Superhydrophobic surface directly created by electrospinning based on hydrophilic material

We describe a method to form hydrophobic surfaces using PHBV (Poly (hydroxybutyrate-co-hydroxyvalerate))—a kind of intrinsically hydrophilic material. The concentration of polymer solutions was varied to control the surface morphology and resultant wetting property. The as-prepared films were characterized by micro-scale valley-and-hill structure, which was formed by aggregating of electrospun beads. The bead morphology changed from smooth to porous and popcorn-like with decreased concentrations. The shape of water droplet on these surfaces had contact angles ranging from 110.7 to 158.1°, with a maximum standard deviation of 2.5°. It was found that both the micro and nanostructure were important to create a superhydrophobic surface.     

A low-cost method to produce superhydrophobic polymer surfaces

Here, we introduce a novel and inexpensive template-based structuring process to create superhydrophobic polymer surfaces adapted from the naturally occurring micro/nano structured surfaces found on the superhydrophobic leaves of the quaking aspen tree. Electroformed nanocrystalline nickel coupons were sandblasted and chemically etched to create a negative reproduction of the aspen leaf surface structure. These nanocrystalline nickel samples were then employed as re-useable templates and pressed against various polymers at elevated temperatures, transferring the desired superhydrophobic structure to their surfaces. This structuring process resulted in water contact angles above 150° and tilt angles below 5° for polyethylene, polypropylene and polytetrafluoroethylene samples. In addition, the effects of temperature, water drop size and surfactant concentration on these pressed polymer surfaces were investigated to assess potential application limitations for these surfaces.     

Superhydrophobic surfaces produced by applying a self-assembled monolayer to silicon micro/nano-textured surfaces

A novel way of producing superhydrophobic surfaces by applying a self-assembled monolayer (SAM) to silicon micro/nano-textured surfaces is presented in this paper. The micro/nano-textured surfaces on silicon substrates were generated by the aluminum-induced crystallization (AIC) of amorphous silicon (a-Si) technique. Octadecyltrichlorosilane (OTS) SAMs were then applied to the textured surfaces by dip coating. The topography and wetting properties of the resulting surfaces were characterized using scanning electron microscopy (SEM) and a video-based contact angle measurement system. The results show that by introducing OTS SAMs on the silicon micro/nano-textured surfaces, superhydrophobic surfaces with water contact angles (WCAs) of 155° were obtained, as compared to the WCAs of OTS-modified smooth silicon surfaces of about 112°. Surface topography was found to directly influence the WCA as predicted by the Cassie-Baxter model.      

仿生超疏水表面的制备及润湿性研究

对植物叶表面的超疏水现象研究表明:植物叶表面的微观结构是引起超疏水的根本原因.设计并利用软刻蚀技术制备了一系列不同参数的光栅微结构表面,对水滴在这些非光滑表面上的接触角进行测量,测量结果表明材料表面几何结构直接影响接触角的大小,通过设计微结构的几何参数可以获得理想的超疏水材料.     

Robust superhydrophobicity of hierarchical ZnO hollow microspheres fabricated by two-step self-assembly

Superhydrophobic and superhydrophilic surfaces have been extensively inves- tigated due to their importance for industrial applications. It has been reported, however, that superhydrophobic surfaces are very sensitive to heat, ultraviolet （UV） light, and electric potential, which interfere with their long-term durability. In this study, we introduce a novel approach to achieve robust superhydrophobic thin films by designing architecture-defined complex nanostructures. A family of ZnO hollow microspheres with controlled constituent architectures in the morphologies of 1D nanowire networks, 2D nanosheet stacks, and 3D mesoporous nanoball blocks, respectively, was synthesized via a two-step self-assembly approach, where the oligomers or the constituent nanostructures with specially designed structures are first formed from surfactant templates, and then further assembled into complex morphologies by the addition of a second co-surfactant. The thin films composed of two-step synthesized ZnO hollow microspheres with different architectures presented superhydrophobicities with contact angles of 150°-155°, superior to the contact angle of 103° for one-step synthesized ZnO hollow microspheres with smooth and solid surfaces. Moreover, the robust superhydrophobicity was further improved by perfluorinated silane surface modification. The perfluorinated silane treated ZnO hollow microsphere thin films maintained excellent hydrophobicity even after 75 h of UV irradiation. The realization of environmentally durable promising solution for their long-term irradiations. superhydrophobic surfaces provides a service under UV or strong solar light     

