Quantification of Viscosity and Capillary Pressure Anomalies for Polar Liquids in 2D Hydrophilic Nano-Confinements

Abstract:

Interest in liquid and interfacial behavior within nano-confinements spans many disciplines. Geophysical interest originates from a desire to understand flow mechanisms through hydrocarbon-rich nano-porous shale media, especially communication between fractures and the adjacent nano-porous matrix (imbibition). This work investigates the extent of boundary layer nucleation during polar liquid flows in hydrophilic nano-confinements via discrepancies seen in viscosity and capillary pressure from their bulk values. We perform our experiments in two-dimensional nanochannels of varying size and as small as 30 nm x 60 nm in cross section and still obtain visual data with reflected differential interference contrast (DIC) microscopy. The simple geometry of the nanochannels enables the comparison against analytical transport solutions. By designing a nanochannel experiment that allows us to monitor the rate of fluid imbibition and volume loss of a trapped air pocket the liquid is imbibing into, we are able to decouple capillary pressure and viscosity from imbibition data, as well as gain information about gas partitioning at the meniscus interface. Our current experiments are performed with organic solvents within siliceous nanochannels and the results of the decoupling scheme indicate that for rectangular nanochannels with heights of 60 nm and varying widths, effective viscosity is consistently between 4-12 times higher than the bulk value and capillary pressure is around 50% less than the macroscopic Young-Laplace equation prediction. These results equate to the nucleation of wall boundary layers on the order of tens of molecular layers thick. Structured boundary layers have an inherently increased viscosity compared to the liquid bulk value, resulting in a significant reduction in imbibition efficacy. This presence of approximately 15 nm boundary layers in on the threshold of two different theories – thin bimolecular boundary layers and exclusion zones (thick boundary layers) – and beckons deeper inspection into how surface chemistry and hydrodynamic shearing control the extent of boundary layer termination during liquid flow in hydrophilic two-dimensional nano-confinements and pores.