Factors affecting the spontaneous motion of condensate drops on superhydrophobic copper surfaces

The coalescence-induced condensate drop motion on some superhydrophobic surfaces (SHSs) has attracted increasing attention because of its potential applications in sustained dropwise condensation, water collection, anti-icing, and anticorrosion. However, an investigation of the mechanism of such self-propelled motion including the factors for designing such SHSs is still limited. In this article, we fabricated a series of superhydrophobic copper surfaces with nanoribbon structures using wet chemical oxidation followed by fluorization treatment. We then systematically studied the influence of surface roughness and the chemical properties of as-prepared surfaces on the spontaneous motion of condensate drops. We quantified the "frequency" of the condensate drop motion based on microscopic sequential images and showed that the trend of this frequency varied with the nanoribbon structure and extent of fluorination. More obvious spontaneous condensate drop motion was observed on surfaces with a higher extent of fluorization and nanostructures possessing sufficiently narrow spacing and higher perpendicularity. We attribute this enhanced drop mobility to the stable Cassie state of condensate drops in the dynamic dropwise condensation process that is determined by the nanoscale morphology and local surface energy.     

Preparation of Cu-Coated Stainless Steel Surfaces for Superhydrophobic Investigation

Cu-coated stainless steel surfaces containing micro- and nanoscale binary structures with different surface roughness were successfully fabricated by means of a facile one-step electroless plating technology. The resulting surfaces were modified by the low free energy material HFTHTMS (HFTHTMS = (heptadecafluoro-1,1,2,2-tetrahydrodecyl) trimethoxysilane). The experimental results of wettability exhibit that such unmodified surfaces have a strong adhesive force to water droplets, and their contact angles increase with increasing surface roughness, whereas the modified surfaces by HFTHTMS show the superhydrophobic characteristic with contact angles higher than 150° and sliding angles lower than 5°.     

Preparation of Cu-Coated Stainless Steel Surfaces for Surperhydrophobic Investigation

Cu-coated stainless steel surfaces containing micro- and nanoscale binary structures having different surface roughness were successfully fabricated by means of a facile one-step electroless plating technology, and the resulting surfaces were modified by the low free energy material HFTHTMS (HFTHTMS = (heptadecafluoro-1,1,2,2-tetrahydrodecyl) trimethoxysilane). The experimental results of wettability exhibit that such unmodified surfaces have a strong adhesive force to water droplets, and their contact angles increase with increasing surface roughness, whereas the modified surfaces by HFTHTMS show the superhydrophobic characteristic with contact angles higher than 150° and sliding angles lower than 5°.     

Modeling contact angle hysteresis on chemically patterned and superhydrophobic surfaces

We investigate contact angle hysteresis on chemically patterned and superhydrophobic surfaces, as the drop volume is quasistatically increased and decreased. We consider both two (cylindrical drops) and three (spherical drops) dimensions using analytical and numerical approaches to minimize the free energy of the drop. In two dimensions, we find, in agreement with other authors, a slip, jump, stick motion of the contact line. In three dimensions, this behavior persists, but the position and magnitude of the contact line jumps are sensitive to the details of the surface patterning. In two dimensions, we identify analytically the advancing and receding contact angles on the different surfaces, and we use numerical insights to argue that these provide bounds for the three-dimensional cases. We present explicit simulations to show that a simple average over the disorder is not sufficient to predict the details of the contact angle hysteresis and to support an explanation for the low contact angle hysteresis of suspended drops on superhydrophobic surfaces.     

Formation of superhydrophobic surfaces by biomimetic silicification and fluorination

The amazing water repellency of many biological surfaces, exemplified by lotus leaves, has recently received a great deal of interest. These surfaces, called superhydrophobic surfaces, exhibit water contact angles larger than 150 degrees and a low contact angle hysteresis because of both their low surface energy and heterogeneously rough structures. In this paper, we suggest a biomimetic method, "biosilicification", for generating heterogeneously rough structures and fabricating superhydrophobic surfaces. The superhydrophobic surface was prepared by a combination of the formation of heterogeneously rough, nanosphere-like silica structures through biosilicification and the formation of self-assembled monolayers of fluorosilane on the surface. The resulting surface exhibited the water contact angle of 160.1 degrees and the very low water contact angle hysteresis of only 2.3 degrees, which are definite characteristics of superhydrophobic surfaces. The superhydrophobic property of our system probably resulted from the air trapped in the rough surface. The wetting behavior on the surface was in the heterogeneous regime, which was totally supported by Cassie-Baxter equation.     