A facile process for preparing superhydrophobic films with surface-modified SiO<Subscript>2</Subscript>/nylon 6,6 nanocomposite

A superhydrophobic SiO₂/nylon 6,6 nanocomposite coating was fabricated by a facile casting process. Compared with the intrinsically hydrophilic pure nylon 6,6, the as-prepared coating displayed a superhydrophobic property in the pH range from 1 to 14. It was also found that the resulting water contact angles of the as-prepared surface were always larger than 159°, but the sliding angles had an obvious decrease from about 33.4°–1° as the content of SiO₂ nanoparticles increased. In addition, a transition from the transitional superhydrophobic state between Wenzel’s and Cassie’s state to the Cassie’s state was observed.     

Superhydrophobic Coatings and Their Durability

Superhydrophobic coatings with contact angles (CAs) > 150° and sliding angles (SAs) < 10° have become the focus of research and industrial development studies for water repellency applications. Furthermore, superhydrophobic coatings have shown to reduce ice adhesion by means of their low surface energy chemistry and nano/micro roughness. Superhydrophobicity can be achieved by combining the chemistry and the roughness of the surface, inspired by the lotus leaf composition and structure. Durability enhancement of superhydrophobic surfaces is a critical issue for commercial and industrial applications. Consequently, the use of superhydrophobic surfaces in practical applications is limited due to their poor mechanical abrasion resistance and hostile environmental conditions. Covalent bonding of the micro/nano particles to the binder material was identified as essential for durability enhancement. This review summarizes the state of the art of the design, preparation techniques of durable superhydrophobic coatings and the characterization techniques for durability evaluation.     

Functionalized superhydrophobic coatings with micro-/nanostructured ZnO particles in a sol–gel matrix

Among the methods to create superhydrophobic surfaces by wet chemistry, one of the strategies consists in coating the substrate with a hydrophobic polymer with specific morphology. Such elaborated surfaces are largely developed and can present complex architectures but are generally fragile. Ceramic-based coatings show better durability. In this work, a new route associating inorganic and polymeric parts is used. Surfaces with superhydrophobic properties are prepared with a mixture of zinc oxide (ZnO) particles in a hybrid organic inorganic matrix prepared via sol–gel route. ZnO particles were synthesized by the inorganic polycondensation route and exhibit an appropriate micro-/nanostructure for superhydrophobicity. Sol–gel matrix is obtained by the alkoxide route with aluminum-tri-sec-butoxide (ASB) and (3-glycidoxypropyl)trimethoxysilane (GPTMS). A step of octadecylphosphonic acid (ODP) functionalization on ZnO particles and on film surfaces was employed to considerably improve hydrophobic properties. This new route enables to obtain superhydrophobic coatings that exhibit water contact angles superior to 150°. These coatings show a homogeneous and smooth coverage on aluminum alloy substrate. Results attest the significance of the synergy for superhydrophobic coatings: a micro-/nanostructured surface and an intrinsic hydrophobic property of the material. The durability of the coatings has also been demonstrated with only a slight decrease in hydrophobicity after erosion.     

