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.     

Creation of “Rose Petal” and “Lotus Leaf” Effects on Alumina by Surface Functionalization and Metal‐Ion Coordination

Functional differences between superhydrophobic surfaces, such as lotus leaf and rose petals, are due to the subtle architectural features created by nature. Mimicry of these surfaces with synthetic molecules continues to be fascinating as well as challenging. Herein, we demonstrate how inherently hydrophilic alumina surface can be modified to give two distinct superhydrophobic behaviors. Functionalization of alumina with an organic ligand resulted in a rose‐petal‐like surface (water pinning) with a contact angle of 145° and a high contact angle hysteresis (±69°). Subsequent interaction of the ligand with Zn²⁺ resulted in a lotus‐leaf‐like surface with water rolling behavior owing to high contact angle (165°) and low‐contact‐angle‐hysteresis (±2°). In both cases, coating of an aromatic bis‐aldehyde with alkoxy chain substituents was necessary to emulate the nanowaxy cuticular feature of natural superhydrophobic materials.     

Self-assembled monolayers of dendron thiols for electrodeposition of gold nanostructures: toward fabrication of superhydrophobic/superhydrophilic surfaces and pH-responsive surfaces

This paper describes the fabrication of surfaces with different wettability, superhydrophobic/superhydrophilic, and pH-responsive properties. We used a self-assembled monolayer (SAM) of a dendron thiol as the underlying surface for electrodeposition of gold nanostructures. After this modification with a SAM of n-dodecanethiol or 11-mercaptoundecanol, the surface shows remarkable superhydrophobic properties with a contact angle of about 155 degrees and a tilt angle of less than 2 degrees or superhydrophilic properties with a contact angle of about 0 degrees , respectively. Moreover, a large-scale pH-responsive surface was obtained by modification with 2-(11-mercaptoundecanamido)benzoic acid (7) (MUABA). The pH-responsive behavior was amplified by using rough surfaces.     

Biomimetic superhydrophobic and highly oleophobic cotton textiles

We report a biomimetic procedure to prepare superhydrophobic cotton textiles. By in situ introducing silica particles to cotton fibers to generate a dual-size surface roughness, followed by hydrophobization with polydimethylsiloxane (PDMS), normally hydrophilic cotton has been easily turned superhydrophobic, which exhibits a static water contact angle of 155 degrees for a 10 microL droplet. The roll-off angle of water droplets depends on the droplet volume, ranging from 7 degrees for a droplet of 50 microL to 20 degrees for a 7 microL droplet. When a perfluoroalkyl chain is introduced to the silica particle surface, the superhydrophobic textile also becomes highly oleophobic, as demonstrated by a static contact angle of 140 degrees and a roll-off angle of 24 degrees for a 15 microL sunflower oil droplet.     

Fabrication of superhydrophobic surfaces by dislocation-selective chemical etching on aluminum, copper, and zinc substrates

A surface roughening method by simple chemical etching was developed for the fabrication of superhydrophobic surfaces on three polycrystalline metals, namely aluminum, copper, and zinc. The key to the etching technique was the use of a dislocation etchant that preferentially dissolves the dislocation sites in the grains. The etched metallic surfaces, when hydrophobized with fluoroalkylsilane, exhibited superhydrophobic properties with water contact angles of larger than 150 degrees, as well as roll-off angles of less than 10 degrees for 8-microL drops. Also, the dislocation etching concept introduced here may be helpful in the fabrication of superhydrophobic surfaces on other polycrystalline substrates.     

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.     

Multifunctional polymethylsilsesquioxane (PMSQ) surfaces prepared by electrospinning at the sol-gel transition: superhydrophobicity, excellent solvent resistance, thermal stability and enhanced sound absorption property

Multifunctional superhydrophobic polymethylsilsesquioxane (PMSQ) surfaces with excellent solvent resistance, thermal stability and enhanced sound absorption property were manufactured by electrospinning. The surfaces with various hierarchical morphologies and hydrophobicity were obtained by electrospinning at the different stages of sol-gel transition of PMSQ prepolymer solution. At the stage with a proper viscosity the superhydrophobic PMSQ surface with a contact angle as high as 151° and a sliding angle as low as 8° was prepared. Due to the excellent thermal stability and solvent resistance properties of the cured PMSQ, the resultant surfaces remain superhydrophobicity after thermal treatment at 300 °C and immersion into many solvents. Additionally, an enhanced acoustical performance and ultra water repellency were obtained simultaneously when the traditional acoustical sponge was decorated with the electrospun PMSQ superhydrophobic surface. The robust superhydrophobic PMSQ surfaces may promise practical applications in many fields.     

Design and fabrication of micro-textures for inducing a superhydrophobic behavior on hydrophilic materials

Artificial superhydrophobic surfaces are typically fabricated by tuning the surface roughness of intrinsically hydrophobic surfaces. We report here the design and fabrication of micro-textures for inducing a superhydrophobic behavior on hydrogen-terminated Si surfaces with an intrinsic water contact angle of approximately 74 degrees . The micro-textures consist of overhang structures with well-defined geometries fabricated by microfabrication technologies, which provide positions to support the liquid and prevent the liquid from entering into the indents between the micro-textures. As a result, water is in contact with a composite surface of solid and air, which induces the observed macroscopic superhydrophobic behavior.     

