The stability and growth or dissolution of a single surface nanobubble on a chemically patterned surface are studied by molecular dynamics simulations of binary mixtures consisting of Lennard-Jones (LJ) particles. Our simulations reveal how pinning of the three-phase contact line on the surface can lead to the stability of the surface nanobubble, provided that the concentration of the dissolved gas is oversaturated. We have performed equilibrium simulations of surface nanobubbles at different gas oversaturation levels ζ > 0. The equilibrium contact angle θ is found to follow the theoretical result of Lohse and Zhang (Phys. Rev. E 2015, 91, 031003(R)), namely, sin θ = ζL/L, where L is the pinned length of the footprint and L = 4γ/P is a capillary length scale, where γ is the surface tension and P is the ambient pressure. For undersaturation ζ < 0 the surface nanobubble dissolves and the dissolution dynamics shows a "stick-jump" behavior of the three-phase contact line.

The stability of two neighboring surface nanobubbles on a chemically heterogeneous surface is studied by molecular dynamics (MD) simulations of binary mixtures consisting of Lennard-Jones (LJ) particles. A diffusion equation-based stability analysis suggests that two nanobubbles sitting next to each other remain stable, provided the contact line is pinned, and that their radii of curvature are equal. However, many experimental observations seem to suggest some long-term kind of ripening or shrinking of the surface nanobubbles. In our MD simulations we find that the growth/dissolution of the nanobubbles can occur due to the transfer of gas particles from one nanobubble to another along the solid substrate. That is, if the interaction between the gas and the solid is strong enough, the solid–liquid interface can allow for the existence of a “tunnel” which connects the liquid–gas interfaces of the two nanobubbles to destabilize the system. The crucial role of the gas–solid interaction energy is a nanoscopic element that hitherto has not been considered in any macroscopic theory of surface nanobubbles and may help to explain experimental observations of the long-term ripening.

We study the formation of a nanobubble around a heated nanoparticle in a bulk liquid by using molecular dynamics simulations. The nanoparticle is kept at a temperature above the critical temperature of the surrounding liquid, leading to the formation of a vapor nanobubble attached to it. First, we study the role of both the temperature of the bulk liquid far away from the nanoparticle surface and the temperature of the nanoparticle itself on the formation of a stable vapor nanobubble. We determine the exact conditions under which it can be formed and compare this with the conditions that follow from a macroscopic heat balance argument. Next, we demonstrate the role of dissolved gas on the conditions required for nucleation of a nanobubble and on its growth dynamics. We find that beyond a certain threshold concentration, the dissolved gas dramatically facilitates vapor bubble nucleation due to the formation of gaseous weak spots in the surrounding liquid.

We study the nucleation and growth of a nanobubble on rough surfaces using molecular dynamics simulations. A nanobubble nucleates and grows by virtue of a heterogeneous surface reaction which results in the production of gas molecules near the surface. We study the role of surface roughness in the nucleation and growth behavior of a nanobubble. We perform simulations at various reaction rates and surface morphology and quantified the growth dynamics of a nanobubble. Our simulations show that after the onset of nucleation, the nanobubble grows rapidly with radius following t 1/3 behavior followed by a diffusive growth regime which is marked by t 1/2 growth behavior. This growth behavior remains independent of surface roughness and reaction rates over the range considered in this study. We also quantified the oversaturation of gas required for nucleation of a nanobubble and demonstrated its dependence on the surface morphology.