Superwetting Surfaces under Different Media: Effects of Surface Topography on Wettability

Superwetting surfaces in air, such as superhydrophobic and superoleophobic surfaces that are governed by surface chemical compositions and surface topographies, are one of the most extensively studied topics in this field. However, it is not well‐understood how surface topographies affect the behaviors of immiscible liquids and gases under other kinds of media, although it is significant in diverse fields. The main aim of this work is to systematically investigate the wetting behaviors of liquids (water and oil) and gas (air) on silicon surfaces with different topographies (i.e., smooth, micro, nano, and micro‐/nanostructures) under various media (i.e., air, water, and oil). The contact angles, as well as contact‐angle hysteresis, sliding angles, and adhesive forces, were utilized to evaluate the wettability of these surfaces. As a result, the microstructured surfaces typically exhibit high contact‐angle hysteresis, high sliding angles, and high adhesive forces, whereas the micro‐/nanostructured surfaces display low contact‐angle hysteresis, low sliding angles, and low adhesive forces, even if they have high (>150°) and similar contact angles. Furthermore, when transferring the same surface from one kind of medium to another, different superwetting states can be reversibly switched.     

The role of low-angle grain boundaries in multi-temperature equal channel angular pressing of Mg–3Al–1Zn alloy

Equal channel angular pressing was used to process an AZ31B magnesium alloy (nominally Mg–3Al–1Zn in wt%) at temperatures decreasing from 200 to 150 °C. The resulting microstructure was characterized by electron backscattered diffraction to reveal the role of low-angle grain boundaries in grain refinement. It was found that low-angle grain boundaries with misorientation angles lower than 5° are surrounded by regions of increased strain gradients, which can stimulate the generation of non-basal slip dislocations during the equal channel angular pressing at temperatures of approximately 150 °C. The strain gradients in the vicinity of the grain boundaries with misorientation angles in the range of 5°–10° were less frequent or were completely absent for high-angle grain boundaries with misorientation angles higher than 10°. This article also discusses the importance of low-angle grain boundaries for the generation of non-basal 〈c+a〉 dislocations needed for successful equal channel angular pressing of AZ31B at temperature of 150 °C.     

Design of superhydrophobic ultraoleophobic NyCo

The apparent contact angles of dodecane droplets deposited on a 50:50 nylon:cotton blended woven fabric (NyCo) were measured, and the characteristics required for an ultraoleophobic surface were described. The metastable Cassie–Baxter model, a transition status from the original Cassie–Baxter model to the Wenzel model, was investigated to design ultraoleophobic surfaces and to understand the wetting behavior of such surfaces. Using chemical and geometrical modifications of NyCo, a surface having contact angles to dodecane of greater than 150° and water contact angles of greater than 165° has been prepared. Good agreement between the predicted and measured contact angles was obtained. Developing a superhydrophobic ultraoleophobic material has been achieved by two criteria: a low-surface-energy and a properly designed surface morphology.     

Design of artificial lotus leaves using nonwoven fabric

The apparent contact angles of a droplet deposited on the surfaces of thermal-bonded nonwoven fabrics were presented, and the characteristics required for a superhydrophobic surface were described. For a nonwoven superhydrophobic surface, the Cassie–Baxter model describes the wetting of rough surfaces. Using topological and chemical surface modifications of nylon 6,6 nonwoven fabric, artificial Lotus leaves having water contact angles >150° were prepared. Good agreement between the predictions based on the original Cassie–Baxter model and experiments was obtained. The angle at which a water droplet rolls off the surface has also been used to define a superhydrophobic surface. Superhydrophobic surfaces were prepared by two criteria: a low-surface energy and a properly designed surface roughness.     