Fabrication of superhydrophobic surfaces by self-assembly and their water-adhesion properties

The self-assembled films of methyloctyldimethoxysilane (MODMS) and fluorooctylmethyldimethoxysilane (FODMS) were prepared on silicon surfaces and evaluated with AFM, water contact angle measurement, and X-ray photoelectron spectroscopy. Superhydrophobic surfaces were obtained by cooperation of MODMS and FODMS self-assembly with surface roughening. The results showed that preparing closely packed self-assembled films and fabricating surface nanometer-scale and micrometer-scale binary roughness can achieve superhydrophobic films with a water contact angle larger than 156 degrees. The difference between solution deposition and chemical vapor deposition is also investigated. Moreover, superhydrophobic surfaces created with MODMS and FODMS show the different water-adhesion effects, which could have great significance on liquid microtransport in microfluid devices.     

Beyond the lotus effect: roughness influences on wetting over a wide surface-energy range

To enhance our understanding of liquids in contact with rough surfaces, a systematic study has been carried out in which water contact angle measurements were performed on a wide variety of rough surfaces with precisely controlled surface chemistry. Surface morphologies consisted of sandblasted glass slides as well as replicas of acid-etched, sandblasted titanium, lotus leaves, and photolithographically manufactured golf-tee shaped micropillars (GTMs). The GTMs display an extraordinarily stable, Cassie-type hydrophobicity, even in the presence of hydrophilic surface chemistry. Due to pinning effects, contact angles on hydrophilic rough surfaces are shifted to more hydrophobic values, unless roughness or surface energy are such that capillary forces become significant, leading to complete wetting. The observed hydrophobicity is thus not consistent with the well-known Wenzel equation. We have shown that the pinning strength of a surface is independent of the surface chemistry, provided that neither capillary forces nor air enclosure are involved. In addition, pinning strength can be described by the axis intercept of the cosine-cosine plot of contact angles for rough versus flat surfaces with the same surface chemistries.     

A facial approach to fabricate superhydrophobic aluminum surface

A facial chemical etching method was developed for fabricating superhydrophobic aluminum surfaces. The resultant surfaces were characterized by scanning electron microscopy, water contact angle (WCA) measurement, and optical methods. The surfaces of the modified aluminum substrates exhibit superhydrophobicity, with a WCA of 154.8° ± 1.6° and a water sliding angle of about 5°. The etched surfaces have binary structure consisting of the irregular microscale plateaus and caves in which there are the nanoscale block‐like convexes and hollows. The superhydrophobicity of aluminum substrates occurs only in some structures in which the plateaus and caves are appropriately ordered. The resulted surfaces have good self‐cleaning properties. The results demonstrate that it is possible to construct superhydrophobic surface on hydrophilic substrates by tailoring the surface structure to providing more spaces to trap air. Copyright © 2009 John Wiley & Sons, Ltd.     

Superhydrophobic polyolefin surfaces: controlled micro- and nanostructures

Superhydrophobic polyolefin surfaces were prepared by simultaneous micro- and nanostructuring. Electropolished aluminum foil was microstructured with a micro working robot and then anodized in polyprotic acid. The surface microstructure can be tailored by adjusting the settings of the micro working robot and the nanostructure by adjusting the parameters of the anodization procedure. Surface structuring was done by injection molding where a microstructured anodized aluminum oxide mold insert was used to pattern the surfaces. Structuring had a marked effect on the contact angle between the injection-molded polyolefins and water. When the optimized microstructure was covered with nanostructure, the static contact angle between polypropylene and water obtained a value of about 165 degrees and the sliding angle decreased to about 2.5 degrees. The superhydrophobic state was achieved.     

Direct catalytic route to superhydrophobic polyethylene films

Polyethylene films grow on a flat silica surface modified by the bis(imino)pyridyl iron(II) catalyst during ethylene polymerization in toluene solvent. The resulting films show superhydrophobic properties. Advancing water contact angle as high as 169 degrees and sliding angles as low as 2 degrees are obtained on these films. SEM images reveal special surface structures of these films containing micrometer-sized islands, submicrometer particles on the islands, and stress nanofibers between the islands, which render superhydrophobicity to the polyethylene surfaces. After the submicrometer particles and stress nanofibers are removed by annealing, the superhydrophobic properties of the polymer films disappear.     

Superhydrophobic surfaces using selected zinc oxide microrod growth on ink-jetted patterns

The synthesis and properties of superhydrophobic surfaces based on binary surface topography made of zinc oxide (ZnO) microrod-decorated micropatterns are reported. ZnO is intrinsically hydrophilic but can be utilized to create hydrophobic surfaces by creating artificial roughness via microstructuring. Micron scale patterns consisting of nanocrystalline ZnO seed particles were applied to glass substrates with a modified ink-jet printer. Microrods were then grown on the patterns by a hydrothermal process without any further chemical modification. Water contact angle (WCA)(1) up to 153° was achieved. Different micro array patterned surfaces with varying response of static contact angle or sessile droplet analysis are reported.     

