No Arabic abstract
When a drop of water is placed on a rough surface, there are two possible extreme regimes of wetting: the one called Cassie-Baxter (CB) with air pockets trapped underneath the droplet and the one characterized by the homogeneous wetting of the surface, called the Wenzel (W) state. A way to investigate the transition between these two states is by means of evaporation experiments, in which the droplet starts in a CB state and, as its volume decreases, penetrates the surfaces grooves, reaching a W state. Here we present a theoretical model based on the global interfacial energies for CB and W states that allows us to predict the thermodynamic wetting state of the droplet for a given volume and surface texture. We first analyze the influence of the surface geometric parameters on the droplets final wetting state with constant volume, and show that it depends strongly on the surface texture. We then vary the volume of the droplet keeping fixed the geometric surface parameters to mimic evaporation and show that the drop experiences a transition from the CB to the W state when its volume reduces, as observed in experiments. To investigate the dependency of the wetting state on the initial state of the droplet, we implement a cellular Potts model in three dimensions. Simulations show a very good agreement with theory when the initial state is W, but it disagrees when the droplet is initialized in a CB state, in accordance with previous observations which show that the CB state is metastable in many cases. Both simulations and theoretical model can be modified to study other types of surface.
We investigate the transition between the Cassie-Baxter and Wenzel states of a slowly evaporating, micron-scale drop on a superhydrophobic surface. In two dimensions analytical results show that there are two collapse mechanisms. For long posts the drop collapses when it is able to overcome the free energy barrier presented by the hydrophobic posts. For short posts, as the drop loses volume, its curvature increases allowing it to touch the surface below the posts. We emphasise the importance of the contact line retreating across the surface as the drop becomes smaller: this often preempts the collapse. In a quasi-three dimensional simulation we find similar behaviour, with the additional feature that the drop can de-pin from all but the peripheral posts, so that its base resembles an inverted bowl.
Self-cleaning surfaces often make use of superhydrophobic coatings that repel water. Here, we report a hydrophobic Si nanospring surface, that effectively suppresses wetting by repelling water droplets. We investigated the dynamic response of Si nanospring arrays fabricated by glancing angle deposition. The vertical standing nanospring arrays were approximately 250 nm tall and 60 nm apart, which allowed the droplets to rebound within a few milliseconds after contact. Amazingly, the morphology of the nanostructures influences the impact dynamics. The rebound time and coefficient of restitution were also found to be higher for Si nanosprings than vertical SI columns. It has been proposed that the restoring force of the Si nanosprings may be responsible for the water droplet rebound and can be explained by considering the droplet/nanospring surface as a coupled spring system. These nanospring surfaces may find applications in self-cleaning windows, liquid-repellent exteriors, glass panels of solar cells, and antifouling agents for roof tiling.
In this article we report the atypical and anomalous evaporation kinetics of saline sessile droplets on surfaces with elevated temperatures. In a previous we showed that saline sessile droplets evaporate faster compared to water droplets when the substrates are not heated. In the present study we discover that in the case of heated surfaces, the saline droplets evaporate slower than the water counterpart, thereby posing a counter-intuitive phenomenon. The reduction in the evaporation rates is directly dependent on the salt concentration and the surface wettability. Natural convection around the droplet and thermal modulation of surface tension is found to be inadequate to explain the mechanisms. Flow visualisations using particle image velocimetry PIV reveals that the morphed advection within the saline droplets is a probable reason behind the arrested evaporation. Infrared thermography is employed to map the thermal state of the droplets. A thermosolutal Marangoni based scaling analysis is put forward. It is observed that the Marangoni and internal advection borne of thermal and solutal gradients are competitive, thereby leading to the overall decay of internal circulation velocity, which reduces the evaporation rates. The theoretically obtained advection velocities conform to the experimental results. This study sheds rich insight on a novel yet anomalous species transport behaviour in saline droplets.
Contrasting with its sluggish behavior on standard solids, water is extremely mobile on superhydrophobic materials, as shown for instance by the continuous acceleration of drops on tilted water-repellent leaves. For much longer substrates, however, drops reach a terminal velocity that results from a balance between weight and friction, allowing us to question the nature of this friction. We report that the relationship between force and terminal velocity is non-linear. This is interpreted by showing that classical sources of friction are minimized, so that the aerodynamical resistance to motion becomes dominant, which eventually explains the matchless mobility of water. Our results are finally extended to viscous liquids, also known to be unusually quick on these materials.
Rough or textured hydrophobic surfaces are dubbed superhydrophobic due to their numerous desirable properties, such as water repellency and interfacial slip. Superhydrophobicity stems from an aversion for water to wet the surface texture, so that a water droplet in the superhydrophobic Cassie state, contacts only the tips of the rough hydrophobic surface. However, superhydrophobicity is remarkably fragile, and can break down due to the wetting of the surface texture to yield the Wenzel state under various conditions, such as elevated pressures or droplet impact. Moreover, due to large energetic barriers that impede the reverse (dewetting) transition, this breakdown in superhydrophobicity is widely believed to be irreversible. Using molecular simulations in conjunction with enhanced sampling techniques, here we show that on surfaces with nanoscale texture, water density fluctuations can lead to a reduction in the free energetic barriers to dewetting by circumventing the classical dewetting pathways. In particular, the fluctuation-mediated dewetting pathway involves a number of transitions between distinct dewetted morphologies, with each transition lowering the resistance to dewetting. Importantly, an understanding of the mechanistic pathways to dewetting and their dependence on pressure, allows us to augment the surface texture design, so that the barriers to dewetting are eliminated altogether and the Wenzel state becomes unstable at ambient conditions. Such robust surfaces, which defy classical expectations and can spontaneously recover their superhydrophobicity, could have widespread importance, from underwater operation to phase change heat transfer applications.