Raul A. Rica

Abstract: A model of the electro-diffusion of ions in porous electrodes is applied to analyze the dynamics of capacitive-mixing extraction of energy from salinity gradients with carbon porous electrodes. The complex time-evolution of the cell voltage observed in experiments is satisfactorily described. The asymmetry on the duration of the solution-change steps performed in open circuit is found to be due to the nonlinear voltage-concentration relationship of the electric double layers and to a current that redistributes the counterions along the depth of the electrode leading to nonuniform charge and salt adsorption. The validated model is an essential tool for the design and optimization of renewable energy extraction by this technique. �© 2012 American Chemical Society.

Abstract: The effect of the volume fraction of solids on the concentration polarization around spheroidal particles has been recently investigated using data on the low frequency dielectric dispersion (LFDD) of suspensions [Rica et al., Soft Matter, 2011, 7, 3286]. In this work, we extend our previous experimental analysis including new measurements at different surface charge together with dynamic electrophoretic mobility determinations. This joint study allows us to detect two �± relaxations, due to the two characteristic dimensions of our rod-like particles, in addition to the Maxwell-Wagner-O�Konski relaxation and the inertial effects on the electrophoretic mobility. Available theoretical models for the polarization of a single rod are extended to consider particle-particle interactions, this leading to the estimation of the zeta potential and the characteristic size and geometry of the particles. The most significant result of the LFDD experiments is the different trend of low and high frequency relaxations with volume fraction. Calculation of the concentration polarization maps around the spheroidal particle suggests that such different trends can be explained by the different extent of the polarization clouds along both semiaxes. �© 2012 The Royal Society of Chemistry.

Abstract: Purpose. A computer model was developed to test the assumption that diffuse neural loss can result in the field loss pattern characteristic of glaucoma. Methods. The anterior visual pathways comprised the retinal ganglion cells, and their axons up to the optic nerve head (ONH) were modeled in a computer program. Axon resistance to stress was accounted for depending on the location on the ONH, taking into consideration the presence or absence of vessels in the area. Damage patterns were applied to the axons at the ONH, and the corresponding dendritic fields were removed accordingly. A visual field was extracted and represented on a gray scale after a predetermined stage of damage was reached. Two patterns of damage were considered, a diffuse damage produced by randomly removing fibers and an ordered anteroposterior elimination. Results. Random damage never rendered a pattern loss. Ordered centrifugal fiber loss may produce a radial pattern more conspicuous when the vessels are endowed with a protective role. In both cases, scotomas tend to be detectable earlier in more peripheral locations, attributable to the increasing size of the receptive fields with eccentricity. Conclusions. The model shows that pattern loss typical of glaucoma cannot be solely the result of a random loss of fibers. Anteroposterior damage of the ONH can explain radial progression of scotomas if a protective role is introduced for the central vessels. Copyright �© 2011 American Academy of Optometry.

Abstract: We present the first experimental results on the effect of the particles content (up to �ž = 20% volume fraction of solids) in the low frequency dielectric dispersion (LFDD) of suspensions of hematite (a-Fe 2O 3) prolate spheroidal colloids. Two �±-relaxations, each one associated to a characteristic dimension of the particles, are clearly observed, but they present different dependencies with volume fraction. Accounting for particle-particle interactions, in terms of models for spheres, allows a comprehensive interpretation of the mechanisms involved, suggesting the presence of a nematic phase in our suspensions. �© The Royal Society of Chemistry 2011.

Abstract: This paper describes an investigation on the electric permittivity of concentrated suspensions of non-spherical particles, specifically prolate spheroids. It is first discussed how the determination of the frequency (��) dependence of the electric permittivity (a phenomenon traditionally known as LFDD or low-frequency dielectric dispersion) can provide ample information on the properties of the dispersed material (shape, size, state of aggregation, conductivity) and of its interface with the (typically aqueous) medium. The basic quantities are the strength and frequency dependence of the dipole moment induced by the applied field, and its dimensionless counterpart, the dipole coefficient, C*(��). It is explicitly shown how the (complex) relative permittivity of the suspension, �µr* (��), can be calculated from it. Two theoretical models on the polarizability of spheroidal colloidal particles will be used as theoretical starting point; one of them (Model I) explicitly considers two relaxations of the permittivity, each associated to one of the particle axes. The other (Model II) is a semi-analytical theory that yields an LFDD practically independent of the axial ratio of the particles. Both models are aimed to be used if the suspensions are dilute (low volume fraction of solids, ��symbol), and here they are generalized to concentrated systems by means of a previously published approximate evaluation of the permittivity of concentrated suspensions. Experiments are performed in the 1 kHz-1 MHz frequency range on suspensions of elongated goethite particles; the effects of ionic strength, pH, and volume fraction are investigated, and the two models are fitted to the data. In reality, taking into account that the particles are non-uniformly charged (a fact that contributes to their instability), two zeta potentials (roughly representing the lateral surface and the tip of the spheroid) are used as parameters. The results indicate that, when experimental conditions are optimal (high ionic strength and low zeta potential), the suspensions do indeed display two relaxations, that we ascribe to the long axis (and to flocs likely present in suspension) and to the short one. The permittivity increases with ionic strength, a result found with other systems, and compatible with a zeta potential that, on the average, decreases with ionic strength, an equally well known result, consequence of electric double layer compression. Another reasonable finding is the increase of estimated average dimensions and the decrease of electrokinetic potentials when the pH is close to the isoelectric point of goethite (around pH 9). The increase in volume fraction, finally, produces an overall increase in the permittivity, and the approximate model used for the evaluation of volume fraction variations can describe properly these effects, with basically constant zeta potentials and dimensions. �© 2009 Elsevier Inc. All rights reserved.

