Electroconvective viscous fingering in a single polyelectrolyte fluid on a charge selective surface.

When a low-viscosity fluid displaces into a higher-viscosity fluid, the liquid-liquid interface becomes unstable causing finger-like patterns. This viscous fingering instability has been widely observed in nature and engineering systems with two adjoined fluids. Here, we demonstrate a hitherto-unrealizable viscous fingering in a single fluid-solid interface. In a single polyelectrolyte fluid on a charge selective surface, selective ion rejection through the surface initiates i) stepwise ion concentration and viscosity gradient boundaries in the fluid and ii) electroconvective vortices on the surface. As the vortices grow, the viscosity gradient boundary pushes away from the surface, resulting viscous fingering. Comparable to conventional one with two fluids, i) a viscosity ratio ([Formula: see text]) governs the onset of this electroconvective viscous fingering, and ii) the boundary properties (finger velocity and rheological effects) - represented by [Formula: see text], electric Rayleigh ([Formula: see text]), Schmidt ([Formula: see text]), and Deborah ([Formula: see text]) numbers - determine finger shapes (straight v.s. ramified, the onset length of fingering, and relative finger width). With controllable onset and shape, the mechanism of electroconvective viscous fingering offers new possibilities for manipulating ion transport and dendritic instability in electrochemical systems.