Superhydrophobic effects of self-assembled monolayers on micropatterned surfaces: 3-D arrays mimicking the lotus leaf

The contact angle of water has been measured on a series of self-assembled monolayers (SAM) on thermally evaporated and sputter coated silver surfaces. It is found that micropatterning the surface using nanosphere lithography leads to large increases in the contact angle and generates superhydrophobic surfaces with contact angles >150 degrees. The type of functional groups on the SAMs, the metal island size, and the metal island thickness all contribute to the measured contact angle. The maximum contact angle found was 161 degrees for a fluorinated alkanethiol on 80 nm thick silver islands.     

Influence of n-hexanol and n-octanol on wetting properties and air entrapment at superhydrophobic surfaces

Superhydrophobic surfaces have recently attracted a lot of attention due to their self-cleaning properties. The superhydrophobic surfaces used in our studies were prepared using a mixed inorganic-organic coating. In order to check how short chain surface active agents affect the surface energy of such surfaces, their wettability (sessile drop technique) and the kinetics of the three phase contact formation were studied. It was found that with increasing concentrations of n-hexanol and n-octanol the surface energy of these surfaces was only slightly changed, i.e. a small decrease in contact angle values with increasing solution concentration was detected. Even for the most concentrated n-hexanol and n-octanol solutions, the contact angles were in the range 145-155° and the drop rolled off, indicating that the studied surfaces stayed superhydrophobic. Air bubbles, upon collision with such superhydrophobic surfaces, spread over the superhydrophobic surface within milliseconds in the studied solutions.     

Several surfaces with special wettability: Influence on spreading and motion of W/O emulsion droplets

Physical and chemical modifications were made on the surface of the aluminum sheet to change the surface properties and superhydrophobic–hydrophilic wettability gradient surface was made on the perspex surface by using microstructure-pattering technique and self-assembled-monolayer method. By using high-speed video camera system and optical tensiometer, this paper discusses the influence of special surfaces with different wettability on spreading and motion of water, oil, and W/O emulsion droplets both experimentally and theoretically. In addition, the paper also discusses the influence of the superhydrophobic–hydrophilic wettability gradient on fluidity of W/O emulsion droplets and the coalescence process of droplets. The results showed that the contact angle of W/O emulsion droplets on the modified surfaces was related to the water and oil distribution at the three-phase line. On the wettability gradient surface, the droplet moved spontaneously when the droplet was located at the junction of the gradient. A quasi-steady theoretical model was used to analyze the driving and resistant forces acting on a droplet to improve the understanding of the self-transport behavior of the droplets.     

Effects of contact angle hysteresis on ice adhesion and growth on superhydrophobic surfaces under dynamic flow conditions

In this paper, the icephobic properties of superhydrophobic surfaces are investigated under dynamic flow conditions using a closed-loop low-temperature wind tunnel. Superhydrophobic surfaces were prepared by coating aluminum and steel substrate plates with nano-structured hydrophobic particles. The superhydrophobic plates, along with uncoated controls, were exposed to a wind tunnel air flow of 12 m/s and ?7 °C with deviations of ±1 m/s and ±2.5 °C, respectively, containing micrometer-sized (～50 μm in diameter) water droplets. The ice formation and accretion were observed by CCD cameras. Results show that the superhydrophobic coatings significantly delay ice formation and accretion even under the dynamic flow condition of highly energetic impingement of accelerated supercooled water droplets. It is found that there is a time scale for this phenomenon (delay in ice formation) which has a clear correlation with contact angle hysteresis and the length scale of the surface roughness of the superhydrophobic surface samples, being the highest for the plate with the lowest contact angle hysteresis and finest surface roughness. The results suggest that the key for designing icephobic surfaces under the hydrodynamic pressure of impinging droplets is to retain a non-wetting superhydrophobic state with low contact angle hysteresis, rather than to only have a high apparent contact angle (conventionally referred to as a “static” contact angle).     

Reversible superhydrophobic to superhydrophilic conversion of Ag@TiO2 composite nanofiber surfaces

A new type of superhydrophobic material consisting of a surface with supported Ag@TiO(2) core-shell nanofibers has been prepared at low temperature by plasma-enhanced chemical vapor deposition (PECVD). The fibers are formed by an inner nanocrystalline silver thread which is covered by a TiO(2) overlayer. Water contact angles depend on the width of the fibers and on their surface concentration, reaching a maximum wetting angle close to 180 degrees for a surface concentration of approximately 15 fibers microm(-2) and a thickness of 200 nm. When irradiated with UV light, these surfaces become superhydrophilic (i.e., 0 degrees contact angle). The decrease rate of the contact angle depends on both the crystalline state of the titania and on the size of the individual TiO(2) domains covering the fibers. To the best of our knowledge, this is one of the few examples existing in the literature where a superhydrophobic surface transforms reversibly into a superhydrophilic one as an effect of light irradiation.