Water-Repellent Approaches for 3-D Printed Internal Passages

In this work, two different manufacturing approaches are presented that create water-repellency (hydrophobicity and super-hydrophobicity) for acrylonitrile butadiene styrene (ABS) structures. In particular, this is the first study to render three-dimensional (3-D) printed ABS surfaces with internal flow paths to be superhydrophobic. The first approach uses standard wet-based chemical processing for surface preparation after which a fluorocarbon layer is deposited by dip coating or with vapor deposition. This first approach creates hydrophobic surfaces with roll-off angles of less than 30°. In the second approach, the ABS structures are dip-coated with a commercial rubber coating solution and subsequently surface-modified by reactive ion etching (RIE) with fluorinated gases to render the samples superhydrophobic, with roll-off angles as low as 6°. In order to further enhance their water-repellency, the dip-coating rubber solution is mixed with polytetrafluoroethylene (PTFE) colloidal dispersions to form a nanocomposite layer prior to the RIE process. The PTFE particles induce surface roughness as well as hydrophobicity. The modified surfaces created by the two approaches are further characterized by scanning electron microscopy and water drainage performance. Water drainage (prevention of water retention) is especially important for high thermal efficiency of 3-D printed heat exchangers. However, water-repellency for ABS is also interesting for a broader range of applications that use this material.     

Fabrication of superhydrophobic and oleophobic zinc coating on steel surface

In this work, a simple method, including electrodeposition and chemical modification, for fabrication of a superhydrophobic and oleophobic coating on steel substrate is reported. The surface morphology of this coating showed concave structure, and the contact angles of water and glycerol on this coating surface were about 153.57° and 149.32°, respectively. In addition, the water droplet was easy to roll on this coating surface, and the sliding angle was smaller than 10°. The contact angle of the water/ethanol droplet with different surface tension, from 56 to 36?mN?m^?1, was also >130° on this coating surface, indicating this as superhydrophobic and oleophobic coating surface with good lyophobicity. Moreover, this coating surface had excellent non-sticking property for the water droplet under a certain external pressure, self-cleaning property and long-term stability.     

Superhydrophobic Coatings for Technical Applications

Water repellent coatings developed in this work showed that two superimposed rough structures are required to generate superhydrophoby with WCA >150°. A micro rough surface overcoated with a submicro or nano rough hydrophobic material behave similar to the hierarchical structures found on leafs of some plants which generate the highly mobile Cassie/Baxter droplets. Coatings of inorganic and organic materials were performed by thermal spraying (inorganic materials) and spraycoating (organic materials) on sandblasted metal, mainly stainless steel, surfaces. Hierarchical roughness structures were developed by thermal treatment of pure and composite fluoropolymeric layers. Such hierarchical superhydrophobic coating systems showed water contact angles between 160° and 170°. The coatings have good mechanical stability and can be applied in numerous technical applications.     

Design and development of anti-icing textile surfaces

An anti-icing material can be created by mimicking one of nature’s best known performances superhydrophobicity that is observed at many plant leaves. The anti-icing properties of a superhydrophobic surface depend on the surface morphology as well as the surface tension of the substrate. This implies that both the chemistry and the topography of the anti-icing coating material are important. Therefore, the relationship between the anti-icing properties and the morphology of a superhydrophobic surface should be understood and the study has to be extended beyond the bio-inspired superhydrophobic properties of the materials to similar properties toward ice. In this research, fluorosilane-treated superhydrophobic textile nonwoven fabric is prepared via wet-processing, and the anti-icing properties of the surface are observed and compared to those of three controls: an untreated fabric, a fluorosilane-treated smooth surface, and an untreated film. In order to evaluate anti-icing properties of superhydrophobic surfaces, super-cooled water was dropped on the surface of the prepared superhydrophobic fabric and all three controls. In addition, water drops were deposited on a superhydrophobic surface and the controls, and then the samples along with water drops were placed in a freezer to make the water drops completely freeze. After the samples were removed from the freezer, they were placed on a plate inclined at 45° to compare the ice removal process of the superhydrophobic surface with those of the controls. It was found that a superhydrophobic surface, which was created by combining low surface energy and micro/nano rough structures, could provide anti-icing properties to the surface.     

