Traditional models of electrokinetic transport in porous media are based on homogenized material properties, which neglect any macroscopic effects of microscopic fluctuations. This perspective is taken not only for convenience, but also motivated by the expectation of irrotational electro-osmotic flow, proportional to the electric field, for uniformly charged surfaces (or constant zeta potential) in the limit of thin double layers. Here, we show that the inherent heterogeneity of porous media generally leads to macroscopic vortex patterns, which have important implications for convective transport and mixing. These vortical flows originate due to competition between pressure-driven and electro-osmotic flows, and their size are characterized by the correlation length of heterogeneity in permeability or surface charge. The appearance of vortices is controlled by a single dimensionless control parameter, defined as the ratio of a typical electro-osmotic velocity to the total mean velocity.
Possible mechanisms of overlimiting current in unsupported electrolytes, exceeding diffusion limitation, have been intensely studied for their fundamental significance and applications to desalination, separations, sensing, and energy storage. In bulk membrane systems, the primary physical mechanism is electro-convection, driven by electro-osmotic instability on the membrane surface. It has recently been predicted that confinement by charged surfaces in microchannels or porous media favors two new mechanisms, electro-osmotic flow (EOF) and surface conduction (SC), driven by large electric fiel…
We discuss an electro-osmotic flow near charged porous coatings of a finite hydrodynamic permeability, impregnated with an outer electrolyte solution. It is shown that their electrokinetic (zeta) potential is generally augmented compared to the surface electrostatic potential, thanks to a large liquid slip at their surface emerging due to an electro-osmotic flow in the enriched by counter-ions porous films. The inner flow shows a very rich behavior controlled by the volume charge density of the coating, its Brinkman length, and concentration of added salt. Interestingly, even for relatively sm…
Patterned surfaces with large effective slip lengths, such as super-hydrophobic surfaces containing trapped gas bubbles, have the potential to greatly enhance electrokinetic phenomena. Existing theories assume either homogeneous flat surfaces or patterned surfaces with thin double layers (compared to the texture correlation length) and thus predict simple surface-averaged, isotropic flows (independent of orientation). By analyzing electro-osmotic flows over striped slip-stick surfaces with arbitrary double-layer thickness, we show that surface anisotropy generally leads to a tensorial electro-…
We study the viscous dissipation in pipe flows in long channels with porous or semipermeable walls, taking into account both the dissipation in the bulk of the channel and in the pores. We give simple closed form expressions for the dissipation in terms of the axially varying flow rate $Q(x)$ and the pressure $p(x)$, generalizing the well known expression $\dot W=Q\,Δp$ for the case of impenetrable walls with constant $Q$ and a pressure difference $Δp$ between the ends of the pipe. When the pressure $p_0$ outside the pipe is constant, the result is the straightforward generalization $\dot W=Δ\…
We consider a coupled system of Navier Stokes, Maxwell Stefan and Poisson Boltzmann equations by incorporating the variation of dielectric constant, which governs the electro osmotic flow in nano channel, describing the evolution of the velocity, concentration and potential fields of dissolved constituents in an aqueous electrolyte solution. We apply the finite difference technique to solve one and two dimensional systems of these equations. The solutions give an extremely accurate prediction of the dielectric constant for a variety of salts and a wide range of concentrations.
