Effective zero-thickness model for a conductive membrane driven by an electric field

The behavior of a conductive membrane in a static (DC) electric field is investigated theoretically. An effective zero-thickness model is constructed based on a Robin-type boundary condition for the electric potential at the membrane, originally developed for electrochemical systems. Within such a framework, corrections to the elastic moduli of the membrane are obtained, which arise from charge accumulation in the Debye layers due to capacitive effects and electric currents through the membrane and can lead to an undulation instability of the membrane. The fluid flow surrounding the membrane is also calculated, which clarifies issues regarding these flows sharing many similarities with flows produced by induced charge electro-osmosis (ICEO). Non-equilibrium steady states of the membrane and of the fluid can be effectively described by this method. It is both simpler, due to the zero thickness approximation which is widely used in the literature on fluid membranes, and more general than previous approaches. The predictions of this model are compared to recent experiments on supported membranes in an electric field.Comment: 14 pages, 5 figure

Frequency response in surface-potential driven electro-hydrodynamics

Using a Fourier approach we offer a general solution to calculations of slip velocity within the circuit description of the electro-hydrodynamics in a binary electrolyte confined by a plane surface with a modulated surface potential. We consider the case with a spatially constant intrinsic surface capacitance where the net flow rate is in general zero while harmonic rolls as well as time-averaged vortex-like components may exist depending on the spatial symmetry and extension of the surface potential. In general the system displays a resonance behavior at a frequency corresponding to the inverse RC time of the system. Different surface potentials share the common feature that the resonance frequency is inversely proportional to the characteristic length scale of the surface potential. For the asymptotic frequency dependence above resonance we find a 1/omega^2 power law for surface potentials with either an even or an odd symmetry. Below resonance we also find a power law omega^alpha with alpha being positive and dependent of the properties of the surface potential. Comparing a tanh potential and a sech potential we qualitatively find the same slip velocity, but for the below-resonance frequency response the two potentials display different power law asymptotics with alpha=1 and alpha~2, respectively.Comment: 4 pages including 1 figure. Accepted for PR

AC electrokinetic phenomena over semiconductive surfaces: effective electric boundary conditions and their applications

Electrokinetic boundary conditions are derived for AC electrokinetic (ACEK) phenomena over leaky dielectric (i.e., semiconducting) surfaces. Such boundary conditions correlate the electric potentials across the semiconductor-electrolyte interface (consisting of the electric double layer (EDL) inside the electrolyte solutions and the space charge layer (SCL) inside the semiconductors) under AC electric fields with arbitrary wave forms. The present electrokinetic boundary conditions allow for evaluation of induced zeta potential contributed by both bond charges (due to electric polarization) and free charges (due to electric conduction) from the leaky dielectric materials. Subsequently, we demonstrate the applications of these boundary conditions in analyzing the ACEK phenomena around a semiconducting cylinder. It is concluded that the flow circulations exist around the semiconducting cylinder and are shown to be stronger under an AC field with lower frequency and around a cylinder with higher conductivity.Comment: 29 pages, 4 figure

Strongly nonlinear dynamics of electrolytes in large ac voltages

We study the response of a model micro-electrochemical cell to a large ac voltage of frequency comparable to the inverse cell relaxation time. To bring out the basic physics, we consider the simplest possible model of a symmetric binary electrolyte confined between parallel-plate blocking electrodes, ignoring any transverse instability or fluid flow. We analyze the resulting one-dimensional problem by matched asymptotic expansions in the limit of thin double layers and extend previous work into the strongly nonlinear regime, which is characterized by two novel features - significant salt depletion in the electrolyte near the electrodes and, at very large voltage, the breakdown of the quasi-equilibrium structure of the double layers. The former leads to the prediction of "ac capacitive desalination", since there is a time-averaged transfer of salt from the bulk to the double layers, via oscillating diffusion layers. The latter is associated with transient diffusion limitation, which drives the formation and collapse of space-charge layers, even in the absence of any net Faradaic current through the cell. We also predict that steric effects of finite ion sizes (going beyond dilute solution theory) act to suppress the strongly nonlinear regime in the limit of concentrated electrolytes, ionic liquids and molten salts. Beyond the model problem, our reduced equations for thin double layers, based on uniformly valid matched asymptotic expansions, provide a useful mathematical framework to describe additional nonlinear responses to large ac voltages, such as Faradaic reactions, electro-osmotic instabilities, and induced-charge electrokinetic phenomena.Comment: 30 pages, 17 eps-figures, RevTe

