Transitions and Instabilities in Imperfect Ion-Selective Membranes.

Numerical investigation of the underlimiting, limiting, and overlimiting current modes and their transitions in imperfect ion-selective membranes with fluid flow through permitted through the membrane is presented. The system is treated as a three layer composite system of electrolyte-porous membrane-electrolyte where the Nernst-Planck-Poisson-Stokes system of equations is used in the electrolyte, and the Darcy-Brinkman approach is employed in the nanoporous membrane. In order to resolve thin Debye and Darcy layers, quasi-spectral methods are applied using Chebyshev polynomials for their accumulation of zeros and, hence, best resolution in the layers. The boundary between underlimiting and overlimiting current regimes is subject of linear stability analysis, where the transition to overlimiting current is assumed due to the electrokinetic instability of the one-dimensional quiescent state. However, the well-developed overlimiting current is inherently a problem of nonlinear stability and is subject of the direct numerical simulation of the full system of equations. Both high and low fixed charge density membranes (low- and high concentration electrolyte solutions), acting respectively as (nearly) perfect or imperfect membranes, are considered. The perfect membrane is adequately described by a one-layer model while the imperfect membrane has a more sophisticated response. In particular, the direct transition from underlimiting to overlimiting currents, bypassing the limiting currents, is found to be possible for imperfect membranes (high-concentration electrolyte). The transition to the overlimiting currents for the low-concentration electrolyte solutions is monotonic, while for the high-concentration solutions it is oscillatory. Despite the fact that velocities in the porous membrane are much smaller than in the electrolyte region, it is further demonstrated that they can dramatically influence the nature and transition to the overlimiting regimes. A map of the bifurcations, transitions, and regimes is constructed in coordinates of the fixed membrane charge and the Darcy number.