Electrokinetic Instability near Charge-Selective Hydrophobic Surfaces

The influence of the texture of a hydrophobic surface on the electro-osmotic slip of the second kind and the electrokinetic instability near charge-selective surfaces (permselective membranes, electrodes, or systems of micro- and nanochannels) is investigated theoretically using a simple model based on the Rubinstein-Zaltzman approach. A simple formula is derived to evaluate the decrease in the instability threshold due to hydrophobicity. The study is complemented by numerical investigations both of linear and nonlinear instabilities near a hydrophobic membrane surface. Theory predicts a significant enhancement of the ion flux to the surface and shows a good qualitative agreement with the available experimental data.

Three-dimensional Coherent Structures of Electrokinetic Instability

A direct numerical simulation of the three-dimensional elektrokinetic instability near a charge selective surface (electric membrane, electrode, or system of micro-/nanochannels) is carried out and analyzed. A special finite-difference method was used for the space discretization along with a semi-implicit $3frac{1}{3}$-step Runge-Kutta scheme for the integration in time. The calculations employed parallel computing. Three characteristic patterns, which correspond to the overlimiting currents, are observed: (a) two-dimensional electroconvective rolls, (b) three-dimensional regular hexagonal structures, and (c) three-dimensional structures of spatiotemporal chaos, which are a combination of unsteady hexagons, quadrangles and triangles. The transition from (b) to (c) is accompanied by the generation of interacting two-dimensional solitary pulses.

Direct Numerical Simulation of Electrokinetic Instability and Transition to Chaotic Motion

A new type of instability - electrokinetic instability - and an unusual transition to chaotic motion near a charge-selective surface was studied by numerical integration of the Nernst-Planck-Poisson-Stokes system and a weakly nonlinear analysis near the threshold of instability. Two kinds of initial conditions were considered: (a) white noise initial conditions to mimic room disturbances and subsequent natural evolution of the solution; (b) an artificial monochromatic ion distribution with a fixed wave number to simulate regular wave patterns. The results were studied from the viewpoint of hydrodynamic stability and bifurcation theory. The threshold of electroconvective movement was found by the linear spectral stability theory, the results of which were confirmed by numerical simulation of the entire system. The following regimes, which replace each other as the potential drop between the selective surfaces increases, were obtained: one-dimensional steady solution; two-dimensional steady electroconvective vortices (stationary point in a proper phase space); unsteady vortices aperiodically changing their parameters (homoclinic contour); periodic motion (limit cycle); and chaotic motion. The transition to chaotic motion did not include Hopf bifurcation. Numerical resolution of the thin concentration polarization layer showed spike-like charge profiles along the surface, which could be, depending on the regime, either steady or aperiodically coalescent. The numerical investigation confirmed the experimentally observed absence of regular (near-sinusoidal) oscillations for the overlimiting regimes. There is a qualitative agreement of the experimental and the theoretical values of the threshold of instability, the dominant size of the observed coherent structures, and the experimental and theoretical volt-current characteristics.