Abstract: Colloidal particles in electrolytes move in response to electric fields (electrophoresis) and salt concentration gradients (diffusiophoresis), and related flows also occur at fixed surfaces (electro-osmosis and diffusio-osmosis, respectively). In isolation, these electrokinetic phenomena are well understood, e.g., electrophoresis without far-field concentration gradients and diffusiophoresis without applied electric fields. When the electrolyte passes direct current, however, concentration gradients accompany the bulk electric field (concentration polarization) and the resulting particle motion, called "electrodiffusiophoresis," involves a nonlinear combination of electrophoresis and diffusiophoresis, depending on ion transference numbers and particle properties. In this work, we analyze the electrodiffusiophoresis of spherical particles in the limit of thin double layers, neglecting surface conduction (Duâ�ª1) and convection (Peâ�ª1), considering both nonpolarizable (fixed charge) and ideally polarizable (induced-charge) surfaces. Via asymptotic approximations and numerical solutions, we develop a physical picture to guide potential applications in electrochemical cells, such as analyte focusing, electrophoretic deposition, and microfluidic mixing near membranes or electrodes. By controlling the mean salt concentration, particle size, current, and concentration gradient, significant motion of particles (or fluid) is possible toward either electrode and toward high or low concentration. �© 2010 American Institute of Physics.

Abstract: In this work we consider how the spheroidal shape of colloidal particles and their concentration in suspension influence their electrokinetic properties in alternating (ac) electric fields, in particular, their electrophoretic mobility, traditionally known as dynamic mobility in the case of ac fields. Elaboration of a formula for the mobility is based on two previous models related to the electrokinetic response of spheroids in dilute suspensions, completed by means of an approximate formula to account for the finite concentration of particles. At the end, semianalytical formulas have been obtained in the form of the classical Helmholtz-Smoluchowski equation for the mobility with three frequencydependent factors, each dealing with inertia relaxation, electric double layer polarization and volume fraction effects. The two resulting expressions differ basically in their consideration of double layer polarization processes, as one considers only Maxwell-Wagner-O�Konski polarization (related to the mismatch between the conductivities of the particles plus their double layers and the liquid medium), and the other also includes the concentration polarization effect. Since in the frequency range typically used in dynamic mobility measurements the latter polarization has already relaxed, both models are capable of accounting for the dynamic mobility data experimentally obtained on elongated goethite particles in the 1-18 MHz frequency range. Results are presented concerning the effects of volume fraction, ionic strength, and pH, and they indicate that the models are good descriptions of the electrokinetics of these systems, and that dynamic mobility is very sensitive not only to the zeta potential of the particles, but also to their concentration, shape, and average size, and to the stability of the suspensions. The effects of ionic strength and pH on the dynamic mobility are very well captured by both models, and a consistent description of the dimensions and zeta potentials of the particles is reached. Increasing the volume fraction of the suspensions produces mobility variations that are only partially described by the theoretical calculations due to the likely flocculation of the particles, mainly associated with the fact that goethite particles are not homogeneously charged, with attraction between positive and negative patches being possible. �© 2009 American Chemical Society.

Abstract: Prompted by the results obtained by Mantegazza et al. [Nature Physics 1 (2005) 103], where the electric birefringence of suspensions of elongated particles was strikingly affected by the presence of a sea of very small (size ratio lower than 10:1) colloidal spheres, we have undertaken an investigation of other electrokinetic phenomena in suspensions containing various relative concentrations of large (Teflon or polystyrene latex) and small (nanometer-sized silica spheres) colloids. We have determined the quantities that might be greatly affected by the size distribution of the particles, mainly in the presence of ac electric fields, since the response of the suspensions will show very characteristic relaxations, dominated in principle by the size of the particles. In this work, we report on measurements of the dielectric dispersion of mixed particles as a function of the concentration, ionic strength, and field frequency. The results indicate that the response is not just a simple combination of those obtained with suspensions of the individual particles, and in fact the presence of even small amounts of the small particles affects considerably the frequency response of the suspensions. �© 2007 Elsevier Inc. All rights reserved.

Abstract: Electroacoustic techniques are promising tools for the size determination and electrokinetic characterization of concentrated colloidal suspensions. When particles are not homogeneous in size and/or density, the dynamic mobility obtained is a kind of average of the mobilities of every particle. In this paper, we try to discern which averaging procedure provides a better description of the dynamic mobility of bidisperse suspensions consisting of a mixture of two very different types of particles. The results show that the amplitude of the sound wave induced by an applied ac field (electrokinetic sonic amplitude) is not just the sum of the amplitudes of the waves generated by every particle but has a larger contribution from the larger particles, although the small size entities considerably influence the behaviour of the latter because of their interference in the fluxes of the fluid and ions around them.