1: Magnetic Particles: Preparation, Properties and Applications: M. Ozaki. 2: Maghemite (gamma-Fe2O3): A Versatile Magnetic Colloidal Material C.J. Serna, M.P. Morales. 3: Dynamics of Adsorption and Oxidation of Organic Molecules on Illuminated Titanium Dioxide Particles Immersed in Water M.A. Blesa, R.J. Candal, S.A. Bilmes. 4: Colloidal Aggregation in Two-Dimensions A. Moncho-Jorda, F. Martinez-Lopez, M.A. Cabrerizo-Vilchez, R. Hidalgo Alvarez, M. Quesada-PMerez. 5: Kinetics of Particle and Protein Adsorption Z. Adamczyk.

Surface and Colloid Science

Nanofluidics has emerged recently in the footsteps of microfluidics, following the quest for scale reduction inherent to nanotechnologies. By definition, nanofluidics explores transport phenomena of fluids at nanometer scales. Why is the nanometer scale specific? What fluid properties are probed at nanometric scales? In other words, why does ‘nanofluidics’ deserve its own brand name? In this critical review, we will explore the vast manifold of length scales emerging for fluid behavior at the nanoscale, as well as the associated mechanisms and corresponding applications. We will in particular explore the interplay between bulk and interface phenomena. The limit of validity of the continuum approaches will be discussed, as well as the numerous surface induced effects occurring at these scales, from hydrodynamic slippage to the various electro-kinetic phenomena originating from the couplings between hydrodynamics and electrostatics. An enlightening analogy between ion transport in nanochannels and transport in doped semi-conductors will be discussed (156 references).

http://ilm-perso.univ-lyon1.fr/~lbocquet/ChemSocRev-Bocquet-2010.pdf

Nanofluidics, from bulk to interfaces

http://web.mit.edu/bazant/www/papers/pdf/Bazant_2009_ACIS_preprint.pdf

Towards an understanding of induced-charge electrokinetics at large applied voltages in concentrated solutions

Common to liquids, solids and substances in between the former two is that if a stress is applied to them, they will strain. Stress may be visualized by placing a small amount of fluid between two parallel plates. When one plate slides over the other, forces act on the fluid dependent upon the rate of the plate movement. This causes a shear stress on the liquid. Recall laminar flow of fluids through a tubular vessel. Strain is the response to the stress. If solids are elastic, they deform and return to their original shape. Since fluids are not elastic and, hence, viscous, their deformation is irreversible.

Introduction to rheology

The classical Poisson-Boltzmann (PB) theory of electrolytes assumes a dilute solution of point charges with mean-field electrostatic forces. Even for very dilute solutions, however, it predicts absurdly large ion concentrations (exceeding close packing) for surface potentials of only a few tenths of a volt, which are often exceeded, e.g. in microfluidic pumps and electrochemical sensors. Since the 1950s, several modifications of the PB equation have been proposed to account for the finite size of ions in equilibrium, but in this two-part series, we consider steric effects on diffuse charge dynamics (in the absence of electro-osmotic flow). In this first part, we review the literature and analyze two simple models for the charging of a thin double layer, which must form a condensed layer of close-packed ions near the surface at high voltage. A surprising prediction is that the differential capacitance typically varies non-monotonically with the applied voltage, and thus so does the response time of an electrolytic system. In PB theory, the capacitance blows up exponentially with voltage, but steric effects actually cause it to decrease above a threshold voltage where ions become crowded near the surface. Other nonlinear effects in PB theory are also strongly suppressed by steric effects: The net salt adsorption by the double layers in response to the applied voltage is greatly reduced, and so is the tangential "surface conduction" in the diffuse layer, to the point that it can often be neglected compared to bulk conduction (small Dukhin number).