Mimicking the lotus effect: influence of double roughness structures and slender pillars

Surface roughness is known to amplify hydrophobicity. The apparent contact angle of a drop on a rough surface is often modeled using either Wenzel's or Cassie's formulas. These formulas, along with an appropriate energy analysis, are critical in designing superhydrophobic substrates for applications in microscale devices. In this paper we propose that double (or multiple) roughness structures or slender pillars are appropriate surface geometries to develop "self-cleaning" surfaces. The key motivation behind the double structured roughness is to mimic the microstructure of superhydrophobic leaves (such as lotus). Theoretical analysis similar to that presented in the paper can be used to obtain optimal geometric parameters for the rough surface. The calculation procedure should result in surface geometries with excellent water repellent properties.     

Ratchetlike slip angle anisotropy on printed superhydrophobic surfaces

The fabrication and properties of superhydrophobic surfaces that exhibit ratchet-like anisotropic slip angle behavior is described. The surface is composed of arrays of poly(dimethylsiloxane) (PDMS) posts fabricated by a type of 3D printing. By controlling the dispense parameters, regular arrays of asymmetric posts were deposited such that the slope of the posts was varied from 0 to 50 relative to the surface normal. Advancing and receding contact angles as well as slip angles were measured as a function of the post slope and droplet volume. Ratchetlike slip angle anisotropy was observed on surfaces composed of sloped features. The maximum slip angle difference (for a 180° tilt angle variation) was 32° for 20 μL droplets on surfaces with posts fabricated with a slope of 50°. This slip angle anisotropy is attributed to an increase in the triple contact line (TCL) length as the droplet is tilted in a direction against the post slope whereas the TCL decreases continuously when the drop travels in a direction parallel to the post slope. The increasing length of the TCL creates an increased energy barrier that accounts for the higher slip angles in this direction.     

Superhydrophilic and superhydrophobic nanostructured surfaces via plasma treatment

Polyethylene terephthalate (PET) films have been structured with isolated nanofibrils and fibril bundles using oxidative plasma treatments with increasing etching ratios. The transition from fibrils to bundles was smooth and it was associated with a significant reduction in the overall top area fraction and with the development of a second organisation level at a larger length scale. This increased complexity was reflected in the surface properties. The surfaces with two-level substructures showed superhydrophilic and superhydrophobic properties depending on the surface chemistry. These properties were preserved during prolonged storage and resisted moderate mechanical stress. By combining different contact angle and drop impact measurements, the optimum surface design and plasma processing parameters for maximizing stability of the superhydrophobic or superhydrophilic properties of the PET films were identified.     

Contact line and contact angle dynamics in superhydrophobic channels

The dynamics of the wetting and movement of a three-phase contact line confined between two superhydrophobic surfaces were studied using a mean-field free-energy lattice Boltzmann model. Principle features of superhydrophobic surfaces, such as trapped vapor/air between rough microstructures, high contact angles, reduced contact angle hysteresis, and low resistance to fluid flow, were all observed. Movement of the three-phase contact line over a well-patterned superhydrophobic surface displays a periodic stick-jump-slip behavior, while the dynamic contact angle changes accordingly from maximum to minimum. Two regimes were found for the flow velocity as a function of surface roughness and can be related directly to the balance between driving force and flow resistance. This work provides a better understanding of dynamic wetting and fluid flow behaviors over superhydrophobic surfaces and hence could be useful in related applications.     

Microtextured superhydrophobic surfaces: a thermodynamic analysis

Superhydrophobic surfaces with a contact angle (CA) larger than 150 degrees have recently attracted great interest in both academic research and practical applications due to their water-repellent or self-cleaning properties. However, thermodynamic mechanisms responsible for the effects of various factors such as surface geometry and chemistry, liquids, and environmental sources have not been well understood. In this study, a pillar microtexture, which has been intensively investigated in experiments, is chosen as a typical example and thermodynamically analyzed in detail. To gain a comprehensive insight into superhydrophobic behavior, the roles of pillar height, width and spacing (or roughness and solid fraction), intrinsic CA, drop size, and vibrational energy are systematically investigated. Free energy (FE) and free energy barrier (FEB) are calculated using a simple and robust model. Based on the calculations of FE and FEB, various CAs, including apparent, equilibrium (stable), advancing and receding CAs, and contact angle hysteresis (CAH) can be determined. Especially, the design of practical superhydrophobic surfaces is emphasized in connection with the transition between noncomposite and composite states; a criterion for judging such transition is proposed. The theoretical results are consistent with the Wenzel's and the Cassie's equations for equilibrium CA values and experimental observations. Furthermore, based on these results and the proposed criterion, some general principles to achieve superhydrophobic performance are suggested.     

