On the influence of electrolytic gradient orientation on phoretic transport in dead-end pores

Abstract

Electrolytic diffusiophoresis refers to directional migration of colloids due to interfacial forces that develop in response to local electrolytic concentration ($c$) gradients. This physicochemical transport provides an efficient alternative in numerous microscale applications where advection-induced transport is infeasible. Phoretic withdrawal and injection in dead-end pores can be controlled by orienting salt gradients into or out of the pore; however, the extent to which this orientation influences spatiotemporal transport patterns is not thoroughly explored. In this study, we find that it has a significant influence: colloidal withdrawal in solute-out mode ($\beta=c_\infty/c_{\text{pore}}<1$) is faster and shallower, whereas the solute-in mode enables deeper withdrawal. Similarly, solute-out injection features rapidly propagating wavefronts, whereas the solute-in mode ($\beta >1$) promotes uniform and gradual injection. Each mode's transport is found to evolve and persist over different time scales. We characterize the performance of these modes and find that while persistence of the solute-out mode strengthens with a growing electrolytic gradient [$\sim \ln(\beta^{-0.4})$], solute-in mode diminishes and eventually its persistence is insensitive to $\beta$. We also incorporate the variable mobility model to examine the impact of large zeta potentials, which intensifies the transport of solute-out mode further and weakens the solute-in mode. Additionally, we investigate how osmotic flows of the two modes affect injection and withdrawal patterns. We find that osmosis-induced mixing can counterintuitively inhibit injection effectiveness in solute-out mode. These insights bring attention to the distinctions between different phoretic transport modes and contribute to the rational design and setup of electrolytic gradients in numerous microscale applications.