Gustavo C. Abade

Short-time dynamics of permeable particles in concentrated suspensions

We study short-time diffusion properties of colloidal suspensions of neutral permeable particles. An individual particle is modeled as a solvent-permeable sphere of interaction radius a and uniform permeability k, with the fluid flow inside the particle described by the Debye-Bueche-Brinkman equation, and outside by the Stokes equation. Using a precise multipole method and the corresponding numerical code HYDROMULTIPOLE that account for higher-order hydrodynamic multipole moments, numerical results are presented for the hydrodynamic function, H(q), the short-time self-diffusion coefficient, D(s), the sedimentation coefficient K, the collective diffusion coefficient, D(c), and the principal peak value H(q(m)), associated with the short-time cage diffusion coefficient, as functions of porosity and volume fraction. Our results cover the full fluid phase regime. Generic features of the permeable sphere model are discussed. An approximate method by Pusey to determine D(s) is shown to agree well with our accurate results. It is found that for a given volume fraction, the wavenumber dependence of a reduced hydrodynamic function can be estimated by a single master curve, independent of the particle permeability, given by the hard-sphere model. The reduced form is obtained by an appropriate shift and rescaling of H(q), parametrized by the self-diffusion and sedimentation coefficients. To improve precision, another reduced hydrodynamic function, h(m)(q), is also constructed, now with the self-diffusion coefficient and the peak value, H(q(m)), of the hydrodynamic function as the parameters. For wavenumbers qa>2, this function is permeability independent to an excellent accuracy. The hydrodynamic function of permeable particles is thus well represented in its q-dependence by a permeability-independent master curve, and three coefficients, D(s), K, and H(q(m)), that do depend on the permeability. The master curve and its coefficients are evaluated as functions of concentration and permeability.

Diffusion, sedimentation, and rheology of concentrated suspensions of core-shell particles

Short-time dynamic properties of concentrated suspensions of colloidal core-shell particles are studied using a precise force multipole method which accounts for many-particle hydrodynamic interactions. A core-shell particle is composed of a rigid, spherical dry core of radius a surrounded by a uniformly permeable shell of outer radius b and hydrodynamic penetration depth κ(-1). The solvent flow inside the permeable shell is described by the Brinkman-Debye-Bueche equation, and outside the particles by the Stokes equation. The particles are assumed to interact non-hydrodynamically by a hard-sphere no-overlap potential of radius b. Numerical results are presented for the high-frequency shear viscosity, η(∞), sedimentation coefficient, K, and the short-time translational and rotational self-diffusion coefficients, D(t) and D(r). The simulation results cover the full three-parametric fluid-phase space of the composite particle model, with the volume fraction extending up to 0.45, and the whole range of values for κb, and a/b. Many-particle hydrodynamic interaction effects on the transport properties are explored, and the hydrodynamic influence of the core in concentrated systems is discussed. Our simulation results show that for thin or hardly permeable shells, the core-shell systems can be approximated neither by no-shell nor by no-core models. However, one of our findings is that for κ(b - a) ≳ 5, the core is practically not sensed any more by the weakly penetrating fluid. This result is explained using an asymptotic analysis of the scattering coefficients entering into the multipole method of solving the Stokes equations. We show that in most cases, the influence of the core grows only weakly with increasing concentration.

Rotational and translational self-diffusion in concentrated suspensions of permeable particles

In our recent work on concentrated suspensions of uniformly porous colloidal spheres with excluded volume interactions, a variety of short-time dynamic properties were calculated, except for the rotational self-diffusion coefficient. This missing quantity is included in the present paper. Using a precise hydrodynamic force multipole simulation method, the rotational self-diffusion coefficient is evaluated for concentrated suspensions of permeable particles. Results are presented for particle volume fractions up to 45% and for a wide range of permeability values. From the simulation results and earlier results for the first-order virial coefficient, we find that the rotational self-diffusion coefficient of permeable spheres can be scaled to the corresponding coefficient of impermeable particles of the same size. We also show that a similar scaling applies to the translational self-diffusion coefficient considered earlier. From the scaling relations, accurate analytic approximations for the rotational and translational self-diffusion coefficients in concentrated systems are obtained, useful to the experimental analysis of permeable-particle diffusion. The simulation results for rotational diffusion of permeable particles are used to show that a generalized Stokes-Einstein-Debye relation between rotational self-diffusion coefficient and high-frequency viscosity is not satisfied.

