Durable,self-cleaning and superhydrophobic bamboo timber surfaces based on TiO2 films combined with fluoroalkylsilane

Decorative materials, including bamboo timber, have been proposed to exploit their superhydrophobic and self-cleaning properties, but a comprehensive appraisal of their environmental adaptability is still deficient. In this paper, a robust and durable superhydrophobic surface was formed on bamboo timber substrate through a process combining chemical solution deposition and chemical modification. The superhydrophobic surface resulted from micro-nanoscale binary-structured TiO₂ films and the assembly of low-surface-energy fluorinated components, which exhibited a water contact angle of 163±1° and a sliding angle of 3±1°. The surface maintained superhydrophobicity after mechanical abrasion against 1500 mesh SiC sandpaper for 800 mm at the applied pressure of 1.2 kPa, indicating good mechanical stability. Moreover, the superhydrophobic surface exhibited good chemical stability against both acidic and basic aqueous solutions (e.g., simulated acid rain). After exposure to atmosphere for more than 180 days, the obtained surface still maintained a contact angle of 155±2° and a sliding angle of 6±2°, revealing good long-term stability. In addition, the as-prepared superhydrophobic surface exhibited almost complete wet self-cleaning of dirt particles with water droplets. It is believed that the method presented in this study can provide a straightforward and effective route to fabricate a large-area, mechanically robust, anticorrosive and self-cleaning superhydrophobic surface on woody materials for a great number of potential applications.     

Tunability of the Adhesion of Water Drops on a Superhydrophobic Paper Surface via Selective Plasma Etching

We report the fabrication of a sticky superhydrophobic paper surface with extremely high contact angle hysteresis: advancing contact angle ～150° (superhydrophobic) and receding contact angle ～10° (superhydrophilic). In addition, we report the controlled tunability of the contact angle hysteresis from 149.8 ± 5.8° to 3.5 ± 1.1°, while maintaining superhydrophobicity, as defined through an advancing contact angle above 150°. The hysteresis was tuned through the controlled fabrication of nano-scale features on the paper fibers via selective plasma etching. The variations in contact angle hysteresis are attributed to a transition of the liquid–surface interaction from a Wenzel state to a Cassie state on the nano-scale, while maintaining a Cassie state on the micro-scale. Superhydrophobic cellulosic surfaces with tunable stickiness or adhesion have potential applications in the control of aqueous drop mobility and the transfer of drops on inexpensive, renewable substrates.     

Preparation of a new superhydrophobic nanofiber film by electrospinning polystyrene mixed with ester modified silicone oil

A new superhydrophobic nanofiber membrane with certain mechanical strength was prepared by electrospinning the polystyrene (PS) with ester modified silicone oil (EMSO). To increase the roughness and tensile strength, the EMSO with low energy as hydrophobic macromolecular substance was added into PS precursor solution. Then during the process of electrospinning, some of the ester modified silicone oil was distribution on the surface of substrate (PS) fiber films to generate double structure which leaded to the superhydrophobicity. We probed into the relationship between the surface wettability, morphologies, mechanical property, and the mass ratios of ester modified silicone oil /PS, and with the increasing of EMSO, the water CA value increased from 135 ± 0.5° to 152 ± 0.2°and the tensile strength grown from 0.23 MPa to 0.92 MPa. The film shows a network structure consisting of numerous randomly oriented fibers, the diameters of which changed from 0.5 μm to 2.0 μm belong to relatively big diameter fibers, which has great significance to the research of superhydrophobic membrane with big diameter fibers and also this method is easy, convenient and environment friendly. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40718.     

Preparation of a Superhydrophobic ZnO Film on ITO Glass via Electrodeposition Followed by Oxidation. Effect of the Deposition Time

This study investigates the fabrication of a stable superhydrophobic surface with low contact angle (CA) hysteresis using ZnO thin films prepared by cathodic electrodeposition and subsequent gaseous oxidation. The deposition time is a crucial factor in nanostructuring and producing surface roughness of the films. Cathodic electrodeposition for 60 s created a number of nanopillars, which exhibited the highest CA value, i.e., 167.9°. The rough ZnO surface displayed not only enhanced water repellency with low CA hysteresis but also excellent superhydrophobic stability. The application of the Cassie–Baxter model demonstrated that the ZnO nanostructure contributed to increasing the area of a water droplet in contact with air, leading to superhydrophobicity. Such a unique textured surface showed a great potential for the engineering of strong superhydrophobic coatings.     

