Induced detachment of coalescing droplets on superhydrophobic surfaces

Coalescence of a falling droplet with a stationary sessile droplet on a superhydrophobic surface is investigated by a combined experimental and numerical study. In the experiments, the droplet diameter, the impact velocity, and the distance between the impacting droplets were controlled. The evolution of surface shape during the coalescence of two droplets on the superhydrophobic surface is captured using high speed imaging and compared with numerical results. A two-phase volume of fluid (VOF) method is used to determine the dynamics of droplet coalescence, shape evaluation, and contact line movement. The spread length of two coalesced droplets along their original center is also predicted by the model and compared well with the experimental results. The effect of different parameters such as impact velocity, center to center distance, and droplet size on contact time and restitution coefficient are studied and compared to the experimental results. Finally, the wetting and the self-cleaning properties of superhydrophobic surfaces have been investigated. It has been found that impinging water drops with very small amount of kinetic impact energy were able to thoroughly clean these surfaces.     

Condensation and freezing of droplets on superhydrophobic surfaces

Superhydrophobic coatings are reported as promising candidates for anti-icing applications. Various studies have shown that as well as having ultra water repellency the surfaces have reduced ice adhesion and can delay water freezing. However, the structure or texture (roughness) of the superhydrophobic surface is subject to degradation during the thermocycling or wetting process. This degradation can impair the superhydrophobicity and the icephobicity of those coatings. In this review, a brief overview of the process of droplet freezing on superhydrophobic coatings is presented with respect to their potential in anti-icing applications. To support this discussion, new data is presented about the condensation of water onto physically decorated substrates, and the associated freezing process which impacts on the freezing of macroscopic droplets on the surface.     

Modeling droplets on superhydrophobic surfaces: equilibrium states and transitions

We present a lattice Boltzmann solution of the equations of motion describing the spreading of droplets on topologically patterned substrates. We apply it to model superhydrophobic behavior on surfaces covered by an array of micrometer-scale posts. We find that the patterning results in a substantial increase in contact angle, from 110 degrees to 156 degrees. The dynamics of the transition from drops suspended on top of the posts to drops collapsed in the grooves is described.     

Dynamic behavior of water droplets on solid surfaces with pillar-type nanostructures

In the present study, we investigated the static and dynamic behavior of water droplets on solid surfaces featuring pillar-type nanostructures by using molecular dynamics simulations. We carried out the computation in two stages. As a result of the first computational stage, an initial water cube reached an equilibrium state at which the water droplet showed different shapes depending on the height and the lateral and gap dimensions of the pillars. In the second computational stage, we applied a constant body force to the static water droplet obtained from the first computational stage and evaluated the dynamic behavior of the water droplet as it slid along the pillar-type surface. The dynamic behavior of the water droplet, which could be classified into three different groups, depended on the static state of the water droplet, the pillar characteristics (e.g., height and the lateral and gap dimensions of the pillars), and the magnitude of the applied body force. We obtained the advancing and receding contact angles and the corresponding contact angle hysteresis of the water droplets, which helped classify the water droplets into the three different groups.     

Impact of picoliter droplets on superhydrophobic surfaces with ultralow spreading ratios

The impact of picoliter-sized water droplets on superhydrophobic CF(4) plasma fluorinated polybutadiene surfaces is investigated with high-speed imaging. Variation of the surface topography by plasmachemical modification enables the dynamics of wetting to be precisely controlled. Final spreading ratios as low as 0.63 can be achieved. A comparison of the maximum spreading ratio and droplet oscillation frequencies to models described in the literature shows that both are found to be much lower than theoretically predicted.     

Evaporation of water droplets on polymer surfaces

The evaporation of water droplets on polymer surfaces was investigated by using a digital image analysis technique. There were three distinct stages in the water evaporation process: a constant contact area mode, a constant contact angle mode, and a mixed mode that is independent of both the initial quantity of water droplets and the hydrophobic properties of the polymer surfaces. The physical factors influencing the first and second transitions in the evaporation process were found to be the attainment of the receding angle on the polymer surfaces and the Marangoni instability in the evaporating water droplets, which result from the concentration gradient of contaminants. This study also provides qualitative information about the microfluid flows inside the evaporating water droplets and the morphology of drying stains on polymer surfaces. The contaminants were found to be concentrated at the perimeter of the stains, in agreement with the observed outward microfluid flow in the mixed mode of the evaporation process.     

