Theory of nonlinear rheology and yielding of dense colloidal suspensions

A first principles approach to the nonlinear flow of dense suspensions is presented which captures shear thinning of colloidal fluids and dynamical yielding of colloidal glasses. The advection of density fluctuations plays a central role, suppressing the caging of particles and speeding up structural relaxation. A mode coupling approach is developed to explore these effects.Comment: 4 pages, 2 figures; slightly corrected version; Phys. Rev. Lett., to be published (2002

Influence of polydispersity on the critical parameters of an effective potential model for asymmetric hard sphere mixtures

We report a Monte Carlo simulation study of the properties of highly asymmetric binary hard sphere mixtures. This system is treated within an effective fluid approximation in which the large particles interact through a depletion potential (R. Roth {\em et al}, Phys. Rev. E{\bf 62} 5360 (2000)) designed to capture the effects of a virtual sea of small particles. We generalize this depletion potential to include the effects of explicit size dispersity in the large particles and consider the case in which the particle diameters are distributed according to a Schulz form having degree of polydispersity 14%. The resulting alteration (with respect to the monodisperse limit) of the metastable fluid-fluid critical point parameters is determined for two values of the ratio of the diameters of the small and large particles: $q\equiv\sigma_s/\bar\sigma_b=0.1$ and $q=0.05$. We find that inclusion of polydispersity moves the critical point to lower reservoir volume fractions of the small particles and high volume fractions of the large ones. The estimated critical point parameters are found to be in good agreement with those predicted by a generalized corresponding states argument which provides a link to the known critical adhesion parameter of the adhesive hard sphere model. Finite-size scaling estimates of the cluster percolation line in the one phase fluid region indicate that inclusion of polydispersity moves the critical point deeper into the percolating regime. This suggests that phase separation is more likely to be preempted by dynamical arrest in polydisperse systems.Comment: 11 pages, 10 figure

Non--Newtonian viscosity of interacting Brownian particles: comparison of theory and data

A recent first-principles approach to the non-linear rheology of dense colloidal suspensions is evaluated and compared to simulation results of sheared systems close to their glass transitions. The predicted scenario of a universal transition of the structural dynamics between yielding of glasses and non-Newtonian (shear-thinning) fluid flow appears well obeyed, and calculations within simplified models rationalize the data over variations in shear rate and viscosity of up to 3 decades.Comment: 6 pages, 2 figures; J. Phys. Condens. Matter to be published (Jan. 2003

Effective Interactions and Volume Energies in Charge-Stabilized Colloidal Suspensions

Charge-stabilized colloidal suspensions can be conveniently described by formally reducing the macroion-microion mixture to an equivalent one-component system of pseudo-particles. Within this scheme, the utility of a linear response approximation for deriving effective interparticle interactions has been demonstrated [M. J. Grimson and M. Silbert, Mol. Phys. 74, 397 (1991)]. Here the response approach is extended to suspensions of finite-sized macroions and used to derive explicit expressions for (1) an effective electrostatic pair interaction between pseudo-macroions and (2) an associated volume energy that contributes to the total free energy. The derivation recovers precisely the form of the DLVO screened-Coulomb effective pair interaction for spherical macroions and makes manifest the important influence of the volume energy on thermodynamic properties of deionized suspensions. Excluded volume corrections are implicitly incorporated through a natural modification of the inverse screening length. By including nonlinear response of counterions to macroions, the theory may be generalized to systematically investigate effective many-body interactions.Comment: 13 pages (J. Phys.: Condensed Matter, in press

Like-charge attraction through hydrodynamic interaction

We demonstrate that the attractive interaction measured between like-charged colloidal spheres near a wall can be accounted for by a nonequilibrium hydrodynamic effect. We present both analytical results and Brownian dynamics simulations which quantitatively capture the one-wall experiments of Larsen and Grier (Nature 385, p. 230, 1997).Comment: 10 pages, 4 figure

Environmental Effects on Corrosion Properties of Alloy 22

During the regulatory life of the Yucca Mountain High Level Nuclear Waste (HLNW) repository the primary engineered barrier that is to prevent release of radioactive material into the environment is proposed to be a Corrosion-Resistant Material (CRM) outer shell covering the Waste Package (WP) container. The current selection for the CRM is Alloy 22 (UNS N06022), a Ni-Cr-Mo-W-Fe alloy. Alloy 22 forms a defective chromic oxide passive film which results in excellent corrosion resistance; the presence of molybdenum in Alloy 22 offers corrosion resistance in reducing environments as well as oxidizing environments

Integration through transients for Brownian particles under steady shear

Starting from the microscopic Smoluchowski equation for interacting Brownian particles under stationary shearing, exact expressions for shear-dependent steady-state averages, correlation and structure functions, and susceptibilities are obtained, which take the form of generalized Green-Kubo relations. They require integration of transient dynamics. Equations of motion with memory effects for transient density fluctuation functions are derived from the same microscopic starting point. We argue that the derived formal expressions provide useful starting points for approximations in order to describe the stationary non-equilibrium state of steadily sheared dense colloidal dispersions.Comment: 17 pages, Submitted to J. Phys.: Condens. Matter; revised version with minor correction

Colloidal electrophoresis: Scaling analysis, Green-Kubo relation, and numerical results

We consider electrophoresis of a single charged colloidal particle in a finite box with periodic boundary conditions, where added counterions and salt ions ensure charge neutrality. A systematic rescaling of the electrokinetic equations allows us to identify a minimum set of suitable dimensionless parameters, which, within this theoretical framework, determine the reduced electrophoretic mobility. It turns out that the salt-free case can, on the Mean Field level, be described in terms of just three parameters. A fourth parameter, which had previously been identified on the basis of straightforward dimensional analysis, can only be important beyond Mean Field. More complicated behavior is expected to arise when further ionic species are added. However, for a certain parameter regime, we can demonstrate that the salt-free case can be mapped onto a corresponding system containing additional salt. The Green-Kubo formula for the electrophoretic mobility is derived, and its usefulness demonstrated by simulation data. Finally, we report on finite-element solutions of the electrokinetic equations, using the commercial software package COMSOL.Comment: To appear in Journal of Physics: Condensed Matter - special issue on occasion of the CODEF 2008 conferenc

Sequential quasi-Monte Carlo: Introduction for Non-Experts, Dimension Reduction, Application to Partly Observed Diffusion Processes

SMC (Sequential Monte Carlo) is a class of Monte Carlo algorithms for filtering and related sequential problems. Gerber and Chopin (2015) introduced SQMC (Sequential quasi-Monte Carlo), a QMC version of SMC. This paper has two objectives: (a) to introduce Sequential Monte Carlo to the QMC community, whose members are usually less familiar with state-space models and particle filtering; (b) to extend SQMC to the filtering of continuous-time state-space models, where the latent process is a diffusion. A recurring point in the paper will be the notion of dimension reduction, that is how to implement SQMC in such a way that it provides good performance despite the high dimension of the problem.Comment: To be published in the proceedings of MCMQMC 201