Steric effects in the dynamics of electrolytes at large applied voltages: I. Double-layer charging

Recent theoretical studies have suggested a significant enhancement in electro-osmotic flows over hydrodynamically slipping surfaces, and experiments have indeed measured O(1) enhancements. In this paper, we investigate whether an equivalent effect occurs in the electrophoretic motion of a colloidal particle whose surface exhibits hydrodynamic slip. To this end, we compute the electrophoretic mobility of a uniformly charged spherical particle with slip length λ as a function of the zeta (or surface) potential of the particle ζ and diffuse-layer thickness κ−1. In the case of a thick diffuse layer, κa⪡1 (where a is the particle size), simple arguments show that slip does lead to an O(1) enhancement in the mobility, owing to the reduced viscous drag on the particle. On the other hand, for a thin-diffuse layer κa⪢1, the situation is more complicated. A detailed asymptotic analysis, following the method of O’Brien [J. Colloid Interface Sci. 92, 204 (1983)], reveals that an O(κλ) increase in the mobility occurs...

The influence of hydrodynamic slip on the electrophoretic mobility of a spherical colloidal particle

The motion of a single Brownian probe particle subjected to a constant external body force and immersed in a dispersion of colloidal particles is studied with a view to providing a simple model for particle tracking microrheology experiments in the active and nonlinear regime. The non-equilibrium configuration of particles induced by the motion of the probe is calculated to first order in the volume fraction of colloidal particles over the entire range of Pe, accounting for hydrodynamic and excluded volume interactions between the probe and dispersion particles. Here, Pe is the dimensionless external force on the probe, or Peclet number, and is a characteristic measure of the degree to which the equilibrium microstructure of the dispersion is distorted. For small Pe, the microstructure (in a reference frame moving with the probe) is primarily dictated by Brownian diffusion and is approximately fore–aft symmetric about the direction of the external force. In the large Pe limit, advection is dominant except in a thin boundary layer in the compressive region of the flow where it is balanced by Brownian diffusion, leading to a highly non-equilibrium microstructure. The computed microstructure is employed to calculate the average translational velocity of the probe, from which the ‘microviscosity’ of the dispersion may be inferred via application of Stokes drag law. For small departures from equilibrium (Pe), the microviscosity ‘force-thins’ proportional to $\hbox{\it Pe}^2$ from its Newtonian low-force plateau. For particles with long-range excluded volume interactions, force-thinning persists until a terminal Newtonian plateau is reached in the limit $\hbox{\it Pe}\,{\rightarrow}\,\infty$. In the case of particles with very short-range excluded volume interactions, the force-thinning ceases at $\hbox{\it Pe}\,{\sim}\, O(1)$, at which point the microviscosity attains a minimum value. Beyond $\hbox{\it Pe}\,{\sim}\, O(1)$, the microstructural boundary layer coincides with the lubrication range of hydrodynamic interactions causing the microviscosity to enter a continuous ‘force-thickening’ regime. The qualitative picture of the microviscosity variation with Pe is in good agreement with theoretical and computational investigations on the ‘macroviscosity’ of sheared colloidal dispersions, and, after appropriate scaling, we are able to make a direct quantitative comparison. This suggests that active tracking microrheology is a valuable tool with which to explore the rich nonlinear rheology of complex fluids.

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Single particle motion in colloidal dispersions: a simple model for active and nonlinear microrheology

The transient deformation of a weakly conducting (‘leaky dielectric’) drop under a uniform DC electric field is computed via an axisymmetric boundary integral method, which accounts for surface charge convection and a finite relaxation time scale over which the drop interface charges. We focus on drops that attain an ultimate oblate (major axis normal to the applied field) steady-state configuration. The computations predict that as the time scale for interfacial charging increases, a shape transition from prolate deformation (major axis parallel to the applied field) to oblate deformation occurs at intermediate times due to the slow buildup of charge at the surface of the drop. Convection of surface charge towards the equator of the drop is shown to weaken the steady-state oblate deformation. Additionally, convection results in sharp shock-like variations in surface charge density near the equator of the drop. Our numerical results are then compared with an experimental system consisting of a millimetre-sized silicone oil drop suspended in castor oil. Agreement in the transient deformation is observed between our numerical results and experimental measurements for moderate electric field strengths. This suggests that both charge relaxation and charge convection are required, in general, to quantify the time-dependent deformation of leaky dielectric drops. Importantly, accurate prediction of the observed modest deformation requires a nonlinear model. Discrepancies between our numerical calculations and experimental results arise as the field strength is increased. We believe that this is due to the observed onset of rotation and three-dimensional flow at such high electric fields in the experiments, which an axisymmetric boundary integral formulation naturally cannot capture.

