly-charged nanoparticles [V. Tohver et al., Proc. Natl. Acad. Sci. U.S.A. 98, 8950 (2001)]. In accordance with the experimental observations, we find that small nanoparticle concentrations induce an effective repulsion that prevents gelation caused by the intrinsic van der Waals attraction between colloids. Higher nanoparticle concentrations induce an attractive potential which is, however, qualitatively different from the regular depletion attraction. We also show how colloid-nanoparticle size asymmetry and nanoparticle charge can be used to manipulate the effective interactions.Comment: Accepted for publication in Physical Review Letters. See also S. Karanikas and A.A. Louis, cond-mat/0411279. Updated to synchronize with published versio

Crystallization and gelation in colloidal systems with short-ranged attractive interactions

We systematically study the relationship between equilibrium and non-equilibrium phase diagrams of a system of short-ranged attractive colloids. Using Monte Carlo and Brownian dynamics simulations we find a window of enhanced crystallization that is limited at high interaction strength by a slowing down of the dynamics and at low interaction strength by the high nucleation barrier. We find that the crystallization is enhanced by the metastable gas-liquid binodal by means of a two-stage crystallization process. First, the formation of a dense liquid is observed and second the crystal nucleates within the dense fluid. In addition, we find at low colloid packing fractions a fluid of clusters, and at higher colloid packing fractions a percolating network due to an arrested gas-liquid phase separation that we identify with gelation. We find that this arrest is due to crystallization at low interaction energy and it is caused by a slowing down of the dynamics at high interaction strength. Likewise, we observe that the clusters which are formed at low colloid packing fractions are crystalline at low interaction energy, but glassy at high interaction energy. The clusters coalesce upon encounter.Comment: 8 pages, 8 figure

Reverse-selective diffusion in nanocomposite membranes

The permeability of certain polymer membranes with impenetrable nanoinclusions increases with the particle volume fraction (Merkel et al., Science, 296, 2002). This intriguing observation contradicts even qualitative expectations based on Maxwell's classical theory of conduction/diffusion in composites with homogeneous phases. This letter presents a simple theoretical interpretation based on classical models of diffusion and polymer physics. An essential feature of the theory is a polymer-segment depletion layer at the inclusion-polymer interface. The accompanying increase in free volume leads to a significant increase in the local penetrant diffusivity, which, in turn, increases the bulk permeability while exhibiting reverse selectivity. This model captures the observed dependence of the bulk permeability on the inclusion size and volume fraction, providing a straightforward connection between membrane microstructure and performance

Entropic torque

Quantitative predictions are presented of a depletion-induced torque and force acting on a single colloidal hard rod immersed in a solvent of hard spheres close to a planar hard wall. This torque and force, which are entirely of entropic origin, may play an important role for the key-lock principle, where a biological macromolecule (the key) is only functional in a particular orientation with respect to a cavity (the lock)

Surface-mediated attraction between colloids

We investigate the equilibrium properties of a colloidal solution in contact with a soft interface. As a result of symmetry breaking, surface effects are generally prevailing in confined colloidal systems. In this Letter, particular emphasis is given to surface fluctuations and their consequences on the local (re)organization of the suspension. It is shown that particles experience a significant effective interaction in the vicinity of the interface. This potential of mean force is always attractive, with range controlled by the surface correlation length. We suggest that, under some circumstances, surface-induced attraction may have a strong influence on the local particle distribution

Supersaturated dispersions of rod-like viruses with added attraction

The kinetics of isotropic-nematic (I-N) and nematic-isotropic (N-I) phase transitions in dispersions of rod-like {\it fd}-viruses are studied. Concentration quenches were applied using pressure jumps in combination with polarization microscopy, birefringence and turbidity measurements. The full biphasic region could be accessed, resulting in the construction of a first experimental analogue of the bifurcation diagram. The N-I spinodal points for dispersions of rods with varying concentrations of depletion agents (dextran) were obtained from orientation quenches, using cessation of shear flow in combination with small angle light scattering. We found that the location of the N-I spinodal point is independent of the attraction, which was confirmed by theoretical calculations. Surprisingly, the experiments showed that also the absolute induction time, the critical nucleus and the growth rate are insensitive of the attraction, when the concentration is scaled to the distance to the phase boundaries.Comment: 13 pages, 14 figures. accepted in Phsical Review