Three-dimensional (3D) AC electro-osmotic (ACEO) pumps have recently been developed that are much faster and more robust than previous planar designs. The basic idea is to create a ``fluid conveyor belt'' by placing opposing ACEO slip velocities at different heights. Current designs involve electrodes with electroplated steps, whose heights have been optimized in simulations and experiments. Here, we consider changing the boundary conditions--rather than the geometry--and predict that flow rates can be further doubled by fabricating 3D features with non-polarizable materials. This amplifies th…
It has been suggested that superhydrophobic surfaces, due to the presence of a no-shear zone, can greatly enhance transport of surface charges, leading to a considerable increase in the streaming potential. This could find potential use in micro-energy harvesting devices. In this paper, we show using analytical and numerical methods, that when a streaming potential is generated in such superhydrophobic geometries, the reverse electro-osmotic flow and hence current generated by this, is significant. A decrease in streaming potential compared to what was earlier predicted is expected. We also sh…
For a dielectric solid surrounded by an electrolyte and positioned inside an externally biased parallel-plate capacitor, we study numerically how the resulting induced-charge electro-osmotic (ICEO) flow depends on the topology and shape of the dielectric solid. In particular, we extend existing conventional electrokinetic models with an artificial design field to describe the transition from the liquid electrolyte to the solid dielectric. Using this design field, we have succeeded in applying the method of topology optimization to find system geometries with non-trivial topologies that maximiz…
This paper details the development of an integrated AC electro-osmotic (ACEO) microfluidic pump for dilute electrolytes consisting of a long serpentine microchannel lined with three dimensional (3D) stepped electrode arrays. Using low AC voltage (1 Volt rms, 1 kHz), power (5 mW) and current (3.5 mA) in water, the pump is capable of generating a 1.4 kPa head pressure, a 100-fold increase over prior ACEO pumps, and a 1.37 mm/sec effective slip velocity over the electrodes without flow reversal. The integrated ACEO pump can utilize low ionic strength solutions such as distilled water as the worki…
Most electrochemical processes, such as electrodialysis, are limited by diffusion, but in porous media, surface conduction and electro-osmotic flow also contribute to ionic fluxes. In this paper, we report experimental evidence for surface-driven over-limiting current (faster than diffusion) and deionization shocks (propagating salt removal) in a porous medium. The apparatus consists of a silica glass frit (1 mm thick with 500 nm mean pore size) in an aqueous electrolyte (CuSO$_4$ or AgNO$_3$) passing ionic current from a reservoir to a cation-selective membrane (Nafion). The current-voltage r…
We study here the curious particle dynamics resulting from electro-osmotic flow around a microchannel junction corner whose dielectric walls are weakly polarizable. The hydrodynamic velocity field is obtained via superposition of a linear irrotational term associated with the equilibrium zeta potentials of both the microchannel and particle surfaces and the non-linear induced-charge electro-osmotic flow which originates from the interaction of the externally applied electric field on the charge cloud it induces at the solid-liquid interface. The particle dynamics are analyzed by considering di…
We report that an electro-osmotic instability of concentration enrichment in curved geometries for an aqueous electrolyte, as opposed to the well-known one, is initiated exclusively at the enriched interface (anode), rather than at the depleted one (cathode). For this instability, the limitation of unrealistically high material Peclet number in planar geometry is eliminated by the strong electric field arising from the line charge singularity. In a model setup of concentric circular electrodes, we show by stability analysis, numerical simulation, and experimental visualization that instability…
We present a "fluid dynamics video" showing results from direct numerical simulations of electrokinetic transport in a binary electrolyte in two systems: (1) next to an ion-selective membrane and (2) around a metallic cylinder. The governing equations are the Poisson--Nernst--Planck and Navier--Stokes and our DNS resolves the time and length scales associated with the thin electric double layers. Our results show transition to chaotic dynamics when the applied voltage across the characteristic length scale is above a threshold of approximately 0.5 Volt. More details, in particular regarding sy…