Nonlinear electrohydrodynamics of slightly deformed oblate drops

The self-propulsion of a spherical squirmer – a model swimming organism that achieves locomotion via steady tangential movement of its surface – is quantified across the transition from viscously to inertially dominated flow. Specifically, the flow around a squirmer is computed for Reynolds numbers (Re) between 0.01 and 1000 by numerical solution of the Navier–Stokes equations. A squirmer with a fixed swimming stroke and fixed swimming direction is considered. We find that fluid inertia leads to profound differences in the locomotion of pusher (propelled from the rear) versus puller (propelled from the front) squirmers. Specifically, pushers have a swimming speed that increases monotonically with Re, and efficient convection of vorticity past their surface leads to steady axisymmetric flow that remains stable up to at least Re = 1000. In contrast, pullers have a swimming speed that is non-monotonic with Re. Moreover, they trap vorticity within their wake, which leads to flow instabilities that cause a decrease in the time-averaged swimming speed at large Re. The power expenditure and swimming efficiency are also computed. We show that pushers are more efficient at large Re, mainly because the flow around them can remain stable to much greater Re than is the case for pullers. Interestingly, if unstable axisymmetric flows at large Re are considered, pullers are more efficient due to the development of a Hill’s vortex-like wake structure

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A squirmer across Reynolds numbers

We calculate the electrophoretic mobility Me of a spherical colloidal particle, using modified Poisson–Nernst–Planck (PNP) equations that account for steric repulsion between finite sized ions, through Bikerman's mean-field model (Bikerman, Phil. Mag., vol. 33, 1942, p. 384). Ion steric effects are controlled by the bulk volume fraction of ions ν, and for ν = 0 the standard PNP equations are recovered. An asymptotic analysis in the thin-double-layer limit reveals at small zeta potentials (ζ < kBT/e ≈ 25 mV) Me to increase linearly with ζ for all ν, as expected from the Helmholtz–Smoluchowski (HS) formula. For larger ζ, however, it is well known that surface conduction of ions within the double layer reduces Me below the HS result. Crucially, however, in the PNP equations surface conduction becomes significant precisely because of the aphysically large and unbounded counter-ion densities predicted at large ζ. In contrast, ion steric effects impose a limit on the counter-ion density, thereby mitigating surface conduction. Hence, Me does not fall as far below HS for finite sized ions (ν ≠ 0). Indeed, at sufficiently large ν, ion steric effects are so dramatic that a maximum in Me is not observed for physically reasonable values of ζ(≤ 10 kBT/e), in stark contrast to the PNP-based calculations of O'Brien & White (J. Chem. Soc. Faraday Trans. II, vol. 74, 1978, p. 1607) and O'Brien (J. Colloid Interface Sci., vol. 92, 1983, p. 204). Finally, by calculating a Dukhin–Bikerman number characterizing the relative importance of surface conduction, we collapse Me versus ζ data for different ν onto a single master curve.

Aditya S. Khair

Papers

The influence of hydrodynamic slip on the electrophoretic mobility of a spherical colloidal particle

Single particle motion in colloidal dispersions: a simple model for active and nonlinear microrheology

Nonlinear electrohydrodynamics of slightly deformed oblate drops

A squirmer across Reynolds numbers

Ion steric effects on electrophoresis of a colloidal particle