One-pot fabrication of robust hydrophobia and superoleophilic cotton fabrics for effective oil-water separation

A one-pot sonochemical irradiation method was developed for the fabrication of superhydrophobic and superoleophilic cotton fabric from a solution consisting of branched silica nanoparticles and tetraethoxysilane-dodecyltrimethoxysilane sol. The silica/sol-coated cotton fabric could be wetted by liquids of low surface tension, but was water repellent with a water contact angle of 159 ± 1.2° and water shedding angle of 6 ± 0.8°. The as-prepared cotton fabric could be used as effective materials for the separation of oil from water with separation efficiency as high as 98.2% and maintained separation efficiency above 94% after 30 separation cycles for the kerosene-water mixture. Moreover, the superhydrophobic and superoleophilic cotton fabric could maintain stable superhydrophobicity after treatment with strong acidic and alkali solutions, and harsh mechanical damage. Therefore, this reported robust superhydrophobic cotton fabric exhibits encouraging practical application for oil-water separation.     

Fabrication of mechanically robust superhydrophobic aluminum surface by acid etching and stearic acid modification

The aluminium surface with multi-scale structure has been fabricated via a facile and rapid solution-phase etching method by HCl/H₂O₂ etchants. After modification with stearic acid solution, the wettability of the etched aluminum surface turns into superhydrophobicity with an optimal water contact angle of 160° ± 2° and a sliding angle of 4° ± 1°. The processing conditions, such as the etching time, modifier types and the concentration of H₂O₂ are investigated to determine their effects on the surface morphology and wettability. As a result, the obtained sample shows excellent anti-adhesion property and bouncing phenomenon of water droplet. It can withstand mechanical abrasion for at least 100 cm under 12.3 kPa, or hydrostatic pressure under 24 ± 1 kPa without losing its superhydrophobicity, suggesting superior mechanical durability. Moreover, the surface also remains superhydrophobicity even after contacting corrosive liquids or long-term exposure in air over 100 days. Such a mechanically durable superhydrophobic aluminum surface can provide a promising practical application in various fields.     

Synthesis of new superhydrophobic nanosilica and investigation of their performance in reinforcement of polysiloxane

We reported a new facile method to synthesize superhydrophobic nanosilica using glycidoxypropyltrimethoxysilane and dodecylamine as treatment agents. Also, we systemically investigate their performance in reinforcement of poly(dimethylsiloxane) (PDMS) rubber. Fourier transform infrared spectrum, contact angle (CA) and thermogravimetric analysis (TGA) measurements were used to characterize the modified nanosilica. Results show that the inherent hydrophilicity of parent nanosilica surface can be greatly altered through this modification method. The CA of as‐prepared superhydrophobic nanosilica can reach 160.2°. The properties of as‐prepared modified nanosilica‐filled PDMS composites were systemically investigated by dynamic rheological test, scanning electron microscopy, TGA, dynamic mechanical analysis. These as‐prepared superhydrophobic nanosilica exhibit uniform dispersion in the PDMS matrix, and their composites also show good mechanical properties and distinct advantage on thermal stability compared with those of the pure silica‐filled PDMS composites. Also described is the probable mechanism for the reinforcement of as‐prepared superhydrophobic nanosilica‐filled PDMS. POLYM. COMPOS., 31:1628–1636, 2010. © 2009 Society of Plastics Engineers     

Enhancement of adhesion,mechanical strength and anti-corrosion by multilayer superhydrophobic coating embedded electroactive PANI/CNF nanocomposite

Traditional insulative coatings usually suffer from pitting corrosion in harsh corrosive environment. Herein, in this work, electroactive polyaniline/carboxylated carbon nanofiber (PANI/CNF) nanocomposite was prepared via in situ chemical polymerization and first incorporated into superhydrophobic coating with better barrier effect. Multilayer coatings were constructed by facial spraying using polyphenylene sulfide (PPS) and ethylene tetrafluoroethylene (ETFE) with gradient weight ratios as film-forming materials. The composite coating with 40 wt% ETFE in top layer (denoted as ETFE-40) possesses best superhydrophobicity and highest oleophobicity with water contact angle (CA) and glycerol CA of 160° and 155° as well as low water sliding angle (SA) and glycerol SA of 2.2° and 8.8°, respectively. The lotus-like nano/micro structures, low surface energy material ETFE and modification of 1H,1H,2H,2H-perfluorooctyltriethoxysilane (POTS) should contribute to the superior liquid repellency. Especially, robust mechanical strength and durable anti-wettability are obtained with high WCA of 151° and glycerol CA of 147° after 8000 cycles abrasion. The composite coating also exhibits strong adhesion and superior self-cleaning. The enhanced electrochemical corrosion resistance of the coating in 3.5 wt% NaCl solution can be attributed to the outstanding barrier function of superhydrophobic surface and the passivation effect of electroactive PANI/CNF. This novel and effective coating system would definitely benefit the development of robust protective coating and promise wider engineering application.     