Microdroplet growth mechanism during water condensation on superhydrophobic surfaces

By promoting dropwise condensation of water, nanostructured superhydrophobic coatings have the potential to dramatically increase the heat transfer rate during this phase change process. As a consequence, these coatings may be a facile method of enhancing the efficiency of power generation and water desalination systems. However, the microdroplet growth mechanism on surfaces which evince superhydrophobic characteristics during condensation is not well understood. In this work, the sub-10 μm dynamics of droplet formation on nanostructured superhydrophobic surfaces are studied experimentally and theoretically. A quantitative model for droplet growth in the constant base (CB) area mode is developed. The model is validated using optimized environmental scanning electron microscopy (ESEM) imaging of microdroplet growth on a superhydrophobic surface consisting of immobilized alumina nanoparticles modified with a hydrophobic promoter. The optimized ESEM imaging procedure increases the image acquisition rate by a factor of 10-50 as compared to previous research. With the improved imaging temporal resolution, it is demonstrated that nucleating nanodroplets coalesce to create a wetted flat spot with a diameter of a few micrometers from which the microdroplet emerges in purely CB mode. After the droplet reaches a contact angle of 130-150°, its base diameter increases in a discrete steplike fashion. The droplet height does not change appreciably during this steplike base diameter increase, leading to a small decrease of the contact angle. Subsequently, the drop grows in CB mode until it again reaches the maximum contact angle and increases its base diameter in a steplike fashion. This microscopic stick-and-slip motion can occur up to four times prior to the droplet coalescence with neighboring drops. Lastly, the constant contact angle (CCA) and the CB growth models are used to show that modeling formation of a droplet with a 150° contact angle in the CCA mode rather than in the CB mode severely underpredicts both the drop formation time and the average heat transfer rate through the drop.     

Molecular dynamics simulations of water droplets on polymer surfaces

Molecular dynamics simulations were used to study the wetting of polymer surfaces with water. Contact angles of water droplets on crystalline and two amorphous polyethylene (PE) and poly(vinyl chloride) (PVC) surfaces were extracted from atomistic simulations. Crystalline surfaces were produced by duplicating the unit cell of an experimental crystal structure, and amorphous surfaces by pressing the bulk polymer step by step at elevated temperature between two repulsive grid surfaces to a target density. Different-sized water droplets on the crystalline PE surface revealed a slightly positive line tension on the order of 10(-12)-10(-11) N, whereas droplets on crystalline PVC did not yield a definite line tension. Microscopic contact angles produced by the simple point charge (SPC) water model were mostly a few degrees smaller than those produced by the extended SPC model, which, as the model with lowest bulk energy, presents an upper boundary for contact angles. The macroscopic contact angle for the SPC model was 94 degrees on crystalline PVC and 113 degrees on crystalline PE. Amorphicity of the surface increased the water contact angle on PE but decreased it on PVC, for both water models. If the simulated contact angles on crystalline and amorphous surfaces are combined in proportion to the crystallinity of the polymer in question, simulated values in relatively good agreement with measured values are obtained.     

Nanostructures increase water droplet adhesion on hierarchically rough superhydrophobic surfaces

Hierarchical roughness is known to effectively reduce the liquid-solid contact area and water droplet adhesion on superhydrophobic surfaces, which can be seen for example in the combination of submicrometer and micrometer scale structures on the lotus leaf. The submicrometer scale fine structures, which are often referred to as nanostructures in the literature, have an important role in the phenomenon of superhydrophobicity and low water droplet adhesion. Although the fine structures are generally termed as nanostructures, their actual dimensions are often at the submicrometer scale of hundreds of nanometers. Here we demonstrate that small nanometric structures can have very different effect on surface wetting compared to the large submicrometer scale structures. Hierarchically rough superhydrophobic TiO(2) nanoparticle surfaces generated by the liquid flame spray (LFS) on board and paper substrates revealed that the nanoscale surface structures have the opposite effect on the droplet adhesion compared to the larger submicrometer and micrometer scale structures. Variation in the hierarchical structure of the nanoparticle surfaces contributed to varying droplet adhesion between the high- and low-adhesive superhydrophobic states. Nanoscale structures did not contribute to superhydrophobicity, and there was no evidence of the formation of the liquid-solid-air composite interface around the nanostructures. Therefore, larger submicrometer and micrometer scale structures were needed to decrease the liquid-solid contact area and to cause the superhydrophobicity. Our study suggests that a drastic wetting transition occurs on superhydrophobic surfaces at the nanometre scale; i.e., the transition between the Cassie-Baxter and Wenzel wetting states will occur as the liquid-solid-air composite interface collapses around nanoscale structures. Consequently, water adheres tightly to the surface by penetrating into the nanostructure. The droplet adhesion mechanism presented in this paper gives valuable insight into a phenomenon of simultaneous superhydrophobicity and high water droplet adhesion and contributes to a more detailed comprehension of superhydrophobicity overall.     

Extreme resistance of superhydrophobic surfaces to impalement: reversible electrowetting related to the impacting/bouncing drop test

The paper reports on the comparison of the wetting properties of superhydrophobic silicon nanowires (NWs), using drop impact impalement and electrowetting (EW) experiments. A correlation between the resistance to impalement on both EW and drop impact is shown. From the results, it is evident that when increasing the length and density of NWs (i) the thresholds for drop impact and EW irreversibility increase and (ii) the contact-angle hysteresis after impalement decreases. This suggests that the structure of the NW network could allow for partial impalement, hence preserving the reversibility, and that EW acts the same way as an external pressure. The most robust of our surfaces shows a threshold to impalement higher than 35 kPa, while most of the superhydrophobic surfaces tested so far have impalement thresholds smaller than 10 kPa.     