Analytic expressions for the speed, flux, microrotation, stress, and couple stress in a micropolar fluid exhibiting steady, symmetric and one-dimensional electro-osmotic flow in a uniform cylindrical microcapillary were derived under the constraint of the Debye-Hueckel approximation, which is applicable when the cross-sectional radius of the microcapillary exceeds the Debye length, provided that the zeta potential is sufficiently small in magnitude. As the aciculate particles in a micropolar fluid can rotate without translation, micropolarity influences fluid speed, fluid flux, and one of the …
Since its prediction fifteen years ago, electro-osmotic instability has been attributed to non-equilibrium electro-osmosis related to the extended space charge which develops at the limiting current in the course of concentration polarization at a charge-selective interface. This attribution had a double basis. Firstly, it has been recognized that equilibrium electro-osmosis cannot yield instability for a perfectly charge-selective solid. Secondly, it has been shown that non-equilibrium electro-osmosis can. First theoretical studies in which electro-osmotic instability was predicted and analyz…
In this paper we present electro-osmotic (EO) flow within a more traditional fluid mechanics framework. Specifically, the modified Bernoulli equation (viz. the energy equation, the mechanical energy equation, the pipe flow equation, etc.) is shown to be applicable to EO flows if an electrical potential energy term is also included. The form of the loss term in the modified Bernoulli equation is unaffected by the presence of an electric field; i.e., the loss term still represents the effect of wall shear stress, which can be represented via a friction factor. We show that that the friction fact…
We show that an electric field parallel to an electrically neutral surface can generate flow of electrolytic mixtures in small channels. We term this solvo-osmotic flow, since the flow is induced by the asymmetric preferential solvation of ions at the liquid-solid interface. The generated flow is comparable in magnitude to the ubiquitous electro-osmotic flow at charged surfaces, but for a fixed surface charge density, it differs qualitatively in its dependence on ionic strength. Solvo-osmotic flow can also be sensitively controlled with temperature. We derive a modified Helmholtz-Smoluchowski …
We demonstrate the existence of a fluid-structure instability arising from the interaction of electro-osmotic flow with an elastic substrate. Considering the case of flow within a soft fluidic chamber, we show that above a certain electric field threshold, negative gauge pressure induced by electro-osmotic flow causes the collapse of its elastic walls. We combine experiments and theoretical analysis to elucidate the underlying mechanism for instability and identify several distinct dynamic regimes. The understanding of this instability is important for the design of electrokinetic systems cont…
Numerical analyses of transient electro-osmosis of a typical non-Newtonian liquid induced by DC and AC electric fields in a rectangular microchannel are conducted in the framework of continuum fluid mechanics. The famous power-law constitutive model is used to express the fluid dynamic viscosity in terms of the velocity gradient. Transient start-up characteristics of electro-osmotic power-law liquid flow in rectangular microchannels are simulated by using finite element method. Under a DC electric field, it is found out and the fluid is more inert to the external electric field and the steady-…
We derive from kinetic theory, fluid mechanics, and thermodynamics the minimal continuum-level equations governing the flow of a binary, non-electrolytic mixture in an isotropic porous medium with osmotic effects. For dilute mixtures, these equations are linear and in this limit provide a theoretical basis for the widely-used semi-empirical relations of Kedem and Katchalsky (1958), which have hitherto been validated experimentally but not theoretically. The above linearity between the fluxes and the driving forces breaks down for concentrated or non-ideal mixtures, for which our equations go b…
An electrokinetic (zeta) potential of charged permeable porous films on solid supports generally exceeds their surface potential, which often builds up to a quite high value itself. Recent work provided a quantitative understanding of zeta potentials of thick, compared to the extension of an inner electrostatic diffuse layer, porous films. Here, we consider porous coatings of a thickness comparable or smaller than that of the inner diffuse layer. Our theory, which is valid even when electrostatic potentials become quite high and accounts for a finite hydrodynamic permeability of the porous mat…
Colloidal capsules can sustain an external osmotic pressure; however, for a sufficiently large pressure, they will ultimately buckle. This process can be strongly influenced by structural inhomogeneities in the capsule shells. We explore how the time delay before the onset of buckling decreases as the shells are made more inhomogeneous; this behavior can be quantitatively understood by coupling shell theory with Darcy's law. In addition, we show that the shell inhomogeneity can dramatically change the folding pathway taken by a capsule after it buckles.