Surface nanodroplets are important units for lab-on-a-chip devices, compartmentalised catalytic reactions, high-resolution near-field imaging, and many others. Solvent exchange is a simple solution-based bottom-up approach for producing surface nanodroplets by displacing a good solvent of the droplet liquid by a poor one in a narrow channel in the laminar regime. The droplet size is controlled by the solution composition and the flow conditions during the solvent exchange. In this paper, we investigated the effects of local microfluidic structures on the formation of surface nanodroplets. The microstructures consist of a microgap with a well-defined geometry, embedded on the opposite microchannel wall, facing the substrate where nucleation takes place. For a given channel height, the dimensionless control parameters were the Peclet number of the flow, the ratio between the gap height and the channel height, and the aspect ratio between the gap length and the channel height. We found and explained three prominent features in the surface nanodroplet distribution at the surface opposite to the microgap: (i) enhanced volume of the droplets; (ii) asymmetry as compared to the location of the gap in the spatial droplet distribution with increasing Pe; (iii) reduced exponent of the effective scaling law of the droplet size with Pe. The droplet size also varied with the aspect and height ratios of the microgap at a given Pe value. Our simulations of the profile of oversaturation in the channel reveal that the droplet size distribution may be attributed to the local flow patterns induced by the gap. Finally, in a tapered microchannel, a gradient of surface nanodroplet size was obtained. Our work shows the potential for controlling nanodroplet size and spatial organization on a homogeneous surface in a bottom-up approach by simple microfluidic structures.

In this paper we study the formation of nanodrops on curved surfaces (both convex and concave) by means of molecular dynamics simulations, where the particles interact via a Lennard-Jones potential. We find that the contact angle is not affected by the curvature of the substrate, in agreement with previous experimental findings. This means that the change in curvature of the drop in response to the change in curvature of the substrate can be predicted from simple geometrical considerations, under the assumption that the drop's shape is a spherical cap, and that the volume remains unchanged through the curvature. The resulting prediction is in perfect agreement with the simulation results, for both convex and concave substrates. In addition, we calculate the line tension, namely by fitting the contact angle for different size drops to the modified Young equation. We find that the line tension for concave surfaces is larger than for convex surfaces, while for zero curvature it has a clear maximum. This feature is found to be correlated with the number of particles in the first layer of the liquid on the surface. * d.lohse@utwente.nl

The dissolution of a multicomponent nanodrop in a sparingly miscible liquid is studied by molecular dynamics (MD) simulations. We studied both binary and ternary systems, in which nanodroplets are formed from one and two components, respectively. Whereas for a single-component droplet the dissolution can easily be calculated, the situation is more complicated for a multicomponent drop, as the interface concentrations of the drop constituents depend on the drop composition, which changes with time. In this study, the variation of the interface concentration with the drop composition is determined from independent 'numerical experiments', which are then used in the theoretical model for the dissolution dynamics of a multicomponent drop. The MD simulations reveal that when the interaction strengths between the drop constituents and the surrounding bulk liquid are significantly different, the concentration of the more soluble component near the drop interface may become larger than in the drop bulk. This effect is the larger the smaller the drop radius. While the present study is limited to binary and ternary systems, the same method can be easily extended to a larger number of components.

Surface droplets in the microscale are of great interest for their relevance in broad droplet-based technologies. Derived from the Ouzo effect, the solvent exchange process is a simple bottom-up approach to produce surface nano-/micro-droplets by the nucleation and growth mechanism. The oil oversaturation pulse is created as a good solvent (ethanol) for the oil displaced by a poor solvent (water) in the flow cell. In this work, we investigated the formation of surface droplets on a one-dimensional substrate (a single hydrophobic fiber with a diameter of 10 μm) in a flow. The droplet growth on the microfiber is enhanced as the fiber is perpendicular to the external flow direction, due to the coupled effects between the droplet formation and the local flow. On the other hand, the droplet growth exhibits different growth dynamics when the fiber is placed parallel to the external flow direction. The general trend that surface droplets grow faster on a fiber at higher flow rates is consistent with the situation on planar substrates. The coupled interactions between the growing droplets and the local flow conditions during the solvent exchange process were further revealed in the simulations. The findings from this work will be valuable for the design and utilization of the solvent exchange process to produce surface nanodroplets on a microfiber under flow conditions and thus broaden the droplet-based application fields.