Facile preparation of superhydrophobic polyester surfaces with fluoropolymer/SiO2 nanocomposites based on vinyl nanosilica hydrosols

A facile method to prepare superhydrophobic fluoropolymer/SiO₂ nanocomposites coating on polyester (PET) fabrics was presented. The vinyl nanosilica (V? SiO₂) hydrosols were prepared via one‐step water‐based sol‐gel reaction with vinyl trimethoxy silane as the precursors in the presence of the base catalyst and composite surfactant. Based on the V? SiO₂ hydrosol, a fluorinated acrylic polymer/silica (FAP/SiO₂) nanocomposite was prepared by emulsion polymerization. The FAP/SiO₂ nanocomposites were coated onto the polyester fabrics by one‐step process to achieve superhydrophobic surfaces. The results showed that silica nanoparticles were successfully incorporated into the FAP/SiO₂ nanocomposites, and a specific surface topography and a low surface free energy were simultaneously introduced onto PET fibers. The prepared PET fabric showed excellent superhydrophobicity with a water contact angle of 151.5° for a 5 μL water droplet and a water shedding angle of 12° for a 15 μL. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40340.     

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.     

Superhydrophobic antireflective coating with high transmittance

The aim of this study is to fabricate a superhydrophobic antireflective (AR) coating that can be deposited on the covering of a solar cell system. First, AR coatings were synthesized on glass substrates with an average transmittance over 96% by layer-by-layer deposition of polyelectrolyte. Superhydrophobic sol gel was prepared by hydrolyzing tetraethoxysilane and then reacting it with hexamethyldisilazane. The sol gel, aged at 20°C for 96 h, was used to spin-coat a superhydrophobic film with a water contact angle of 163° and a transmittance of ~91%. The superhydrophobic sol gel was spin-coated on the top of an AR coating to form a superhydrophobic AR coating on a glass substrate. The average transmittance, advancing contact angle, and contact angle hysteresis of the superhydrophobic AR coating, which was spin-coated from sol gel aged for 96 h or 168 h, were 94.5 ± 0.7%, 154.0° ± 1.5°, and 15.4° ± 0.3° or 96.4 ± 0.2%, 158.4° ± 4.4°, and 1.8° ± 0.3°, respectively. Strategies for obtaining a superhydrophobic AR coating are discussed herein.     

Fabrication of superhydrophobic and self cleaning PVA-silica fiber coating on 304L SS surfaces by electrospinning

In this work superhydrophobic coating with self cleaning property is fabricated on 304L SS samples directly using a simple one step electrospinning process followed by silane treatment by using polyvinyl alcohol (PVA) and tetraethyl orthosilicate solution. A maximum water contact angle of 169.2° ± 2.1° is obtained at an electrospinning potential of 15 kV for 2 h, with a distance of 18 cm between the collector and needle. The hierarchical nanostructures thus formed on 304L SS composed of poly(vinyl alcohol)-silica microbeads and nanofibers. The surface morphologies are optimized by varying the electrospinning voltage, time, distance between needle and the collector and aging duration of the precursors. Attenuated total reflectance-infrared spectroscopy studies at different stages of preparation confirmed the presence of PVA/SiO₂ composite nanofibers deposited on the 304L SS surface. The reaction of SiO₂ nanofibers with hexamethyl disilazane resulted in the formation of Si O Si bonds that provided water repellent property. The developed SHP surface coating on 304L SS sample showed dynamic bouncing of water droplets and excellent self cleaning performance. The sample retained the SHP behavior in chloride solutions with different ionic strengths and pH.     

Fabrication of superhydrophobic transparent cyclic olefin copolymer (COC)-SiO2 nanocomposite surfaces

A superhydrophobic cyclic olefin copolymer (COC) nanocomposite coating was produced with a very simple and easy method. Self-cleaning superhydrophobic COC surfaces were obtained by only adding surface hydrophobized SiO₂ nanoparticles by dip coating method. The influence of concentration of SiO₂ and the coating temperatures on the wettability of the surfaces were investigated. The surface wettability of the coatings was examined with the contact angle measurements and the surface roughness and morphology were analyzed by using atomic force microscope and scanning electron microscopy analysis. Surfaces with certain amounts of COC and SiO₂ showed superhydrophobic character with high water contact angle of 169⁰. Also, the obtained superhydrophobic surfaces show superior water repellent, high transparency, and self-cleaning characteristics.     

