Nanoscale Contact Line Pinning Boosted by Ångström-Scale Surface Heterogeneity.

The pinning effect plays an important role in many fluidic systems but remains poorly understood, especially at the nanoscale. In this study, we measured the contact angles of glycerol nanodroplets on three different substrates using atomic force microscopy. By comparison of the shapes of the three-dimensional images of droplets, we found that a possible origin of the long-discussed deviation of the contact angles of nanodroplets from the macroscopic value is the pinning force induced by ångström-scale surface heterogeneity. It was also revealed that the pinning forces acting on glycerol nanodroplets on a silicon dioxide surface are up to twice as large as those acting on macroscale droplets. On a substrate where the effect of pinning was strong, an unexpected irreversible change from an irregularly shaped droplet to an atomically flat liquid film occurred. This was explained by the transition of the dominant force from liquid/gas interfacial tension to an adsorption force.

Random but limited pressure of graphene liquid cells.

Even though many researchers have used graphene liquid cells for atomic-resolution observation of liquid samples in the last decade, no one has yet simultaneously measured their three-dimensional shape and pressure. In this study, we have done so with an atomic force microscope, for cells with base radii of 20-134 nm and height of 3.9-21.2 nm. Their inner pressure ranged from 1.0 to 63 MPa but the maximum value decreased as the base radius increased. We discuss the mechanism that results in this inverse relationship by introducing an adhesive force between the graphene membranes. Also, the sample preparation procedure used in this experiment is highly reproducible and transferable to a wide variety of substrates.

Quantifying interfacial tensions of surface nanobubbles: How far can Young's equation explain?

Nanobubbles at solid-liquid interfaces play a key role in various physicochemical phenomena and it is crucial to understand their unique properties. However, little is known about their interfacial tensions due to the lack of reliable calculation methods. Based on mechanical and thermodynamic insights, we quantified for the first time the liquid-gas, solid-liquid, and solid-gas interfacial tensions of submicron-sized nitrogen bubbles at graphite-water interfaces using molecular dynamics (MD) analysis. It was revealed that Young's equation holds even for nanobubbles with different radii. We found that the liquid-gas and solid-liquid interfacial tensions were not largely affected by the gas density inside the nanobubbles. In contrast, the size effect on the solid-gas interfacial tension was observed, namely, the value dramatically decreased upon an increase in the gas density due to gas adsorption on the solid surface. However, our quantitative evaluation also revealed that the gas density effect on the contact angles is negligible when the footprint radius is larger than 50 nm, which is a typical range observed in experiments, and thus the flat shape and stabilization of submicron-sized surface bubbles observed in experiments cannot be explained only by the changes in interfacial tensions due to the van der Waals interaction-induced gas adsorption, namely by Young's equation without introducing the pinning effect. Based on our analysis, it was clarified that additional factors such as the differences in the studied systems are needed to explain the unresolved open issues - a satisfactory explanation for the nanobubbles in MD simulations being ultradense, non-flat, and stable without pinning.

Pinning in a Contact and Noncontact Manner: Direct Observation of a Three-Phase Contact Line Using Graphene Liquid Cells.

Pinning of a three-phase contact line at the nanoscale cannot be explained by conventional macroscale theories and thus requires an experimental insight to understand this phenomenon. We performed in-situ transmission electron microscopy observation of the three-phase contact lines of bubbles inside graphene liquid cells to experimentally investigate the causes of nanoscale pinning. In our observations, the three-phase contact line was not affected by the 0.6 nm-thick inhomogeneity of the graphene surface, but thicker metal nanoparticles with diameters of 2-10 nm and nanoflakes caused pinning of the gas-liquid interface. Notably, we found that flake-like objects can cause pinning that prevents the bubble overcome the flake object in a noncontact state, with a 2 nm-thick liquid film between them and the bubble. This phenomenon can be explained by the repulsive force obtained using the Derjaguin, Landau, Verwey, and Overbeek theory. We also observed that the flake temporally prevented the gas-liquid interface moving away from the flake. We discussed the physical mechanism of the attractive force-like phenomenon by considering the nanoconfinement effect of the liquid sandwiched by two graphene sheets and the hydration layer formed near the solid surface.

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.

Reflected Laser Interferometry: A Versatile Tool to Probe Condensation of Low-Surface-Tension Droplets.