High-frequency viscosity of concentrated porous particles suspensions

We determine the high-frequency limiting shear viscosity, eta(infinity), in colloidal suspensions of rigid, uniformly porous spheres of radius a as a function of volume fraction phi and (inverse) porosity parameter x. Our study covers the complete fluid-state regime. The flow inside the spheres is modeled by the Debye-Bueche-Brinkman equation using the boundary condition that fluid velocity and stress change continuously across the sphere surfaces. The many-sphere hydrodynamic interactions in concentrated systems are fully accounted for by a precise hydrodynamic multipole method encoded in our HYDROMULTIPOLE program extended to porous particles. A truncated virial expansion is used to derive an accurate and easy-to-use generalized Saito; formula for eta(infinity). The simulation data are used to test the performance of two simplifying effective particle models. The first model describes the effective particle as a nonporous sphere characterized by a single effective radius a(eff)(x)<a. In the more refined second model, the porous spheres are modeled as spherical annulus particles with an inner hydrodynamic radius a(eff)(x) defining the nonporous dry core and characterizing hydrodynamic interactions, and an outer excluded volume radius a characterizing the unchanged direct interactions. Only the second model is in a satisfactory agreement with the simulation data.

High-frequency viscosity and generalized Stokes–Einstein relations in dense suspensions of porous particles

We study the high-frequency limiting shear viscosity, η∞, of colloidal suspensions of uncharged porous particles. An individual particle is modeled as a uniformly porous sphere with the internal solvent flow described by the Debye-Bueche-Brinkman equation. A precise hydrodynamic multipole method with a full account of many-particle hydrodynamic interactions encoded in the HYDROMULTIPOLE program extended to porous particles, is used to calculate η∞ as a function of porosity and concentration. The second-order virial expansion for η∞ is derived, and its range of applicability assessed. The simulation results are used to test the validity of generalized Stokes-Einstein relations between η∞ and various short-time diffusion coefficients, and to quantify the accuracy of a simplifying cell model calculation of η∞. An easy-to-use generalized Saitô formula for η∞ is presented which provides a good description of its porosity and concentration dependence.

Broadening of Cloud Droplet Spectra through Eddy Hopping: Turbulent Adiabatic Parcel Simulations

AbstractThis paper investigates spectral broadening of droplet size distributions through a mechanism referred to as the eddy hopping. The key idea, suggested a quarter century ago, is that droplets arriving at a given location within a turbulent cloud follow different trajectories and thus experience different growth histories and that this leads to a significant spectral broadening. In this study, the adiabatic parcel model with superdroplets is used to contrast droplet growth with and without turbulence. Turbulence inside the parcel is described by two parameters: (i) the dissipation rate of the turbulent kinetic energy e and (ii) the linear extent of the parcel L. As expected, an adiabatic parcel without turbulence produces extremely narrow droplet spectra. In the turbulent parcel, a stochastic scheme is used to account for vertical velocity fluctuations that lead to local supersaturation fluctuations for each superdroplet. These fluctuations mimic the impact of droplets hopping turbulent eddies in a ...

The short-time self-diffusion coefficient of a sphere in a suspension of rigid rods

The short-time self-diffusion coefficient of a sphere in a suspension of rigid rods is calculated in first order in the rod volume fraction phi. For low rod concentrations, the correction to the Einstein diffusion constant of the sphere due to the presence of rods is a linear function of phi with the slope alpha proportional to the equilibrium averaged mobility diminution trace of the sphere interacting with a single freely translating and rotating rod. The two-body hydrodynamic interactions are calculated using the so-called bead model in which the rod of aspect ratio p is replaced by a stiff linear chain of touching spheres. The interactions between spheres are calculated using the multipole method with the accuracy controlled by a multipole truncation order and limited only by the computational power. A remarkable accuracy is obtained already for the lowest truncation order, which enables calculations for very long rods, up to p=1000. Additionally, the bead model is checked by filling the rod with smaller spheres. This procedure shows that for longer rods the basic model provides reasonable results varying less than 5% from the model with filling. An analytical expression for alpha as a function of p is derived in the limit of very long rods. The higher order corrections depending on the applied model are computed numerically. An approximate expression is provided, valid for a wide range of aspect ratios.

Rotational self-diffusion in suspensions of charged particles: simulations and revised Beenakker–Mazur and pairwise additivity methods

To the present day, the Beenakker-Mazur (BM) method is the most comprehensive statistical physics approach to the calculation of short-time transport properties of colloidal suspensions. A revised version of the BM method with an improved treatment of hydrodynamic interactions is presented and evaluated regarding the rotational short-time self-diffusion coefficient, D, of suspensions of charged particles interacting by a hard-sphere plus screened Coulomb (Yukawa) pair potential. To assess the accuracy of the method, elaborate simulations of D have been performed, covering a broad range of interaction parameters and particle concentrations. The revised BM method is compared in addition with results by a simplifying pairwise additivity (PA) method in which the hydrodynamic interactions are treated on a two-body level. The static pair correlation functions required as input to both theoretical methods are calculated using the Rogers-Young integral equation scheme. While the revised BM method reproduces the general trends of the simulation results, it systematically and significantly underestimates the rotational diffusion coefficient. The PA method agrees well with the simulation data at lower volume fractions, but at higher concentrations D is likewise underestimated. For a fixed value of the pair potential at mean particle distance comparable to the thermal energy, D increases strongly with increasing Yukawa potential screening parameter.