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Liquid imbibition, the capillary-pressure-driven flow of a liquid into a gas, provides a mechanism for studying the effects of solid-liquid and solid-liquid-gas interfaces on nanoscale transport. Deviations from the classic Washburn equation for imbibition are generally observed for nanoscale imbibition, but the identification of the origin of these irregularities in terms of transport variables varies greatly among investigators. We present an experimental method and corresponding image and data analysis scheme that enable the determination of independent effective values of nanoscale capillary pressure, liquid viscosity, and interfacial gas partitioning coefficients, all critical transport variables, from imbibition within nanochannels. Experiments documented herein are performed within two-dimensional siliceous nanochannels of varying size and as small as 30 nm × 60 nm in cross section. The wetting fluid used is the organic solvent isopropanol and the nonwetting fluid is air, but investigations are not limited to these fluids. Optical data of dynamic flow are rare in geometries that are nanoscale in two dimensions due to the limited resolution of optical microscopy. We are able to capture tracer-free liquid imbibition with reflected differential interference contrast microscopy. Results with isopropanol show a significant departure from bulk transport values in the nanochannels: reduced capillary pressures, increased liquid viscosity, and nonconstant interfacial mass-transfer coefficients. The findings equate to the nucleation of structured, quasi-crystalline boundary layers consistently ∼10-25 nm in extent. This length is far thicker than the boundary layer range prescribed by long-range intermolecular force interactions. Slower but linear imbibition in some experimental cases suggests that structured boundary layers may inhibit viscous drag at confinement walls for critical nanochannel dimensions. Probing the effects of nanoconfinement on the definitions of capillary pressure, viscosity, and interfacial mass transfer is critical in determining and improving the functionality and fluid transport efficacy of geological, biological, and synthetic nanoporous media and materials.

Due to diagenesis, pores in subsurface rocks such as sandstones exhibit varying degrees of surface roughness in the forms of authigenic cement coatings and mineral dissolution. Previous work describing capillary trapping in porous media has primarily focused on pore‐space geometry, wettability, and fluid viscosity contrast, while acknowledging, but not quantifying, the potential impact of surface roughness. We introduce a method to implement surface roughness with controlled variation of hillock density and heights into glass microfluidic chips and investigate surface roughness impacts on gas trapping following imbibition of water into air. We demonstrate that surface roughness with hillock height‐to‐pore‐depth ratios (herein called Ω) less than a media‐dependent threshold (Ω = 6%–10% in the micromodels) does not promote nonwetting phase (gas) trapping. By contrast, rougher micromodels with Ω values larger than the aforementioned roughness threshold show a dramatic increase in the saturation of trapped gas (gas saturation values up to 64%) due to an observed change in imbibition dynamics from binary filling to pendular‐ring formation within pore throats as well as capillary pinning within pore bodies. Furthermore, when the micromodel intermediate capillary number results are compared to Land's model, only the roughest microfluidics chips (Ω > 10%) fall within the literature‐described values of the characteristic trapping constant, C, implying that surface roughness is also a key gas trapping control, independent of or in addition to pore‐space geometry and wettability. An a priori menisci stability criterion and a heuristic explanation based on local contact angle variations are proposed to explain surface roughness‐induced trapping.

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We observed that imbibition of various Rhodamine B-doped wetting liquids in an array of different-sized, horizontal, two-dimensional silica nanochannels terminated within the channels as a function of hydraulic diameter and liquid type. This front termination is not predicted by the classic Washburn equation for capillary flow, which establishes diffusive dynamics in horizontal channels. Various explanations for the anomalous static imbibition measurements were negated; hydrodynamics, thermodynamics, surface chemistry and mechanics were all taken into consideration for this analysis. The atypical imbibition data are explained by deformed menisci and decreased effective channel diameters. These occurrences are due to the enhanced influence of the following phenomena at the nanoscale: surface forces at fluid-solid boundaries, the presence of quasi-crystalline thin films or boundary regions, and potential solid surface or boundary layer deformation due to meniscus-induced negative pressures (suction). We introduce a phenomenological model which demonstrates how van der Waals forces, common to all interfaces, lead to local menisci deformation and an average reduction in capillary pressure. An expression for the approximate capillary pressure of a symmetric nanoscale meniscus in a cylindrical pore space is derived; its difference from the macroscopic capillary pressure can be expressed by an effective contact angle. Precursor films, adsorbed films and elastocapillary deformation decrease effective diameter, exacerbating meniscus deformation and increases in effective viscosity; we also describe local models and effective values for these phenomena. The findings can be scaled to imbibition and two-phase flow in nanoporous media.