Experimental investigation of dropwise condensation of low-surface-tension liquids remains prone to error owing to the imaging difficulties caused by the typically low droplet height. Using reflection interference contrast microscopy in confocal mode, we demonstrate a noninvasive framework to accurately capture this condensation dynamics of volatile liquids with low surface tension. The capability of the developed framework is demonstrated in studying the condensation dynamics of acetone, where it accurately describes the growth mechanism of condensed microdroplets with excellent spatiotemporal resolution even for submicron-range drop height and a three-phase contact angle of <5°. From experimentally obtained interferograms, the framework can reconstruct three-dimensional topography of the microdroplets even when the contact line of the droplet is distorted due to strong local pinning. The obtained results exhibit excellent quantitative agreement with several theoretically predicted trends. The proposed protocol overcomes the limitation of conventional techniques (e.g., optical imaging/environmental scanning electron microscopy) and provides an efficient alternative for studying the condensation of low-surface-tension liquids under atmospheric conditions.

Gas molecules sandwiched in hydration layers at graphite/water interfaces.

Hydration structures are ubiquitous at solid/liquid interfaces and play a key role in various physicochemical and biological phenomena. Recently, it has been reported that dissolved gas molecules attracted to hydrophobic surfaces form adsorbed gas layers. Although a hydration structure and adsorbed gas layers coexist on the surface, the relationships between them remain unknown. In this study, we investigated a highly ordered pyrolytic graphite/pure water interface with and without adsorbed gas layers using frequency-modulation atomic force microscopy. We penetrated the adsorbed gas layers with the strong load force of the AFM tip and thereby obtained the frequency shift curves inside them. By comparing the curves with those measured on a bare HOPG surface, we found that the adsorbed gas layers were located at regions where the molecular density of water was low and were sandwiched between hydration layers with high water density. Moreover, the distance between adjacent hydration layers was larger than that predicted by simulations and was the same with and without the adsorbed gas layers. We propose that gas molecules on the hydrophobic surface interact with the hydration structure before forming the adsorbed gas layers, and extend the distance between hydration layers.

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.

Precursor-Film-Mediated Thermocapillary Motion of Low-Surface-Tension Microdroplets.

In contrast to microdroplet condensation with high contact angles, the one with low contact angles remains unclear. In this study, we investigated dynamics of microdroplet condensation of low-surface-tension liquids on two flat substrate surfaces by using reflection interference confocal microscopy. Spontaneous migration toward relatively larger droplets was first observed for the microdroplets nucleated on the hydrophilic quartz surface. The moving microdroplets showed a contact angle hysteresis of ∼0.5°, which is much lower than the values observed on typical flat substrates and is within the range observed on slippery lubricant-infused porous surfaces. Because the microdroplets on the hydrophobic polydimethylsiloxane surface did not move, we concluded that the ultrathin precursor film is formed only on the hydrophilic surface, which reduces a resistive force to migration. Also, reduced size of droplets promotes the thermocapillary motion, which is induced by a gradient in local temperature inside a small microdroplet arising due to the difference in size of adjacent droplets.

Zigzag gas phases on holey adsorbed layers.

We report for the first time a zigzag-shaped gas phase at a highly-ordered pyrolytic graphite/water interface. The novel shape of the gaseous domain is triggered by the holes of the underlying solid-like layers, which are composed of air molecules. Specifically, many holes were created by heating in the thin solid-like layers, which roughened them. The gas domains that formed on these layers deformed from circular to zigzag-shaped as the contact lines expanded while avoiding the holes of the underlying layers. We explained the formation and growth processes of these gas structures in terms of thin film growth, which varies with the mobility of the constituent molecules.

Nanoscale pinning effect evaluated from deformed nanobubbles.

Classical thermodynamics theory predicts that nanosized bubbles should disappear in a few hundred microseconds. The surprisingly long lifetime and stability of nanobubbles are therefore interesting research subjects. It has been proposed that the stability of nanobubbles arises through pinning of the three-phase contact line, which results from intrinsic nanoscale geometrical and chemical heterogeneities of the substrate. However, a definitive explanation of nanobubble stability is still lacking. In this work, we examined the stability mechanism by introducing a "pinning force." We investigated nanobubbles at a highly ordered pyrolytic graphite/pure water interface by peak force quantitative nano-mechanical mapping and estimated the pinning force and determined its maximum value. We then observed the shape of shrinking nanobubbles. Because the diameter of the shrinking nanobubbles was pinned, the height decreased and the contact angle increased. This phenomenon implies that the stability results from the pinning force, which flattens the bubble through the pinned three-phase contact line and prevents the Laplace pressure from increasing. The pinning force can also explain the metastability of coalesced nanobubbles, which have two semispherical parts that are joined to form a dumbbell-like shape. The pinning force of the semispherical parts was stronger than that of the joint region. This result demonstrates that the contact line of the semispherical parts is pinned strongly to keep the dumbbell-like shape. Furthermore, we proposed a nanobubble generation mechanism for the solvent-exchange method and explained why the pinning force of large nanobubbles was not initially at its maximum value, as it was for small nanobubbles.