Hydrophobic recovery of femtosecond laser processed silicone rubber insulator surfaces

This article demonstrates the loss and recovery in hydrophobicity of silicone rubber insulator surface processed by a femtosecond laser. The two stages of the wettability conversion were investigated. First, a rough micro/nano structure was formed on the original hydrophobic sample surface processed by the femtosecond laser, and the water contact angle on the surface was reduced from ~ 110° to a minimum of ~ 35°. This hydrophilicity loss was due to the increase in the hydrophilic  OH groups and the reduction of the hydrophobic  CH₃ groups on the surfaces. Second, the roughened samples were stored in a natural ambient environment. Over a certain storage time, the surface hydrophobicity recovered gradually and evolved into a superhydrophobic state. It was found that the migration of low molecular weight cycle and/or linear siloxane oligomers resulted in the recovery of the hydrophobicity property. Coupled with the increase of surface roughness caused by laser irradiation, the further evolution of the hydrophobicity was promoted. Moreover, the higher temperature accelerates the recovery of the surface hydrophobicity. The research on the conversion mechanism of the wettability on the silicone rubber insulator surface processed by femtosecond laser is of great significance for improving its reliability in practical applications.     

High stability superhydrophobic glass-ceramic surface with micro–nano hierarchical structure

Inspired by the surface structure of lotus leaves, micro–nano hierarchical surface structures have been widely used for designing superhydrophobic surfaces. However, the conventionally designed superhydrophobic surface structures are fragile. In this study, a layer of micron-sized mullite whiskers was grown using molten salt on the surface of BaAl₂Si₂O₈ (BAS) glass ceramics. Subsquently, SiO₂ nanoparticles modified with 1H,1H,2H,2H-perfluorodecyltriethoxysilane were sprayed onto the whisker layer to form a superhydrophobic surface. The nanoparticles exhibit superhydrophobicity, which is protected by the whisker layer containing pores and bulges. This prohibits direct contact between the nanoparticles and external objects. Contact and rolling angle tests indicated that the surface contact angle of the micro–nano hierarchical structure is 158° and the rolling angle is less than 10°. The stability of the superhydrophobic surface was tested through ultraviolet light, long-time immersion in solutions with various pH values, water scouring, and sandpaper abrasion. The results showed that the contact angle is greater than 150°. This study is expected to provide a simple and effective method for fabricating superhydrophobic surfaces on ceramics on a large scale.     

Superhydrophobic surfaces: a review on fundamentals,applications, and challenges

Superhydrophobicity is the tendency of a surface to repel water drops. A surface is qualified as a superhydrophobic surface only if the surface possesses a high apparent contact angle (>150°), low contact angle hysteresis (<10°), low sliding angle (<5°) and high stability of Cassie model state. Efforts have been made to mimic the superhydrophobicity found in nature (for example, lotus leaf), so that artificial superhydrophobic surfaces could be prepared for a variety of applications. Due to their versatile use in many applications, such as water-resistant surfaces, antifogging surfaces, anti-icing surfaces, anticorrosion surfaces etc., many methods have been developed to fabricate them. In this article, the fundamental principles of superhydrophobicity, some of the recent works in the preparation of superhydrophobic surfaces, their potential applications, and the challenges confronted in their new applications are reviewed and discussed.     

Superhydrophobicity of a three-tier roughened texture of microscale carbon fabrics decorated with silica spheres and carbon nanotubes

A stable superhydrophobic surface with low contact angle hysteresis using microscale carbon fabrics decorated with submicroscale silica (SiO₂) spheres and carbon nanotubes (CNTs) is created. Without any surface treatment, superhydrophobicity is achieved, and a microsized water drop can be suspended on the three-tier roughened surface, leaving an air film underneath the droplet. A modified Cassie–Baxter model analyzes that the combined effect of SiO₂ spheres and CNTs contributes a high area fraction of a water droplet in contact with air, leading to superhydrophobicity. Such a three-tier surface texture has robust superhydrophobic properties.     

