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

Deterministic Brownian motion generated from differential delay equations

This paper addresses the question of how Brownian-like motion can arise from the solution of a deterministic differential delay equation. To study this we analytically study the bifurcation properties of an apparently simple differential delay equation and then numerically investigate the probabilistic properties of chaotic solutions of the same equation. Our results show that solutions of the deterministic equation with randomly selected initial conditions display a Gaussian-like density for long time, but the densities are supported on an interval of finite measure. Using these chaotic solutions as velocities, we are able to produce Brownian-like motions, which show statistical properties akin to those of a classical Brownian motion over both short and long time scales. Several conjectures are formulated for the probabilistic properties of the solution of the differential delay equation. Numerical studies suggest that these conjectures could be "universal" for similar types of "chaotic" dynamics, but we have been unable to prove this.Comment: 15 pages, 13 figure

Electrochemical incineration of wastes

There is an increasing concern regarding the disposal of human wastes in space vehicles. It is of utmost importance to convert such wastes into harmless products which can be recycled into an Environmental Life Support System (CELSS), which incorporates the growth of plants (e.g. wheat) and algae to supplement the diet of the astronauts. Chemical treatments have proven relatively unsatisfactory and tend to be increasingly so with increase of the mission duration. Similarly, the use of heat to destroy wastes and convert them to CO2 by the use of air or oxygen has the disadvantage and difficulty of dissipating heat in a space environment and to the inevitable presence of oxides of nitrogen and carbon monoxide in the effluent gases. In particular, electrochemical techniques offer several advantages including low temperatures which may be used and the absence of any NO and CO in the evolved gases. Successful research has been carried out in the electrochemical oxidation of wastes over the last several years. The major task for 1992 was to conduct parametric studies in preparation for the building of a breadboard system, i.e., an actual practical device to consume the daily waste output of one astronaut in 24 hours, electrochemical incineration of human wastes in space vehicles. One of the main objectives was to decide on the type of three dimensional or other electrode system that would suit this purpose. The various types of electrode systems which were considered for this purpose included: rotating disc electrode, micro-electrode (an array), vibrating electrode, jet electrode, and packed bed electrode

In-depth description of Electrohydrodynamic conduction pumping of dielectric liquids: physical model and regime analysis

In this work, we discuss the fundamental aspects of Electrohydrodynamic (EHD) conduction pumping of dielectric liquids. We build a mathematical model of conduction pumping that can be applied to all sizes, down to microsized pumps. In order to do this, we discuss the relevance of the Electrical Double Layer (EDL) that appears naturally on nonmetallic substrates. In the process, we identify a new dimensionless parameter related to the value of the zeta potential of the substrate-liquid pair, which quantifies the influence of these EDLs on the performance of the pump. This parameter also describes the transition from EHD conduction pumping to electro-osmosis. We also discuss in detail the two limiting working regimes in EHD conduction pumping: ohmic and saturation. We introduce a new dimensionless parameter, accounting for the electric field enhanced dissociation that, along with the conduction number, allows us to identify in which regime the pump operates.Ministerio de Ciencia, Innovación y Universidades PGC2018-099217-B-I0

Evaluation of packed-bed and fluidized-bed cell technology for the destruction and removal of contaminants in alkaline waste solutions. Final report

Disposing of the large quantity of nuclear waste that has been produced within the DOE complex is an area of active research and development. Electrochemical processes have been reported for the treatment of alkaline wastes including the destruction of nitrate and nitrite and the removal of metals such as Tc and Ru. Electrolytic recovery of metals from dilute solution has been reported using conventional porous electrodes such as felt electrode and reticulated electrode, but use of such electrodes is limited. The pores of such electrodes become blocked as a consequence of metal deposition. If an attempt is made to regenerate these electrodes by dissolution of the deposited metals, oxygen evolution on the matrix competes with dissolution of metals deposited within the pores. On the other hand, the use of three dimensional packed-bed and fluidized-bed electrodes having large surface area per unit volume would offer an improvement on felt or reticulated system because of the greater ease of regeneration

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

Non-mean-field theory of anomalously large double-layer capacitance

Mean-field theories claim that the capacitance of the double-layer formed at a metal/ionic conductor interface cannot be larger than that of the Helmholtz capacitor, whose width is equal to the radius of an ion. However, in some experiments the apparent width of the double-layer capacitor is substantially smaller. We propose an alternate, non-mean-field theory of the ionic double-layer to explain such large capacitance values. Our theory allows for the binding of discrete ions to their image charges in the metal, which results in the formation of interface dipoles. We focus primarily on the case where only small cations are mobile and other ions form an oppositely-charged background. In this case, at small temperature and zero applied voltage dipoles form a correlated liquid on both contacts. We show that at small voltages the capacitance of the double-layer is determined by the transfer of dipoles from one electrode to the other and is therefore limited only by the weak dipole-dipole repulsion between bound ions, so that the capacitance is very large. At large voltages the depletion of bound ions from one of the capacitor electrodes triggers a collapse of the capacitance to the much smaller mean-field value, as seen in experimental data. We test our analytical predictions with a Monte Carlo simulation and find good agreement. We further argue that our ``one-component plasma" model should work well for strongly asymmetric ion liquids. We believe that this work also suggests an improved theory of pseudo-capacitance.Comment: 19 pages, 14 figures; some Monte Carlo results and a section about aqueous solutions adde

Collective dynamics in crystalline polymorphs of ZnCl2_{2}: potential modelling and inelastic neutron scattering study

We report a phonon density of states measurement of $\alpha$-ZnCl$_{2}$ using the coherent inelastic neutron scattering technique and a lattice dynamical calculation in four crystalline phases of ZnCl$_{2}$ using a transferable interatomic potential. The model calculations agree reasonably well with the available experimental data on the structures, specific heat, Raman frequencies and their pressure variation in various crystalline phases. The calculated results have been able to provide a fair description of the vibrational as well as the thermodynamic properties of ZnCl$_{2}$ in all its four phases.Comment: Accepted in J. Phys.: Condens. Matte

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