Influence of polar groups on the wetting properties of vertically aligned multiwalled carbon nanotube surfaces

In this work, we have studied superhydrophilic and superhydrophobic transitions on the vertically aligned multiwalled carbon nanotube (VACNT) surfaces. As-grown, the VACNT surfaces were superhydrophobic. Pure oxygen plasma etching modified the VACNT surfaces to generate superhydrophilic behavior. Irradiating the superhydrophilic VACNT surfaces with a CO₂ laser (up to 50?kW?cm^?2) restored the superhydrophobicity to a level that depended on the laser intensity. Contact angle and surface energy measurements by the sessile drop method were used to examine the VACNT surface wetting. X-ray photoelectron spectroscopy (XPS) showed heavy grafting of the oxygen groups onto the VACNT surfaces after oxygen plasma etching and their gradual removal, which also depended on the CO₂ laser intensity. These results show the great influence of polar groups on the wetting behavior, with a strong correlation between the polar part of the surface energy and the oxygen content on the VACNT surfaces. In addition, the CO₂ laser treatment created an interesting cage-like structure that may be responsible for the permanent superhydrophobic behavior observed on these samples.     

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.     

Contact angles of drops on curved superhydrophobic surfaces

Superhydrophobic surfaces have contact angles that exceed 150 degrees and are known to reduce surface fouling, protect surfaces, and improve liquid-liquid separations. Electrospun sub-micron fiber mats can perform as superhydrophobic surfaces. Superhydrophobic behavior is typically measured on planar surfaces, whereas applications may require curved surfaces. This paper discuses the measurement of water contact angles of fiber mats formed on cylindrical surfaces to create superhydrophobic behavior on curved surfaces. Equations are derived that relate the radius of curvature of spherical and cylindrical surfaces and drop size to the observed contact angle on the curved surfaces. Calculations from the equations agree well with experimental observations on spherical surfaces reported in literature and on cylindrical surfaces created in our lab.     

含氟硅丙烯酸酯乳液超疏水膜中疏水基团的梯度分布与表面微观结构研究

利用含氟疏水基团的梯度分布,结合草莓形纳米SiO2粒子提供的双重粗糙表面,制备了具有类"荷叶效应"的超疏水涂膜,水接触角达(174.2±2)°,滞后角几乎接近0°.通过原子力显微镜、扫描电镜和水接触角的测试对膜表面形貌及疏水性能进行了表征;探讨了其表面微观结构与表面疏水性能的关系.草莓形复合粒子在膜表面的无规则排列赋予涂膜表面不同等级的粗糙度,使水滴与涂膜表面接触时能够形成高的空气捕捉率,这种微观结构与疏水基团的梯度分布相结合,赋予了含氟硅丙烯酸酯乳液涂膜表面超疏水性能.     

On the role of the three-phase contact line in surface deformation

Viscoelastic braking theories developed by Shanahan and de Gennes and by others predict deformation of a solid surface at the solid-liquid-air contact line. This phenomenon has only been observed for soft smooth surfaces and results in a protrusion of the solid surface at the three-phase contact line, in agreement with the theoretical predictions. Despite the large (enough to break chemical bonds) forces associated with it, this deformation was not confirmed experimentally for hard surfaces, especially for hydrophobic ones. In this study we use superhydrophobic surfaces composed of an array of silicon nanostructures whose Young modulus is 4 orders of magnitude higher than that of surfaces in earlier recorded viscoelastic braking experiments. We distinguish between two cases: when a water drop forms an adhesive contact, albeit small, with the apparent contact angle θ < 180° and when the drop-surface adhesion is such that the conditions for placing a resting drop on the surface cannot be reached (i.e., θ = 180°). In the first case we show that there is a surface deformation at the three-phase contact line which is associated with a reduction in the hydrophobicity of the surface. For the second case, however, there cannot be a three-phase contact line associated with a drop in contact with the surface, and indeed, if we force-place a drop on the surface by holding it with a needle, no deformation is detected, nor is there a reduction in the hydrophobic properties of the surface. Yet, if we create a long horizontal three-phase contact line by partially immersing the superhydrophobic substrate in a water bath, we see a localized reduction in the hydrophobic properties of the surface in the region where the three-phase contact line used to be. The SEM scan of that region shows a narrow horizontal stripe where the nanorods are no longer there, and instead there is only a shallow structure that is lower than the nanorods height and resembles fused or removed nanorods. Away from that region, either on the part of the surface which was exposed to bulk water or the part which was exposed to air, no change in the hydrophobic properties of the surface is observed, and the SEM scan confirms that the nanorods seem intact in both regions.     

