Effect of entrapped phase on the filling characteristics of closed-end nanopores

Abstract

We investigated the filling dynamics in closed-end capillaries of sub-micron length scale, in which the displacing phase advances at the expense of the entrapped phase. Contrary to common intuition, we reveal that the existence of a displaced phase in a closed-end nano-scale system does not necessarily retard the meniscus advancement over all temporal regimes, unlike what is observed in cases of macro-scale capillaries, but can also sometimes augment the local filling rates. We determined that the combined effect of surface wettability and the displaced phase molecules resulted from the pinning–depinning of the meniscus, and hence, from the local dynamics of capillary filling. We also employed a simple force balance-based model to capture the essential interfacial phenomena governing this behavior, and benchmarked the same with our molecular dynamics simulations. Our results suggest a possible mechanism for modifying the effective wettabilities of nano-scale capillaries without any modification of the surface architecture or chemical treatment of the surface.