A simple method for the fabrication of silica-based superhydrophobic surfaces

The present article reports on a simple and convenient method for the fabrication of superhydrophobic surfaces based on silica particles by spraying the as-prepared silica suspension containing silica sol and silica microspheres on the substrate. The morphologies of the silica particulate coatings could be controlled by varying the silica microsphere concentration. The silica particulate coatings as prepared were exceptionally rough and superhydrophilic, with water contact angles less than 5°. The surface silanol groups of the hydrophilic coatings could be functionalized using 1H,1H,2H,2H-perfluorodecyltriethoxysilane to form hydrophobic groups. The resulting surface showed excellent superhydrophobic property with water contact angle up to 165.6 ± 0.9° and sliding angle of 3.5 ± 0.4°. In addition, the superhydrophobicity of the coating possessed a good stability after 3 months of exposure in air for a wide range of pH values.     

Robust superhydrophobic fabrics by infusing structured polydimethylsiloxane films

Superhydrophobic coatings have large application potential in self-cleaning textiles. Low durability, high cost of fabrication, and environmental concerns over the usage of chemicals such as fluorocarbons limit the utilization of superhydrophobic coatings. This study reports a convenient and inexpensive approach to fabricate robust and fluorine-free superhydrophobic fabrics based on the transfer of structured polymer films and hydrophobic nanoparticles. In this approach, polydimethylsiloxane (PDMS) is infused between sheets of fabric and paper, followed by curing and removal of the paper. This process results in a fabric infused with PDMS whose structure is a negative replica of the paper surface. Then, hydrophobic nanoparticles are sprayed onto the structured PDMS side of the fabric. The infusion of PDMS and subsequent deposition of the hydrophobic nanoparticles enables strong bonding, as shown by the excellent solvent stability of the superhydrophobic fabric under ultrasonication. The proposed approach is universal in that it can be applied to almost any textiles, which upon coating, exhibited superhydrophobicity with a water contact angle of 172° and a sliding angle of 3°. Furthermore, the superhydrophobic fabric showed robust durability against water spray impact and mechanical bending where it can keep superhydrophobicity for at least 200 cycles of each test.     

耐腐蚀超疏水超亲油不锈钢网的制备及其在油水分离过程中的应用

以不锈钢网为基底,通过化学刻蚀法制备微米级粗糙表面,通过一步浸泡法将st9ber法制得的疏水亲油纳米Si O2颗粒沉积到粗糙的不锈钢网表面,制备了具有微纳二级粗糙结构的超疏水超亲油不锈钢网。利用扫描电子显微镜(SEM)、傅里叶变换红外光谱仪(FT-IR)和接触角测量仪(CA)表征了超疏水超亲油不锈钢网的表面形貌、化学组成和润湿性能,并将其用于油水分离过程中。结果表明,疏水亲油纳米Si O2颗粒成功的沉积到不锈钢网表面;水滴在超疏水超亲油不锈钢网上的接触角最大为151°,煤油的接触角为0°;制备的超疏水超亲油不锈钢网不仅能高效的分离不同种类油和水的混合物,还能高效的分离油和腐蚀性液体(强酸或强碱水溶液)的混合物,其耐腐蚀特性可满足复杂环境下的油水分离要求。     

CNCs增强相分离法构建PVDF/PDMS超疏水表面

采用非诱导相分离法，通过将纤维素纳米晶（CNCs）与两种聚合物（聚偏二氟乙烯和聚二甲基硅氧烷）进行结合，利用CNCs之间的静电排斥力及其高比表面积特性，有效降低相分离过程中聚合物的聚集，减小了颗粒尺寸，增强了颗粒分散性，在棉布、木板和玻璃表面构造了精细均匀的微纳米粗糙结构。采用FTIR、SEM、AFM、接触角测量仪、3D光学轮廓仪对CNCs和超疏水表面的形貌、结构和超疏水性进行表征。研究发现，棉布、木板和玻璃表面的水接触角分别最高可达158 °、156.8 °和153.8 °，滚动角最低分别为2 °、2.7 °和3.4 °，呈现出明显的超疏水特征。经过机械摩擦（500余次）、酸碱处理（pH 1～13）、温度变化（–40～40°C）以及紫外光照射（0～320 h）后，基材表面仍具有较好的超疏水性。此外，基材具有优异的自清洁性和油水分离效率，超疏水棉布的最高分离效率可达98.4%。     

