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Register a new userSpontaneous Recovery of Superhydrophobicity on Nanotextured Surfaces
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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.
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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.
Drops deposited on rough and hydrophobic surfaces can stay suspended with gas pockets underneath the liquid, then showing very low hydrodynamic resistance. When this superhydrophobic state breaks down, the subsequent wetting process can show different dynamical properties. A suitable choice of the geometry can make the wetting front propagate in a stepwise manner leading to {it square-shaped} wetted area: the front propagation is slow and the patterned surface fills by rows through a {it zipping} mechanism. The multiple time scale scenario of this wetting process is experimentally characterized and compared to numerical simulations.
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.
Liquid infused surfaces (LIS) exhibit unique properties that make them ideal candidates for a wide range of applications, from anti-fouling and anti-icing coatings to self-healing surfaces and controlled wetting. However, when exposed to realistic environmental conditions, LIS tend to age and progressively lose their desirable properties, potentially compromising their application. The associated ageing mechanisms are still poorly understood, and results reflecting real-life applications are scarce. Here we track the ageing of model LIS composed of glass surfaces functionalized with hydrophobic nanoparticles and infused with silicone oil. The LIS are fully submerged in aqueous solutions and exposed to acoustic pressure waves for set time intervals. The ageing is monitored by periodic measurements of the LIS wetting properties. We also track changes to the LIS nanoscale structure. We find that the LIS rapidly lose their slippery properties due to a combination of oil loss, smoothing of the nanoporous functional layer and substrate degradation when directly exposed to the solution. The oil loss is consistent with water microdroplets entering the oil layer and displacing oil away from the surface. These mechanisms are general and could play a role in the ageing of most LIS.
A simple model was constructed to describe the polar ordering of non-centrosymmetric supramolecular aggregates formed by self assembling triblock rodcoil polymers. The aggregates are modeled as dipoles in a lattice with an Ising-like penalty associated with reversing the orientation of nearest neighbor dipoles. The choice of the potentials is based on experimental results and structural features of the supramolecular objects. For films of finite thickness, we find a periodic structure along an arbitrary direction perpendicular to the substrate normal, where the repeat unit is composed of two equal width domains with dipole up and dipole down configuration. When a short range interaction between the surface and the dipoles is included the balance between the up and down dipole domains is broken. Our results suggest that due to surface effects, films of finite thickness have a none zero macroscopic polarization, and that the polarization per unit volume appears to be a function of film thickness.
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