Superhydrophobic and oleophilic micro‐nano hierarchical Pd‐decorated SiO2 layers

This paper reports a novel fluorinated micro‐nano hierarchical Pd‐decorated SiO₂ structure (hereafter called Pd/SiO₂), which was formed by the deposition of Pd nanoparticles (NPs) on SiO₂ microspheres. The SiO₂ layers with microscale roughness were fabricated by electrospraying a solution prepared using the sol‐gel process. Subsequently, the Pd NPs were deposited using an ultraviolet reduction process. The resulting surfaces exhibited a micro‐nano hierarchical morphology. After fluorination, the micro‐nano hierarchical surface exhibited outstanding water repellency with a water contact angle (WCA) of 170° and a sliding angle <5°, indicating excellent superhydrophobic properties. The layers exhibited good long‐term durability and excellent ultraviolet resistance. Interestingly, the surface was oleophilic (CA of oil ~10°). These results show the potential of employing superhydrophobic fluorinated Pd/SiO₂ layers in smart devices, such as self‐cleanable surfaces and intelligent water/oil separation systems.     

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.     

Preparation, characterization and wettability of porous superhydrophobic poly (vinyl chloride) surface

A porous superhydrophobic poly (vinyl chloride) surface was obtained by a simple approach. The water contact angle and the sliding angle of the superhydrophobic poly(vinyl chloride) surface were 154 ± 2.3o and 7o, respectively. The porous superhydrophobic PVC surface remained superhydrophobic property in the pH range from 1 to 13. When the superhydrophobic PVC surface was immersed in water with the temperatures ranging from 5 °C to 50 °C for 1 h to 30 days, the water contact angle remained higher than 150°. After outdoor exposure for 30 days, the contact angle still remained 150o.     

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.     

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.     

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.     

Preparation and anti‐icing property of a lotus‐leaf‐like superhydrophobic low‐density polyethylene coating with low sliding angle

A lotus‐leaf‐like superhydrophobic low‐density polyethylene (LDPE) coating with low sliding angle was prepared by a facile method. The water contact angle and sliding angle of the as‐prepared superhydrophobic LDPE coating were 156 ± 1.7° and 1°, respectively. The anti‐icing property of the as‐prepared LDPE coating with low sliding angle was investigated in a climatic chamber with a working temperature of ?5°C. The results showed that the superhydrophobic LDPE coating with low sliding angle can largely prevent ice formation on the surface, showing excellent anti‐icing property. The as‐prepared superhydrophobic LDPE coating with good anti‐icing property will be perfectly desirable for outdoor equipments to reduce ice formation on their surfaces in cold seasons. This work will provide a new way to fabricate anti‐icing coating and thus find applications in a variety of fields. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Facile fabrication of superhydrophobic raspberry‐like SIO2/polystyrene composite particles

A facile and novel strategy was reported on the fabrication of raspberry‐like SiO₂/polystyrene (SiO₂/PS) composite particles by emulsion polymerization in the presence of vinyl‐functionalized silica (vinyl‐SiO₂) particles, which were prepared via a one‐step sol–gel process using vinyltriethoxysilane as the precursor. The submicron vinyl‐SiO₂ particles were used as the core, and nanosized PS particles were then adsorbed onto the vinyl‐SiO₂ particles to form raspberry‐like composite particles during the polymerization process. The composition, morphology, and structure of the vinyl‐SiO₂ particles and the SiO₂/PS hybrid particles were characterized by thermogravimetric analysis, nuclear magnetic resonance, Fourier transform infrared spectroscopy, transmission electron microscopy, and scanning electron microscopy. Superhydrophobic surface can be constructed by directly depositing the raspberry‐like SiO₂/PS composite particles on glass substrate, and the water contact angle can be adjusted by the styrene/SiO₂ weight ratio. In addition, the superhydrophobic film possessed a strong adhesive force to pin water droplet on the surface even when the film was turned upside down. POLYM. COMPOS., 2013. © 2012 Society of Plastics Engineers     