Fabrication of Superhydrophobic Surface with Different Metal Films on Aluminum Alloy

A simple technique was developed for the fabrication of a superhydrophobic surface on the aluminum alloy sheets. Different hierarchical structures(Ag, Co, Ni and Zn) were formed on the aluminum surface by the galvanic replacement reactions. After the chemical modification of them with fluorination, the wettability of the surfaces was changed from superhydrophilicity to superhydrophobicity. Scanning electron microscopy(SEM), energy dispersive spectrometry(EDS) and water contact angle measurement were performed to characterize the morphological characteristic, chemical composition and superhydrophobicity of the surfaces. The as-prepared superhydrophobic surfaces showed a water contact angle as high as ca.160° and sliding angle as low as ca.3°. We hope the method to produce superhydrophobic surface can be used in many fields.     

Evaporative properties and pinning strength of laser-ablated, hydrophilic sites on lotus-leaf-like, nanostructured surfaces

Wetting, evaporative, and pinning strength properties of hydrophilic sites on superhydrophobic, nanostructured surfaces were examined. Understanding these properties is important for surface characterization and designing features in self-cleaning, lotus-leaf-like surfaces. Laser-ablated, hydrophilic spots between 250 mum and 2 mm in diameter were prepared on silicon nanowire (NW) superhydrophobic surfaces. For larger circumference pinning sites, initial contact angle measurements resemble the contact angle of the surface within the pinning site: 65-69 degrees . As the drop volume is increased, the contact angles approach the contact angle of the NW surface without pinning sites: 171-176 degrees . The behavior of water droplets on the pinning sites is governed by how much of the water droplet is being influenced by the superhydrophobic NW surfaces versus the hydrophilic areas. During the evaporation of sinapic acid solution, drops are pinned by the spots except for the smaller circumference sites. Pinning strengths of the hydrophilic sites are a linear function of the pinning spot circumference. Protein samples prepared and deposited on the pinning sites for analysis by matrix-assisted laser desorption ionization indicate an improvement in sensitivity from that of a standard plate analysis by a factor of 5.     

Fabrication of superhydrophobic surfaces of n-hexatriacontane

Superhydrophobic surfaces of n-hexatriacontane were fabricated in a single-step process. The low surface energy of n-hexatriacontane together with the randomly distributed micro- and nanoscale roughness features guarantees very large contact angles and a small roll-off angle for water drops. The advantage of n-hexatriacontane superhydrophobic surfaces is their stability in the sense that they are impervious to chemical reactions and retain their wetting characteristics over a long period of time, as confirmed by XPS analysis and contact angle measurements.     

Roughness effects of cellulose and paper substrates on water drop impact and recoil

The impact dynamics of water drops on sized and unsized smooth cellulose films and paper surfaces with controlled roughness levels were studied. The objective was to better understand the effect of roughness on the liquid drop impact dynamics on paper surfaces, isolating from the effect chemical heterogeneity. Drop impact in the first few milliseconds were recorded using high-speed CCD camera and the three-phase contact line movement of the water drop was analyzed. Smooth cellulose film surface and rough paper surface showed similar impact dynamics, suggesting that the surface energy plays a more dominant role than surface roughness. Significantly different dynamic contact angles of water drop on the sized and unsized surfaces were observed during drop impact. The Laplace pressure of the curved spreading front pointing to the centre of a spreading drop on these sized cellulose and paper surfaces reduces the three-phase contact line movement, and leads to smaller maximum spreading diameter. Our results suggest that the water drop spreads on the rough surface is most likely via a “roll-over” action rather than “stick and jump” movements.     

Thermo-responsive superhydrophobic paper using nanostructured cellulose stearoyl ester

Hydrophilic paper was rendered with hydrophobic and superhydrophobic property after the treatment with solutions and nanoparticles of cellulose stearoyl ester (CSE), respectively. Cellulose stearoyl ester with a degree of substitution of 2.99 was synthesized from cellulose using stearoyl chloride. By dip-coating paper in CSE solution of at least 3 mg/ml in toluene, paper became hydrophobic with stable water contact angles of more than 120°. After further spray-coating using CSE nanoparticles that were prepared from CSE solution via nanoprecipitation, paper surface became superhydrophobic with water contact angles of larger than 150°. These superhydrophobic surfaces also exhibited self-cleaning character. Furthermore, the superhydrophobic paper surfaces showed a temperature-responsive character and could be turned hydrophobic after a heat-treatment at 70 °C for 5 min.