The Effects of Inter-particle Attractions on Colloidal Sedimentation

We use a mesoscopic simulation technique to study the effect of short-ranged inter-particle attraction on the steady-state sedimentation of colloidal suspensions. Attractions increase the average sedimentation velocity $v_s$ compared to the pure hard-sphere case, and for strong enough attractions, a non-monotonic dependence on the packing fraction $\phi$ with a maximum velocity at intermediate $\phi$ is observed. Attractions also strongly enhance hydrodynamic velocity fluctuations, which show a pronounced maximum size as a function of $\phi$. These results are linked to a complex interplay between hydrodynamics and the formation and break-up of transient many-particle clusters.Comment: 4 pages 4 figure

Direct numerical simulations for non-Newtonian rheology of concentrated particle dispersions

The non-Newtonian behavior of a monodisperse concentrated dispersion of spherical particles was investigated using a direct numerical simulation method, that takes into account hydrodynamic interactions and thermal fluctuations accurately. Simulations were performed under steady shear flow with periodic boundary conditions in the three directions. The apparent shear viscosity of the dispersions was calculated at volume fractions ranging from 0.31 to 0.56. Shear-thinning behavior was clearly observed at high volume fractions. The low- and high-limiting viscosities were then estimated from the apparent viscosity by fitting these data into a semi-empirical formula. Furthermore, the short-time motions were examined for Brownian particles fluctuating in concentrated dispersions, for which the fluid inertia plays an important role. The mean square displacement was monitored in the vorticity direction at several different Peclet numbers and volume fractions so that the particle diffusion coefficient is determined from the long-time behavior of the mean square displacement. Finally, the relationship between the non-Newtonian viscosity of the dispersions and the structural relaxation of the dispersed Brownian particles is examined

Correlated dynamics of inclusions in a supported membrane

The hydrodynamic theory of heterogeneous fluid membranes is extended to the case of a membrane adjacent to a solid substrate. We derive the coupling diffusion coefficients of pairs of membrane inclusions in the limit of large separation compared to the inclusion size. Two-dimensional compressive stresses in the membrane make the coupling coefficients decay asymptotically as $1/r^2$ with interparticle distance $r$. For the common case, where the distance to the substrate is of sub-micron scale, we present expressions for the coupling between distant disklike inclusions, which are valid for arbitrary inclusion size. We calculate the effect of inclusions on the response of the membrane and the associated corrections to the coupling diffusion coefficients to leading order in the concentration of inclusions. While at short distances the response is modified as if the membrane were a two-dimensional suspension, the large-distance response is not renormalized by the inclusions.Comment: 15 page

Micro-evaporators for kinetic exploration of phase diagrams

We use pervaporation-based microfluidic devices to concentrate species in aqueous solutions with spatial and temporal control of the process. Using experiments and modelling, we quantitatively describe the advection-diffusion behavior of the concentration field of various solutions (electrolytes, colloids, etc) and demonstrate the potential of these devices as universal tools for the kinetic exploration of the phases and textures that form upon concentration

The Electric Double Layer Structure Around Charged Spherical Interfaces

We derive a formally simple approximate analytical solution to the Poisson-Boltzmann equation for the spherical system via a geometric mapping. Its regime of applicability in the parameter space of the spherical radius and the surface potential is determined, and its superiority over the linearized solution is demonstrated.Comment: 7 pages, 5 figure

Investigation of qq-dependent dynamical heterogeneity in a colloidal gel by x-ray photon correlation spectroscopy

We use time-resolved X-Photon Correlation Spectroscopy to investigate the slow dynamics of colloidal gels made of moderately attractive carbon black particles. We show that the slow dynamics is temporally heterogeneous and quantify its fluctuations by measuring the variance $\chi$ of the instantaneous intensity correlation function. The amplitude of dynamical fluctuations has a non-monotonic dependence on scattering vector $q$, in stark contrast with recent experiments on strongly attractive colloidal gels [Duri and Cipelletti, \textit{Europhys. Lett.} \textbf{76}, 972 (2006)]. We propose a simple scaling argument for the $q$-dependence of fluctuations in glassy systems that rationalizes these findings.Comment: Final version published in PR

Nonlinear effects in charge stabilized colloidal suspensions

Molecular Dynamics simulations are used to study the effective interactions in charged stabilized colloidal suspensions. For not too high macroion charges and sufficiently large screening, the concept of the potential of mean force is known to work well. In the present work, we focus on highly charged macroions in the limit of low salt concentrations. Within this regime, nonlinear corrections to the celebrated DLVO theory [B. Derjaguin and L. Landau, Acta Physicochem. USSR {\bf 14}, 633 (1941); E.J.W. Verwey and J.T.G. Overbeck, {\em Theory of the Stability of Lyotropic Colloids} (Elsevier, Amsterdam, 1948)] have to be considered. For non--bulklike systems, such as isolated pairs or triples of macroions, we show, that nonlinear effects can become relevant, which cannot be described by the charge renormalization concept [S. Alexander et al., J. Chem. Phys. {\bf 80}, 5776 (1984)]. For an isolated pair of macroions, we find an almost perfect qualitative agreement between our simulation data and the primitive model. However, on a quantitative level, neither Debye-H\"uckel theory nor the charge renormalization concept can be confirmed in detail. This seems mainly to be related to the fact, that for small ion concentrations, microionic layers can strongly overlap, whereas, simultaneously, excluded volume effects are less important. In the case of isolated triples, where we compare between coaxial and triangular geometries, we find attractive corrections to pairwise additivity in the limit of small macroion separations and salt concentrations. These triplet interactions arise if all three microionic layers around the macroions exhibit a significant overlap. In contrast to the case of two isolated colloids, the charge distribution around a macroion in a triple is found to be anisotropic.Comment: 10 pages, 9 figure

Viscoelasticity of two-layer-vesicles in solution

The dynamic shape relaxation of the two-layer-vesicle is calculated. In additional to the undulation relaxation where the two bilayers move in the same direction, the squeezing mode appears when the gap between the two bilayers is small. At large gap, the inner vesicle relaxes much faster, whereas the slow mode is mainly due to the outer layer relaxation. We have calculated the viscoelasticity of the dilute two-layer-vesicle suspension. It is found that for small gap, the applied shear drives the undulation mode strongly while the slow squeezing mode is not much excited. In this limit the complex viscosity is dominated by the fast mode contribution. On the other hand, the slow mode is strongly driven by shear for larger gap. We have determined the crossover gap which depends on the interaction between the two bilayers. For a series of samples where the gap is changed systematically, it is possible to observe the two amplitude switchings

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