Drop detachment and motion on fuel cell electrode materials

Liquid water is pushed through flow channels of fuel cells, where one surface is a porous carbon electrode made up of carbon fibers. Water drops grow on the fibrous carbon surface in the gas flow channel. The drops adhere to the superficial fiber surfaces but exhibit little penetration into the voids between the fibers. The fibrous surfaces are hydrophobic, but there is a substantial threshold force necessary to initiate water drop motion. Once the water drops begin to move, however, the adhesive force decreases and drops move with minimal friction, similar to motion on superhydrophobic materials. We report here studies of water wetting and water drop motion on typical porous carbon materials (carbon paper and carbon cloth) employed in fuel cells. The static coefficient of friction on these textured surfaces is comparable to that for smooth Teflon. But the dynamic coefficient of friction is several orders of magnitude smaller on the textured surfaces than on smooth Teflon. Carbon cloth displays a much smaller static contact angle hysteresis than carbon paper due to its two-scale roughness. The dynamic contact angle hysteresis for carbon paper is greatly reduced compared to the static contact angle hysteresis. Enhanced dynamic hydrophobicity is suggested to result from the extent to which a dynamic contact line can track topological heterogeneities of the liquid/solid interface.     

沉积熔融法制备超疏水微结构表面

传统超疏水表面制备技术都有着各自的缺点,如加工成本高、受加工设备精度影响大、形貌尺寸随机性大。为得到低成本、形貌尺寸相对可控的超疏水微结构表面,提出了新型制备技术——沉积熔融法。通过金属颗粒悬浊液的自然沉积使微纳尺寸的颗粒均匀分布在金属表面,经熔融、再结晶使其与金属表面结合,再采用低表面能高分子修饰,制备出超疏水微结构表面。通过此方法采用锡铅合金在以黄铜、45号钢、6063铝合金基底上制备了超疏水微结构表面,并发现了金属基底材质与微结构表面的疏水性能之间没有必然关系。当微米尺寸的颗粒直径越小,制备的微结构表面的疏水性就越大。此外,相较于传统超疏水表面加工方法,沉积熔融法可实现微米级形貌的制备,且具有加工效率高、工艺简单、成本低廉、不影响原工件强度等优点,但其难以在弧形表面上应用的问题需要进一步研究。     

Micro and nano-texturization of intermetallic oxide alloys by a single anodization step: preparation of artificial self-cleaning surfaces

Micro- and nanostructures of Ti-γCu (γ = 0, 30, 50, 70, and 100 wt %) intermetallic alloys were produced through a single anodization step. It was found that the original alloy composition influences the final oxide morphology obtained after anodization which presented formation of a microstructure with nanotubes, nanoparticles or nanopillars on the surface. Pure Ti and Cu oxide metals and their alloys presented hydrophilic or superhydrophilic properties immediately after anodization. When the anodized pure metal and/or Ti-γCu surfaces were functionalized with trimethoxypropylsilane (TPMSi), by dipping and coating with a thin perfluorinated layer, the treated substrates became in all cases superhydrophobic (water contact angles in the range of 152-166°), showing excellent self-cleaning properties with hysteresis below 3°. These results can be explained by a combination of nanomicro morphologies with low surface energy compounds in the topmost monolayers. The decrease in hysteresis was associated with a higher M-OH bond concentration on the anodized surfaces, which allowed for more complete TMPSi coating coverage. This study also indicates that easy and effective fabrication of superhydrophobic surfaces in pure metals and alloys is possible without involving traditional multistep processes.     

透明超疏水玻璃表面的制备及性能研究

目的研究透明超疏水玻璃的制备及性能。方法以纳米二氧化硅和无水乙醇为原料制成半透明乳液,然后将乳液喷涂在玻璃表面,再通过接触角测试、透光率测试仪等手段对玻璃表面的性能进行研究。结果在玻璃基材表面构建了与水滴接触角高达158°±2°,滚动角低至1°的透明超疏水表面。当喷涂液中纳米二氧化硅的质量分数为1.5%时,获得的超疏水玻璃表面具有优异的防水性、抗污易清洁性和透明性。结论在玻璃基底上制备透明超疏水表面可以大大提高玻璃表面的防水、防污性,并使玻璃表面更易于清洁,有利于减少玻璃包装材料清洗时的用水量和洗涤剂用量,从而增强玻璃包装材料的生态环保效应。