Wetting of structured hydrophobic surfaces by water droplets

Super-hydrophobic surfaces may arise due to an interplay between the intrinsic, relatively high, contact angle of the more or less hydrophobic solid surface employed and the geometric features of the solid surface. In the present work, this relationship was investigated for a range of different surface geometries, making use of surface free energy minimization. As a rule, the free energy minima (and maxima) occur when the Laplace and Young conditions are simultaneously fulfilled. Special effort has been devoted to investigating the free energy barriers present between the Cassie-Baxter (heterogeneous wetting) and Wenzel (homogeneous wetting) modes. The predictions made on the basis of the model calculations compare favorably with experimental results presented in the literature.     

Mass-producible superhydrophobic surfaces

Mass-producible superhydrophobic surfaces with remarkably identical appearance and efficiency through a mold fabrication and hot embossing process are reported.     

Shape-gradient composite surfaces: water droplets move uphill

The approach of water droplets self-running horizontally and uphill without any other forces was proposed by patterning the shape-gradient hydrophilic material (i.e., mica) to the hydrophobic matrix (i.e., wax or low-density polyethylene (LDPE)). The shape-gradient composite surface is the best one to drive water droplet self-running both at the high velocity and the maximal distance among four different geometrical mica/wax composite surfaces. The driving force for the water droplets self-running includes: (1) the great difference in wettability of surface materials, (2) the low contact angle hysteresis of surface materials, and (3) the space limitation of the shape-gradient transportation area. Furthermore, the average velocity and the maximal distance of the self-running were mainly determined by the gradient angle (alpha), the droplet volume, and the difference of the contact angle hysteresis. Theoretical analysis is in agreement with the experimental results.     

Investigating the interface of superhydrophobic surfaces in contact with water

Neutron reflectivity (NR) is used to probe the solid, liquid, vapor interface of a porous superhydrophobic (SH) surface submerged in water. A low-temperature, low-pressure technique was used to prepare a rough, highly porous organosilica aerogel-like film. UV/ozone treatments were used to control the surface coverage of hydrophobic organic ligands on the silica framework, allowing the contact angle with water to be continuously varied over the range of 160 degrees (superhydrophobic) to <10 degrees (hydrophilic). NR shows that the superhydrophobic nature of the surface prevents infiltration of water into the porous film. Atomic force microscopy and density functional theory simulations are used in combination to interpret the NR results and help establish the location, width, and nature of the SH film-water interface.     

Sliding of water droplets on hydrophobic surfaces with various hydrophilic region sizes

Four patterned surfaces with hydrophilic areas of different sizes were prepared using photolithography with a smooth octadecyltrimethoxysilane (ODS) hydrophobic coating. The hydrophilic area in the surfaces was aligned hexagonally with a constant area fraction. The sliding angle and contact angle hysteresis of the water droplets increased concomitantly with increasing pattern size. The increase of the contact line distortion between defects at the receding side plays an important role in this trend. The droplet sliding velocity also increased concomitantly with increasing pattern size. This trend was simulated by a simple flow model. The contribution of the interface between the ODS region and the hydrophilic area was deduced from this trend. This study demonstrated the different size dependency of the chemical surface defects for sliding behavior between the critical moment at which a droplet slides down and the period when a droplet is sliding.     

Modeling receding contact lines on superhydrophobic surfaces

We use mesoscale simulations to study the depinning of a receding contact line on a superhydrophobic surface patterned by a regular array of posts. For the simulations to be feasible, we introduce a novel geometry where a column of liquid dewets a capillary bounded by a superhydrophobic plane that faces a smooth hydrophilic wall of variable contact angle. We present results for the dependence of the depinning angle on the shape and spacing of the posts and discuss the form of the meniscus at depinning. We find, in agreement with ref 17 , that the local post concentration is a primary factor in controlling the depinning angle and show that the numerical results agree well with recent experiments. We also present two examples of metastable pinned configurations where the posts are partially wet.     

Laser-induced nanoscale superhydrophobic structures on metal surfaces

The combination of a dual-scale (nano and micro) roughness with an inherent low-surface energy coating material is an essential factor for the development of superhydrophobic surfaces. Ultrashort pulse laser (USPL) machining/structuring is a promising technique for obtaining the dual-scale roughness. Sheets of stainless steel (AISI 304 L SS) and Ti-6Al-4V alloys were laser-machined with ultraviolet laser pulses of 6.7 ps, with different numbers of pulses per irradiated area. The surface energy of the laser-machined samples was reduced via application of a layer of perfluorinated octyltrichlorosilane (FOTS). The influence of the number of pulses per irradiated area on the geometry of the nanostructure and the wetting properties of the laser-machined structures has been studied. The results show that with an increasing number of pulses per irradiated area, the nanoscale structures tend to become predominantly microscale. The top surface of the microscale structures is seen covered with nanoscale protrusions that are most pronounced in Ti-6Al-4V. The laser-machined Ti-6Al-4V surface attained superhydrophobicity, and the improvement in the contact angle was >27% when compared to that of a nontextured surface.