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Register a new userDC electrokinetics for spherical particles in salt-free concentrated suspensions including ion size effects
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Rafael Roa n Fisica Aplicada I
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We study the electrophoretic mobility of spherical particles and the electrical conductivity in salt-free concentrated suspensions including finite ion size effects. An ideal salt-free suspension is composed of just charged colloidal particles and the added counterions that counterbalance their surface charge. In a very recent paper [Roa et al., Phys. Chem. Chem. Phys., 2011, 13, 3960- 3968] we presented a model for the equilibrium electric double layer for this kind of suspensions considering the size of the counterions, and now we extend this work to analyze the response of the suspension under a static external electric field. The numerical results show the high importance of such corrections for moderate to high particle charges, especially when a region of closest approach of the counterions to the particle surface is considered. The present work sets the basis for further theoretical models with finite ion size corrections, concerning particularly the ac electrokinetics and rheology of such systems.
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We analyze the influence of finite ion size effects in the response of a salt-free concentrated suspension of spherical particles to an oscillating electric field. Salt-free suspensions are just composed of charged colloidal particles and the added counterions released by the particles to the solution, that counterbalance their surface charge. In the frequency domain, we study the dynamic electrophoretic mobility of the particles and the dielectric response of the suspension. We find that the Maxwell-Wagner-OKonski process associated with the counterions condensation layer, is enhanced for moderate to high particle charges, yielding an increment of the mobility for such frequencies. We also find that the increment of the mobility grows with ion size and particle charge. All these facts show the importance of including ion size effects in any extension attempting to improve standard electrokinetic models.
A new modified Poisson-Boltzmann equation accounting for the finite size of the ions valid for realistic salt-free concentrated suspensions has been derived, extending the formalism developed for pure salt-free suspensions [Roa et al., Phys. Chem. Chem. Phys., 2011, 13, 3960-3968] to real experimental conditions. These realistic suspensions include water dissociation ions and those generated by atmospheric carbon dioxide contamination, in addition to the added counterions released by the particles to the solution. The electric potential at the particle surface will be calculated for different ion sizes and compared with classical Poisson-Boltzmann predictions for point-like ions, as a function of particle charge and volume fraction. The realistic predictions turn out to be essential to achieve a closer picture of real salt-free suspensions, and even more important when ionic size effects are incorporated to the electric double layer description. We think that both corrections have to be taken into account when developing new realistic electrokinetic models, and surely will help in the comparison with experiments for low-salt or realistic salt-free systems.
Granular fronts are a common yet unexplained phenomenon emerging during the gravity driven free-surface flow of concentrated suspensions. They are usually believed to be the result of fluid convection in combination with particle size segregation. However, suspensions composed of uniformly sized particles also develop a granular front. Within a large rotating drum, a stationary recirculating avalanche is generated. The flowing material is a mixture of a visco-plastic fluid obtained from a kaolin-water dispersion, with spherical ceramic particles denser than the fluid. The goal is to mimic the composition of many common granular-fluid materials, like fresh concrete or debris flow. In these materials, granular and fluid phases have the natural tendency to segregate due to particle settling. However, through the shearing caused by the rotation of the drum, a reorganization of the phases is induced, leading to the formation of a granular front. By tuning the material properties and the drum velocity, it is possible to control this phenomenon. The setting is reproduced in a numerical environment, where the fluid is solved by a Lattice-Boltzmann Method, and the particles are explicitly represented using the Discrete Element Method. The simulations confirm the findings of the experiments, and provide insight into the internal mechanisms. Comparing the time-scale of particle settling with the one of particle recirculation, a non-dimensional number is defined, and is found to be effective in predicting the formation of a granular front.
Thermoresponsive poly(N-isopropylacrylamide) (PNIPAM) particles of a nearly constant swelling ratio and with polydispersity indices (PDIs) varying over a wide range (7.4% - 48.9%) are synthesized to study the effects of polydispersity on the dynamics of suspensions of soft PNIPAM colloidal particles. The PNIPAM particles are characterized using dynamic light scattering (DLS) and scanning electron microscopy (SEM). The zero shear viscosity ($eta_{0}$) data of these colloidal suspensions, estimated from rheometric experiments as a function of the effective volume fraction $phi_{eff}$ of the suspensions, increases with increase in $phi_{eff}$ and shows a dramatic increase at $phi_{eff}=phi_{0}$. The data for $eta_{0}$ as a function of $phi_{eff}$ fits well to the Vogel-Fulcher-Tammann (VFT) equation. It is observed that increasing PDIs results in increasingly fragile supercooled liquid-like behavior, with the parameter $phi_{0}$, extracted from the fits to the VFT equation, shifting towards higher $phi_{eff}$. The observed increase in fragility is attributed to the prevalence of dynamical heterogeneities (DHs) in these polydisperse suspensions, while the simultaneous shift in $phi_{0}$ is ascribed to the decoupling of the dynamics of the smallest and largest particles. Finally, it is observed that the intrinsic nonlinearity of these suspensions, estimated at the third harmonic near $phi_{0}$ in Fourier transform oscillatory rheological experiments, increases with increase in PDIs. Our results are in agreement with theoretical predictions and simulation results for polydisperse hard sphere colloidal glasses and clearly demonstrate that jammed suspensions of polydisperse colloidal particles can be effectively fluidized with increasing PDIs.
We review recent advances in imaging the flow of concentrated suspensions, focussing on the use of confocal microscopy to obtain time-resolved information on the single-particle level in these systems. After motivating the need for quantitative (confocal) imaging in suspension rheology, we briefly describe the particles, sample environments, microscopy tools and analysis algorithms needed to perform this kind of experiments. The second part of the review focusses on microscopic aspects of the flow of concentrated model hard-sphere-like suspensions, and the relation to non-linear rheological phenomena such as yielding, shear localization, wall slip and shear-induced ordering. Both Brownian and non-Brownian systems will be described. We show how quantitative imaging can improve our understanding of the connection between microscopic dynamics and bulk flow.
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