Observation of Interfacial Instability of an Ultrathin Water Film.

We observed the instability of a few-nanometer-thick water film encapsulated inside a graphene nanoscroll using transmission electron microscopy. The film, that was left after recession of a meniscus, formed ripples along the length of the nanoscroll with a distance only 20%-44% of that predicted by the classical Plateau-Rayleigh instability theory. The results were explained by a theoretical analysis that incorporates the effect of the van der Waals interactions between the water film and the graphene layers. We derived important insights into the behavior of liquid under nanoscale confinement and in nanofluidic systems.

Mechanistic Insights into Nanobubble Merging Studied Using In Situ Liquid-Phase Electron Microscopy.

Nanobubbles have attracted great interest in recent times because of their application in water treatment, surface cleaning, and targeted drug delivery, yet the challenge remains to gain thorough understanding of their unique behavior and dynamics for their utilization in numerous potential applications. In this work, we have used a liquid-phase electron microscopy technique to gain insights into the quasistatic merging of surface nanobubbles. The electron beam environment was controlled in order to suppress any new nucleation and slow down the merging process. The transmission electron microscopy study reveals that merging of closely positioned surface nanobubbles is initiated by gradual localized changes in the physical properties of the region between the adjoining nanobubble boundary. The observed phenomenon is then analyzed and discussed based on the different perceptions: localized liquid density gradient and bridge formation for gas exchange. In this study, it is estimated that the merging of the stable nanobubbles is initiated by the formation of a thin gas layer. This work not only enhances our understanding of the merging process of stable surface nanobubbles but will also lead to exploration of new domains for nanobubble applications.

Dynamic interplay between interfacial nanobubbles: oversaturation promotes anisotropic depinning and bubble coalescence.

Probing the dynamics of nanobubbles is essential to understand their longevity and behavior. Importantly, such an observation requires tools and techniques having high temporal resolutions to capture the intrinsic characteristics of the nanobubbles. In this work, we have used the in situ liquid-phase electron microscopy (LPEM) technique to gain insights into nanobubbles' behavior and their interfacial dynamics. Interestingly, we could observe a freely growing-shrinking nanobubble and a pinned nanobubble under the same experimental conditions, suggesting the possibility of multiple nanobubble stabilization theories and pathways. Remarkably, the study reveals that a freely growing-shrinking nanobubble induces anisotropic depinning in the three-phase contact line of a strongly pinned neighboring nanobubble. The anisotropic depinning is attributed to the differential local gas saturation levels, depending on the relative positioning of the freely growing-shrinking nanobubble. Furthermore, we also observed a unique pull-push phenomenon exhibited by the nanobubble's interfaces, which is attributed to the van der Waals interactions and the electric double layer collectively. The role of the electric double layer in suppressing and delaying the merging is also highlighted in this study. The present work aims to reveal the role of locally varying gas saturation in the depinning of nanobubbles, their longevity due to the electric double layer, and the consequent coalescence, which is crucial to understand the behavior of the nanobubbles. Our findings will essentially contribute to the understanding of these novel nanoscale gaseous domains and their dynamics.

Superstable Ultrathin Water Film Confined in a Hydrophilized Carbon Nanotube.

Fluids confined in a nanoscale space behave differently than in the bulk due to strong interactions between fluid molecules and solid atoms. Here, we observed water confined inside "open" hydrophilized carbon nanotubes (CNT), with diameter of tens of nanometers, using transmission electron microscopy (TEM). A 1-7 nm water film adhering to most of the inner wall surface was observed and remained stable in the high vacuum (order of 10-5 Pa) of the TEM. The superstability of this film was attributed to a combination of curvature, nanoroughness, and confinement resulting in a lower vapor pressure for water and hence inhibiting its vaporization. Occasional, suspended ultrathin water film with thickness of 3-20 nm were found and remained stable inside the CNT. This film thickness is 1 order of magnitude smaller than the critical film thickness (about 40 nm) reported by the Derjaguin-Landau-Verwey-Overbeek theory and previous experimental investigations. The stability of the suspended ultrathin water film is attributed to the additional molecular interactions due to the extended water meniscus, which balances the rest of the disjoining pressures.

Nanoscale Bubble Dynamics Induced by Damage of Graphene Liquid Cells.

Graphene liquid cells provide the highest possible spatial resolution for liquid-phase transmission electron microscopy. Here, in graphene liquid cells (GLCs), we studied the nanoscale dynamics of bubbles induced by controllable damage in graphene. The extent of damage depended on the electron dose rate and the presence of bubbles in the cell. After graphene was damaged, air leaked from the bubbles into the water. We also observed the unexpected directional nucleation of new bubbles, which is beyond the explanation of conventional diffusion theory. We attributed this to the effect of nanoscale confinement. These findings provide new insights into complex fluid phenomena under nanoscale confinement.

Water Confined in Hydrophobic Cup-Stacked Carbon Nanotubes beyond Surface-Tension Dominance.

Water confined in carbon nanotubes (CNTs) can exhibit distinctly different behaviors from the bulk. We report transmission electron microscopy (TEM) observation of water phases inside hydrophobic cup-stacked CNTs exposed to high vacuum. Unexpectedly, we observed stable water morphologies beyond surface-tension dominance, including nanometer thin free water films, complex water-bubble structures, and zigzag-shaped liquid-gas interface. The menisci of the water phases are complex and inflected, where we measured the contact angles on the CNT inner wall to be 68-104°. The superstability of the suspended ultrathin water films is attributed to the strong hydrogen-bonded network among water molecules and adsorption of water molecules on the cup-structured inner wall. The complex water-bubble structure is a result of the stability of free water films and interfacial nanobubbles, and the zigzag edge of the liquid-gas interface is explained by the pinning effect. These experimental findings provide valuable knowledge for the research on fluids under nanoscale confinement.