Reversible Photocontrol of Wood-Surface Wettability Between Superhydrophilicity and Superhydrophobicity Based on a TiO2 Film

The reversible photocontrol of wood-surface wettability between superhydrophilicity and superhydrophobicity based on a TiO₂ film modified with octadecyl trichlorosilane (OTS) was achieved via a facile hydrothermal method at low temperature. Under UV illumination, the wood surface became superhydrophilic with a water contact angle (WCA) of approximately 0°. However, when placed in the dark, a superhydrophobic wood surface with a WCA of approximately 152° was achieved. The mechanism of the reversible photocontrol of wood-surface wettability is discussed in this article. This photocontrolled wood surface may have potential for wood self-cleaning or manipulation in response to indoor humidity.     

Facile and eco-friendly fabrication of hierarchical superhydrophobic coating from eggshell biowaste

This study reports a facile and sustainable approach to fabricate superhydrophobic coating from eggshell biowaste. The coating was prepared by ball milling chicken eggshells, composed of hydrophilic calcium carbonate (CaCO₃), to microsized particles followed by surface hydrophobilizing with stearic acid (C₁₇H₃₅COOH) to form low surface energy nanosized calcium stearate ((C₁₇H₃₅COO)₂Ca) through the esterification of hydroxyl groups (-OH) absorbed on a surface of CaCO₃ with carboxyl groups (–COOH) of stearic acid. Then, a layer of modified eggshell particles dispersed in polystyrene (PS) binder was dip-coated on a substrate. A coated surface with water contact angles of 151° ± 1° on glass and 153° ± 1° on cotton fabric substrates was achieved when a 4:1 weight ratio of the modified eggshell:PS was used. The uniform distribution of the modified eggshell particles throughout the coating led to a surface with high degree of hierarchical micro-nanoscale roughness which resulted in superhydrophobicity. The superhydrophobic eggshell coating showed good environmental stability, self-cleaning, and oil/water separation properties. These results suggest that eggshell biowaste can be utilized for superhydrophobic applications.     

A rapid two-step electroless deposition process to fabricate superhydrophobic coatings on steel substrates

The present study reports a simple, highly effective, and safe two-step electroless deposition process for rapidly fabricating superhydrophobic Ag coatings on steel substrates. The steel plates were first immersed in the 1?mol/L aqueous CuSO₄ solution for 20?s, and then immersed in the 0.03?mol/L aqueous AgNO₃ solution containing 1?wt% fluoroalkylsilane (FAS) for 2?min. The sample surfaces were characterized by energy-dispersive x-ray spectroscopy, Fourier transform infrared spectrophotometry (FTIR), x-ray diffraction, scanning electron microscopy, step profiler, and optical contact angle measurements. The results show that, after the two-step electroless deposition process, the Ag coatings composed of the binary micro/nanometer-scale rough structures containing the FAS molecules with a low surface energy are formed on the steel surfaces. The as-prepared Ag coatings exhibit a good superhydrophobicity with a 163.4?±?1.8° water contact angle and 1.5?±?0.5° rolling angle.     

Stable superhydrophobic surface based on low‐density polyethylene/ethylene‐propylene‐diene terpolymer thermoplastic vulcanizate

Stable superhydrophobic surface based on low‐density polyethylene (LDPE)/ethylene–propylene–diene terpolymer (EPDM) thermoplastic vulcanizate (TPV) was successfully fabricated by using etched aluminum foil as template. The etched aluminum template consisted of micropores and step‐like textures, was obtained by the metallographic sandpaper sanding and the subsequent acid etching. The surface morphology and hydrophobic properties of the series molded TPV surfaces were researched by varying the weight ratio of the LDPE/EPDM TPV. The superhydrophobic LDPE/EPDM TPV surfaces exhibited the microstructures consisting of step‐like textures obtained via molding with etched aluminum template and a large number of fiber‐like structures resulted from the plastic deformation of LDPE matrix. The obtained TPV (LDPE/EPDM weight ratio = 70/30) surface exhibited the remarkable superhydrophobicity, with a contact angle of 152.0° ± 0.7° and a sliding angle of 3.1° ± 0.8°. The molded TPV surface had excellent environmental stability when the pH of water solution was in the range of 1 to 14; moreover, the surface also showed the excellent resistance to various organic solvents. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46241.