No Arabic abstract
In 1983 Felderhof, Ford and Cohen gave microscopic explanation of the famous Clausius-Mossotti formula for the dielectric constant of nonpolar dielectric. They based their considerations on the cluster expansion of the dielectric constant, which relates this macroscopic property with the microscopic characteristics of the system. In this article, we analyze the cluster expansion of Felderhof, Ford and Cohen by performing its resummation (renormalization). Our analysis leads to the ring expansion for the macroscopic characteristic of the system, which is an expression alternative to the cluster expansion. Using similarity of structures of the cluster expansion and the ring expansion, we generalize (renormalize) the Clausius-Mossotti approximation. We apply our renormalized Clausius-Mossotti approximation to the case of the short-time transport properties of suspensions, calculating the effective viscosity and the hydrodynamic function with the translational self-diffusion and the collective diffusion coefficient. We perform calculations for monodisperse hard-sphere suspensions in equilibrium with volume fraction up to 45%. To assess the renormalized Clausius-Mossotti approximation, it is compared with numerical simulations and the Beenakker-Mazur method. The results of our renormalized Clausius-Mossotti approximation lead to comparable or much less error (with respect to the numerical simulations), than the Beenakker-Mazur method for the volume fractions below $ phi approx 30% $ (apart from a small range of wave vectors in hydrodynamic function). For volume fractions above $phi approx 30 %$, the Beenakker-Mazur method gives in most cases lower error, than the renormalized Clausius-Mossotti approximation.
We present a comprehensive computational study of the short-time transport properties of bidisperse neutral colloidal suspensions and the corresponding porous media. Our study covers bidisperse particle size ratios up to $4$, and total volume fractions up to and beyond the monodisperse hard-sphere close packing limit. The many-body hydrodynamic interactions are computed using conventional Stokesian Dynamics (SD) via a Monte-Carlo approach. We address suspension properties including the short-time translational and rotational self-diffusivities, the instantaneous sedimentation velocity, the wavenumber-dependent partial hydrodynamic functions, and the high-frequency shear and bulk viscosities; and porous media properties including the permeability and the translational and rotational hindered diffusivities. We carefully compare the SD computations with existing theoretical and numerical results. For suspensions, we also explore the range of validity of various approximation schemes, notably the Pairwise Additive (PA) approximations with the Percus-Yevick structural input. We critically assess the strengths and weaknesses of the SD algorithm for various transport properties. For very dense systems, we discuss in detail the interplay between the hydrodynamic interactions and the structures due to the presence of a second species of a different size.
Diffusion in bidisperse Brownian hard-sphere suspensions is studied by Stokesian Dynamics (SD) computer simulations and a semi-analytical theoretical scheme for colloidal short-time dynamics, based on Beenakker and Mazurs method [Physica 120A, 388 (1983) & 126A, 349 (1984)]. Two species of hard spheres are suspended in an overdamped viscous solvent that mediates the salient hydrodynamic interactions among all particles. In a comprehensive parameter scan that covers various packing fractions and suspension compositions, we employ numerically accurate SD simulations to compute the initial diffusive relaxation of density modulations at the Brownian time scale, quantified by the partial hydrodynamic functions. A revised version of Beenakker and Mazurs $deltagamma$-scheme for monodisperse suspensions is found to exhibit surprisingly good accuracy, when simple rescaling laws are invoked in its application to mixtures. The so-modified $deltagamma$ scheme predicts hydrodynamic functions in very good agreement with our SD simulation results, for all densities from the very dilute limit up to packing fractions as high as $40%$.
We report on a comprehensive theory-simulation-experimental study of collective and self-diffusion in suspensions of charge-stabilized colloidal spheres. In simulation and theory, the spheres interact by a hard-core plus screened Coulomb pair potential. Intermediate and self-intermediate scattering functions are calculated by accelerated Stokesian Dynamics simulations where hydrodynamic interactions (HIs) are fully accounted for. The study spans the range from the short-time to the colloidal long-time regime. Additionally, Brownian Dynamics simulation and mode-coupling theory (MCT) results are generated where HIs are neglected. It is shown that HIs enhance collective and self-diffusion at intermediate and long times, whereas at short times self-diffusion, and for certain wavenumbers also collective diffusion, are slowed down. MCT significantly overestimate the slowing influence of dynamic particle caging. The simulated scattering functions are in decent agreement with our dynamic light scattering (DLS) results for suspensions of charged silica spheres. Simulation and theoretical results are indicative of a long-time exponential decay of the intermediate scattering function. The approximate validity of a far-reaching time-wavenumber factorization of the scattering function is shown to be a consequence of HIs. Our study of collective diffusion is amended by simulation and theoretical results for the self-intermediate scattering function and the particle mean squared displacement (MSD). Since self-diffusion is not assessed in DLS measurements, a method to deduce the MSD approximately in DLS is theoretically validated.
The aggregation of attractive colloids has been extensively studied from both theoretical and experimental perspectives as the fraction of solid particles is changed, and the range, type and strength of attractive or repulsive forces between particles varies. The resulting gels consisting of disordered assemblies of attractive colloidal particles, have also been investigated with regards to percolation, phase separation, and the mechanical characteristics of the resulting fractal networks. Despite tremendous progress in our understanding of the gelation process, and the exploration of different routes for arresting the dynamics of attractive colloids, the complex interplay between convective transport processes and many-body effects in such systems has limited our ability to drive the system towards a specific configuration. Here we study a model attractive colloidal system over a wide range of particle characteristics and flow conditions undergoing aggregation far from equilibrium. The complex multiscale dynamics of the system can be understood using a Time-Rate-Transformation diagram adapted from understanding of materials processing in block copolymers, supercooled liquids and much stiffer glassy metals to direct targeted assembly of attractive colloidal particles.
We present an experimental study of short-time diffusion properties in fluid-like suspensions of monodisperse charge-stabilized silica spheres suspended in DMF. The static structure factor S(q), the short-time diffusion function, D(q), and the hydrodynamic function, H(q), in these systems have been probed by combining X-ray photon correlation spectroscopy experiments with static small-angle X-ray scattering. Our experiments cover the full liquid-state part of the phase diagram, including deionized systems right at the liquid-solid phase boundary. We show that the dynamic data can be consistently described by the renormalized density fluctuation expansion theory of Beenakker and Mazur over a wide range of concentrations and ionic strengths. In accord with this theory and Stokesian dynamics computer simulations, the measured short-time properties cross over monotonically, with increasing salt content, from the bounding values of salt-free suspensions to those of neutral hard spheres. Moreover, we discuss an upper bound for the hydrodynamic function peak height of fluid systems based on the Hansen-Verlet freezing criterion.