In this paper we report the theory describing the electro-osmotic flow in charged nanopores with constant radius and charge density driven by alternating current. We solve the ion and solution transport in unsteady conditions as described by the Navier-Stokes and Nernst-Planck equations considering the electrical potential inside the charged nanopore uniform in the radial direction (Uniform Potential model approximation). We derive the transport equation system in the case in which the pore is connected to two boundary diffusion layers and the cations and anions have different diffusion coeffi…
Electroosmotic pumping of fluid through a nanopore that traverses an insulating membrane is considered. The density of surface charge on the membrane is assumed uniform, and sufficiently low for the Poisson-Boltzmann equation to be linearized. The reciprocal theorem gives the flow rate generated by an applied weak electric field, expressed as an integral over the fluid volume. For a circular hole in a membrane of zero thickness, an analytical result is possible up to quadrature. For a membrane of arbitrary thickness, the full Poisson--Nernst--Planck--Stokes system of equations is solved numeri…
The differential migration of ions in an applied electric field is the basis for separation of chemical species by capillary electrophoresis. Axial diffusion of the concentration peak limits the separation efficiency. Electromigration dispersion is observed when the concentration of sample ions is comparable to that of the background ions. Under such conditions, the local electrical conductivity is significantly altered in the sample zone making the electric field, and therefore, the ion migration velocity concentration dependent. The resulting nonlinear wave exhibits shock like features, and,…
Physical parameters characterising electrokinetic transport in a confined electrolyte solution are reconstructed from the generic transport coefficients obtained within the classical non-equilibrium statistical thermodynamic framework. The electro-osmotic flow, the diffusio-osmotic flow, the osmotic current, as well as the pressure-driven Poiseuille-type flow, the electric conduction, and the ion diffusion, are described by this set of transport coefficients. The reconstruction is demonstrated for an aqueous NaCl solution between two parallel charged surfaces with a nanoscale gap, by using the…
We give a general theoretical description of electro-osmotic flow at striped super-hydrophobic surfaces in a thin double layer limit, and derive a relation between the electro-osmotic mobility and hydrodynamic slip-length tensors. Our analysis demonstrates that electro-osmotic flow shows a very rich behavior controlled by slip length and charge at the gas sectors. In case of uncharged liquid-gas interface, the flow is the same or inhibited relative to flow in homogeneous channel with zero interfacial slip. By contrast, it can be amplified by several orders of magnitude provided slip regions ar…
The electro-osmotic flow through a channel between two undulated surfaces induced by an external electric field is investigated. The gap of the channel is very small and comparable to the thickness of the electrical double layers. A lattice Boltzmann simulation is carried out on the model consisting of the Poisson equation for electrical potential, the Nernst--Planck equation for ion concentration, and the Navier--Stokes {\color{black}equations} for flows of the electrolyte solution. An analytical model that predicts the flow rate is also derived under the assumption that the channel width is …
The electrolyte (comprising of solute ions and solvents) flow-through the porous media is frequently encountered in nature or in many engineering applications, such as the electrochemical systems, manufacturing of composites, geothermal engineering, soil pollution. In this study, we provide a new general theory for the electrochemical flows-through porous media. We use static method and set up two representative elementary volumes (REVs). One is the macroscopic REV of the mixture of the porous media and the electrolyte, while the other is the microscopic REV in the electrolyte fluid. The estab…
We present a numerical study of nonlinear electrokinetic transport in porous media, focusing on the role of heterogeneity in a porous microstructure on ion concentration polarization and over-limiting current. For simplicity, the porous medium is modeled as a network of long, thin charged cylindrical pores, each governed by one-dimensional effective transport equations. For weak surface conduction, when sufficiently large potential is applied, we demonstrate that electrokinetic transport in a porous network can be dominated by electroconvection via internally induced flow loops, which is not p…
Thermo-osmotic flows - flows generated in micro and nanofluidic systems by thermal gradients - could provide an alternative approach to harvest waste heat. However, such use would require massive thermo-osmotic flows, which are up to now only predicted for special and expensive materials. There is thus an urgent need to design affordable nanofluidic systems displaying large thermo-osmotic coefficients. In this paper we propose a general model for thermo-osmosis of aqueous electrolytes in charged nanofluidic channels, taking into account hydrodynamic slip, together with the different solvent an…
Unrestricted particle transport through microfluidic channels is of paramount importance to a wide range of applications, including lab-on-a-chip devices. In this article, we study using video microscopy the electro-osmotic aggregation of colloidal particles at the opening of a micrometer-sized silica channel in presence of a salt gradient. Particle aggregation eventually leads to clogging of the channel, which may be undone by a time-adjusted reversal of the applied electric potential. We numerically model our system via the Stokes-Poisson-Nernst-Planck equations in a geometry that approximat…