Nonlinear electrochemical relaxation around conductors

We analyze the simplest problem of electrochemical relaxation in more than one dimension - the response of an uncharged, ideally polarizable metallic sphere (or cylinder) in a symmetric, binary electrolyte to a uniform electric field. In order to go beyond the circuit approximation for thin double layers, our analysis is based on the Poisson-Nernst-Planck (PNP) equations of dilute solution theory. Unlike most previous studies, however, we focus on the nonlinear regime, where the applied voltage across the conductor is larger than the thermal voltage. In such strong electric fields, the classical model predicts that the double layer adsorbs enough ions to produce bulk concentration gradients and surface conduction. Our analysis begins with a general derivation of surface conservation laws in the thin double-layer limit, which provide effective boundary conditions on the quasi-neutral bulk. We solve the resulting nonlinear partial differential equations numerically for strong fields and also perform a time-dependent asymptotic analysis for weaker fields, where bulk diffusion and surface conduction arise as first-order corrections. We also derive various dimensionless parameters comparing surface to bulk transport processes, which generalize the Bikerman-Dukhin number. Our results have basic relevance for double-layer charging dynamics and nonlinear electrokinetics in the ubiquitous PNP approximation.Comment: 25 pages, 17 figures, 4 table

Diffuse-Charge Dynamics in Electrochemical Systems

The response of a model micro-electrochemical system to a time-dependent applied voltage is analyzed. The article begins with a fresh historical review including electrochemistry, colloidal science, and microfluidics. The model problem consists of a symmetric binary electrolyte between parallel-plate, blocking electrodes which suddenly apply a voltage. Compact Stern layers on the electrodes are also taken into account. The Nernst-Planck-Poisson equations are first linearized and solved by Laplace transforms for small voltages, and numerical solutions are obtained for large voltages. The ``weakly nonlinear'' limit of thin double layers is then analyzed by matched asymptotic expansions in the small parameter $\epsilon = \lambda_D/L$, where $\lambda_D$ is the screening length and $L$ the electrode separation. At leading order, the system initially behaves like an RC circuit with a response time of $\lambda_D L / D$ (not $\lambda_D^2/D$), where $D$ is the ionic diffusivity, but nonlinearity violates this common picture and introduce multiple time scales. The charging process slows down, and neutral-salt adsorption by the diffuse part of the double layer couples to bulk diffusion at the time scale, $L^2/D$. In the ``strongly nonlinear'' regime (controlled by a dimensionless parameter resembling the Dukhin number), this effect produces bulk concentration gradients, and, at very large voltages, transient space charge. The article concludes with an overview of more general situations involving surface conduction, multi-component electrolytes, and Faradaic processes.Comment: 10 figs, 26 pages (double-column), 141 reference

Electrostatic and electrokinetic contributions to the elastic moduli of a driven membrane

We discuss the electrostatic contribution to the elastic moduli of a cell or artificial membrane placed in an electrolyte and driven by a DC electric field. The field drives ion currents across the membrane, through specific channels, pumps or natural pores. In steady state, charges accumulate in the Debye layers close to the membrane, modifying the membrane elastic moduli. We first study a model of a membrane of zero thickness, later generalizing this treatment to allow for a finite thickness and finite dielectric constant. Our results clarify and extend the results presented in [D. Lacoste, M. Cosentino Lagomarsino, and J. F. Joanny, Europhys. Lett., {\bf 77}, 18006 (2007)], by providing a physical explanation for a destabilizing term proportional to \kps^3 in the fluctuation spectrum, which we relate to a nonlinear ($E^2$) electro-kinetic effect called induced-charge electro-osmosis (ICEO). Recent studies of ICEO have focused on electrodes and polarizable particles, where an applied bulk field is perturbed by capacitive charging of the double layer and drives flow along the field axis toward surface protrusions; in contrast, we predict "reverse" ICEO flows around driven membranes, due to curvature-induced tangential fields within a non-equilibrium double layer, which hydrodynamically enhance protrusions. We also consider the effect of incorporating the dynamics of a spatially dependent concentration field for the ion channels.Comment: 22 pages, 10 figures. Under review for EPJ