Capillary filling dynamics in closed-end carbon nanotubes—Defying the classical Lucas–Washburn paradigm

The emergence of two-dimensional (2D) materials such as carbon nanotubes (CNTs) offers the possibility of exploring new regimes of capillarity and wetting that remained inaccessible with traditional microfluidic and nanofluidic substrates. Here, we bring out the non-intuitive capillary filling regimes in closed-end CNTs using molecular-level investigations. Contrary to the existing understanding of the advancing liquid meniscus getting retarded by the viscous resistance offered by an entrapped vapor phase in a three-dimensional capillary, here the liquid meniscus is shown to accelerate toward the later stages of the dynamic wetting, which is attributed to the modified surface friction due to a 2D interface. This apparently counterintuitive observation is qualitatively linked to the local pressure fluctuations across the meniscus caused by the spontaneous bombardment of the entrapped vapor molecules, which may ramify into hitherto unexplored phenomena of a shape-reversed meniscus advancing in the 2-D pore. We further develop a simple analytical model to represent the essential physics of the resulting capillary filling dynamics, featuring significant deviations from the classical Lucas-Washburn paradigm. These results may turn out to be imperative in realizing new regimes of capillarity in 2D materials in multifarious applications, ranging from energy storage and water filtration to thin film flows in integrated electronics and photonic devices.