A simple analytical model of a layered system comprised of a single passage of a serpentine flow channel and a parallel underlying porous electrode (or porous layer) is proposed. This analytical model is derived from Navier-Stokes motion in the flow channel and Darcy-Brinkman model in the porous layer. The continuities of flow velocity and normal stress are applied at the interface between the flow channel and the porous layer. The effects of the inlet volumetric flow rate, thickness of the flow channel and thickness of a typical carbon fiber paper porous layer on the volumetric flow rate with…
We demonstrate the phenomenon of induced-charge capacitive deionization (ICCDI) that occurs around a porous and conducting particle immersed in an electrolyte, under the action of an external electric field. The external electric field induces an electric dipole in the porous particle, leading to its capacitive charging by both cations and anions at opposite poles. This regime is characterized by a long charging time which results in significant changes in salt concentration in the electrically neutral bulk, on the scale of the particle. We qualitatively demonstrate the effect of advection on …
Microchannel with porous wall has various microfluidic applications including iontophoresis, diagnostic devices, etc. In order to have an efficient and better design of such devices, exact quantification of velocity field in the microchannel needs to be established. In the present study, an analytical solution of velocity field in a microchannel with porous wall was obtained for a Newtonian fluid in case of a combined electroosmotic and pressure driven flow using perturbation technique. The velocity profile was reduced to well known solutions for three asymptotic cases, namely, purely electroo…
A two-scale model is presented to simulate the dynamic ion transport and adsorption processes in porous electrodes used for capacitive deionization (CDI). At the pore scale, the Stokes equation governing water flow in porous CDI electrodes is solved using the lattice Boltzmann method and Nernst-Planck equations describing ion transport is solved using the finite volume method. The ion adsorption process is considered at the surface of carbon electrodes. At the continuum scale, Darcy equation and advection-diffusion equation governing water flow and solute transport through CDI cells are solved…
We revisit the classical problem of diffusion-limited ion transport to a membrane (or electrode) by considering the effects of charged side walls. Using simple mathematical models and numerical simulations, we identify three basic mechanisms for over-limiting current in a microchannel: (i) {\it surface conduction} carried by excess counterions, which dominates for very thin channels, (ii) convection by {\it electro-osmotic flow} on the side walls, which dominates for thicker channels and transitions to (iii) {\it electro-osmotic instability} on the membrane end in very thick channels. These in…
We show that an electro-osmotic flow near the slippery hydrophobic surface depends strongly on the mobility of surface charges, which are balanced by counter-ions of the electrostatic diffuse layer. For a hydrophobic surface with immobile charges the fluid transport is considerably amplified by the existence of a hydrodynamic slippage. In contrast, near the hydrophobic surface with mobile adsorbed charges it is also controlled by an additional electric force, which increases the shear stress at the slipping interface. To account for this, we formulate electro-hydrodynamic boundary conditions a…
In this work, a two-dimensional mathematical model is developed to study the flow patterns and volumetric flow penetrations in the flow channel over the porous electrode layered system in vanadium flow battery with serpentine flow field design. The flow distributions at the interface between the flow channel and porous electrode are examined. It is found that the non-linear pressure distributions can distinguish the interface flow distributions under the ideal plug flow and ideal parabolic flow inlet boundary conditions. However, the volumetric flow penetration within the porous electrode bene…
Experimental two-phase invasion percolation flow patterns were observed in hydrophobic micro-porous networks designed to model fuel cell specific porous media. In order to mimic the operational conditions encountered in the porous electrodes of polymer electrolyte membrane fuel cells (PEMFCs), micro-porous networks were fabricated with corresponding microchannel size distributions. The inlet channels were invaded homogeneously with flow rates corresponding to fuel cell current densities of 1.0 to 0.1 A/cm2 (Ca 10e-7-10e-8). A variety of fractal breakthrough patterns were observed and analyzed …
A novel 3-electrode cell type is introduced to run parametrical studies of H$_2$ evolution in an alkaline electrolyte on porous electrodes. Electrochemical methods combined with a high-speed optical measurement system are applied simultaneously to characterize the electrodes and the bubble dynamics in terms of bubble size distribution and coverage of the working electrode. Three different cathodes made of expanded nickel are investigated at applied current densities of |j| = 10 to 200 mA cm$^{-2}$ without forced flow and at a flow rate of 5 ml min$^{-1}$. The applied current density is found t…
Multicomponent gas transport is investigated with unprecedented precision by AC impedance analysis of porous YSZ anode-supported solid oxide fuel cells. A fuel gas mixture of H2-H2O-N2 is fed to the anode, and impedance data are measured across the range of hydrogen partial pressure (10-100%) for open circuit conditions at three temperatures (800C, 850C and 900C) and for 300mA applied current at 800C. For the first time, analytical formulae for the diffusion resistance (Rb) of three standard models of multicomponent gas transport (Fick, Stefan-Maxwell, and Dusty Gas) are derived and tested aga…
