Glasses in hard spheres with short-range attraction

We report a detailed experimental study of the structure and dynamics of glassy states in hard spheres with short-range attraction. The system is a suspension of nearly-hard-sphere colloidal particles and non-adsorbing linear polymer which induces a depletion attraction between the particles. Observation of crystallization reveals a re-entrant glass transition. Static light scattering shows a continuous change in the static structure factors upon increasing attraction. Dynamic light scattering results, which cover 11 orders of magnitude in time, are consistent with the existence of two distinct kinds of glasses, those dominated by inter-particle repulsion and caging, and those dominated by attraction. Samples close to the `A3 point' predicted by mode coupling theory for such systems show very slow, logarithmic dynamics.Comment: 22 pages, 18 figure

Phase diagram for a mixture of colloids and polymers with equal size

We present the phase diagram of a colloid-polymer mixture in which the radius a of the colloidal spheres is approximately the same as the radius R of a polymer coil (q=R/a1). A three-phase coexistence region is experimentally observed, previously only reported for colloid-polymer mixtures with smaller polymer chains (q0.6). A recently developed generalized free-volume theory (GFVT) for mixtures of hard spheres and non-adsorbing excluded-volume polymer chains gives a quantitative description of the phase diagram. Monte Carlo simulations also agree well with experimen

Phase behaviour of colloid + polymer mixtures

A new treatment of the phase behaviour of a colloid + nonadsorbing polymer mixture is described. The calculated phase diagrams show marked polymer partitioning between coexisting phases, an effect not considered in the usual effective-potential approaches to this problem. We also predict that under certain conditions an area of three-phase coexistence should appear in the phase diagram

Dynamics in Colloidal Liquids near a Crossing of Glass- and Gel-Transition Lines

Within the mode-coupling theory for ideal glass-transitions, the mean-squared displacement and the correlation function for density fluctuations are evaluated for a colloidal liquid of particles interacting with a square-well potential for states near the crossing of the line for transitions to a gel with the line for transitions to a glass. It is demonstrated how the dynamics is ruled by the interplay of the mechanisms of arrest due to hard-core repulsion and due to attraction-induced bond formation as well as by a nearby higher-order glass-transition singularity. Application of the universal relaxation laws for the slow dynamics near glass-transition singularities explains the qualitative features of the calculated time dependence of the mean-squared displacement, which are in accord with the findings obtained in molecular-dynamics simulation studies by Zaccarelli et. al [Phys. Rev. E 66, 041402 (2002)]. Correlation functions found by photon-correlation spectroscopy in a micellar system by Mallamace et. al [Phys. Rev. Lett. 84, 5431 2000)] can be interpreted qualitatively as a crossover from gel to glass dynamics.Comment: 13 pages, 12 figure

Dynamic density functional study of a driven colloidal particle in polymer solutions

The Dynamic Density Functional (DDF) theory and standard Brownian dynamics simulations (BDS) are used to study the drifting effects of a colloidal particle in a polymer solution, both for ideal and interacting polymers. The structure of the stationary density distributions and the total induced current are analyzed for different drifting rates. We find good agreement with the BDS, which gives support to the assumptions of the DDF theory. The qualitative aspect of the density distribution are discussed and compared to recent results for driven colloids in one-dimensional channels and to analytical expansions for the ideal solution limit

Phase separation in star polymer-colloid mixtures

We examine the demixing transition in star polymer-colloid mixtures for star arm numbers f=2,6,16,32 and different star-colloid size ratios. Theoretically, we solve the thermodynamically self-consistent Rogers-Young integral equations for binary mixtures using three effective pair potentials obtained from direct molecular computer simulations. The numerical results show a spinodal instability. The demixing binodals are approximately calculated, and found to be consistent with experimental observations.Comment: 4 pages, 4 figures, submitted to PR

Simulation study of Non-ergodicity Transitions: Gelation in Colloidal Systems with Short Range Attractions

Computer simulations were used to study the gel transition occurring in colloidal systems with short range attractions. A colloid-polymer mixture was modelled and the results were compared with mode coupling theory expectations and with the results for other systems (hard spheres and Lennard Jones). The self-intermediate scattering function and the mean squared displacement were used as the main dynamical quantities. Two different colloid packing fractions have been studied. For the lower packing fraction, $\alpha$-scaling holds and the wave-vector analysis of the correlation function shows that gelation is a regular non-ergodicity transition within MCT. The leading mechanism for this novel non-ergodicity transition is identified as bond formation caused by the short range attraction. The time scale and diffusion coefficient also show qualitatively the expected behaviour, although different exponents are found for the power-law divergences of these two quantities. The non-Gaussian parameter was also studied and very large correction to Gaussian behaviour found. The system with higher colloid packing fraction shows indications of a nearby high-order singularity, causing $\alpha$-scaling to fail, but the general expectations for non-ergodicity transitions still hold.Comment: 13 pages, 15 figure

Evidence for Unusual Dynamical Arrest Scenario in Short Ranged Colloidal Systems

Extensive molecular dynamics simulation studies of particles interacting via a short ranged attractive square-well (SW) potential are reported. The calculated loci of constant diffusion coefficient $D$ in the temperature-packing fraction plane show a re-entrant behavior, i.e. an increase of diffusivity on cooling, confirming an important part of the high volume-fraction dynamical-arrest scenario earlier predicted by theory for particles with short ranged potentials. The more efficient localization mechanism induced by the short range bonding provides, on average, additional free volume as compared to the hard-sphere case and results in faster dynamics.Comment: 4 pages, 3 figure

Non-monotonic variation with salt concentration of the second virial coefficient in protein solutions

The osmotic virial coefficient $B_2$ of globular protein solutions is calculated as a function of added salt concentration at fixed pH by computer simulations of the ``primitive model''. The salt and counter-ions as well as a discrete charge pattern on the protein surface are explicitly incorporated. For parameters roughly corresponding to lysozyme, we find that $B_2$ first decreases with added salt concentration up to a threshold concentration, then increases to a maximum, and then decreases again upon further raising the ionic strength. Our studies demonstrate that the existence of a discrete charge pattern on the protein surface profoundly influences the effective interactions and that non-linear Poisson Boltzmann and Derjaguin-Landau-Verwey-Overbeek (DLVO) theory fail for large ionic strength. The observed non-monotonicity of $B_2$ is compared to experiments. Implications for protein crystallization are discussed.Comment: 43 pages, including 17 figure

Capillary Condensation and Interface Structure of a Model Colloid-Polymer Mixture in a Porous Medium

We consider the Asakura-Oosawa model of hard sphere colloids and ideal polymers in contact with a porous matrix modeled by immobilized configurations of hard spheres. For this ternary mixture a fundamental measure density functional theory is employed, where the matrix particles are quenched and the colloids and polymers are annealed, i.e. allowed to equilibrate. We study capillary condensation of the mixture in a tiny sample of matrix as well as demixing and the fluid-fluid interface inside a bulk matrix. Density profiles normal to the interface and surface tensions are calculated and compared to the case without matrix. Two kinds of matrices are considered: (i) colloid-sized matrix particles at low packing fractions and (ii) large matrix particles at high packing fractions. These two cases show fundamentally different behavior and should both be experimentally realizable. Furthermore, we argue that capillary condensation of a colloidal suspension could be experimentally accessible. We find that in case (ii), even at high packing fractions, the main effect of the matrix is to exclude volume and, to high accuracy, the results can be mapped onto those of the same system without matrix via a simple rescaling.Comment: 12 pages, 9 figures, submitted to PR