A facile process for fabrication of environmentally safe superhydrophobic surfaces

Superhydrophobic coatings have opened new vistas in the field of self-cleaning surfaces by having improved performance, robustness and preservation of cleaning agents including water. Presently, fluoropolymers are extensively explored and used for this purpose. However, the major drawback accompanying fluoropolymers is formation of environmentally persistent and toxic compounds, viz. PFOA (perfluorooctanoic acid) and PFOS (perfluorooctanesulfonic acid) on their degradation raising concern on their use. In the present study, an effort has been made to develop a facile process by using an environmentally safe material. A simple dip coating technique is reported to fabricate superhydrophobic surface. SiO₂ nanoparticles of size 25–30 nm, prepared by sol–gel route, were dip-coated on glass substrate in multilayers followed by coating of a surfactant to achieve homogeneity of SiO₂ layers and enhanced binding with subsequent layer of NUVA-2114 [a commercially used fluorotelomer with chemical composition C₂F₆(CF₂CF₂) _n X]. It was observed that SiO₂ nanoparticles and sodium dodecyl sulfate (SDS) surfactant exhibit a synergistic effect on interface stability at optimized SDS concentration. A water contact angle of 152° is achieved. The established method is simple, scalable, environmentally safe and cost-effective.     

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.     

A new reutilization strategy of waste printed circuit board nonmetal powders for constructing superhydrophobic coatings

Reutilization of waste printed circuit board nonmetal powders (WPCBP) has been one of the major bottlenecks in the comprehensive utilization of electronic wastes. Herein, a new reutilization strategy of WPCBP was innovatively proposed to develop a superhydrophobic coating. Typically, WPCBP@SiO₂ hybrid filler was successfully prepared by the in-situ growth of silica on WPCBP surface, and the structures and compositions of WPCBP@SiO₂ were systematically investigated by SEM, FTIR, and TGA. Then the obtained WPCBP@SiO₂ was combined with polydimethylsiloxane (PDMS) to prepare a superhydrophobic coating. The as-prepared PDMS/WPCBP@SiO₂ coatings exhibited excellent superhydrophobicity and self-cleaning ability, whose static water contact angle (WCA) is more than 150° while the sliding angle (SA) is <10°. In summary, this study provides a green and efficient reutilization strategy of WPCBP in superhydrophobic coatings, which may open up a new opportunity for the high-valued utilization of WPCBP.     

超临界CO2快速膨胀法制备SiO2/聚氨酯超疏水涂层

用超临界CO₂快速膨胀法制备了SiO₂/聚氨酯超疏水涂层。首先用十三氟辛基三乙氧基硅烷（F-硅烷）和γ-(甲基丙烯酰氧基)丙基三甲氧基硅烷（KH-570）改性纳米二氧化硅,制备出含双键的纳米二氧化硅粒子,将其分散在超临界CO₂中,再利用超临界CO₂快速膨胀法将其喷射到双键封端的且已添加了引发剂的聚氨酯涂层表面,通过加热,使纳米二氧化硅粒子接枝在聚氨酯涂层表面,形成稳固粗糙结构,获得了超疏水性质。研究了喷嘴温度、反应釜温度和压力、偶联剂配比、表面粗糙度对涂层疏水性的影响。结果表明：涂层的静态水接触角可达到169.1°±0.6°;在喷嘴和釜内温度都为90℃,釜内压力为16 MPa,F-硅烷和KH-570配比为1∶1,表面粗糙度为7.3 μm时,所制得涂层具有较好的超疏水性,且具有优良的耐刮伤性。该法高效环保,涂层性能优良,适于大面积制备。     

Synthesis of superhydrophobic nanocomposite coating films for self-cleaning glass using nanoemulsion technique

This work aims to fabricate new potent superhydrophobic-hybrid coated nanocomposites used as a self-cleaning coating on the glass surface. Three (styrene/vinyl acetate) copolymers with monomer molar ratios of 0.06:0.17, 0.12:0.11, and 0.17:0.06 denoted as Z1-, Z2-, and Z3-copolymers were synthesized using the emulsion phase inversion concentration (EPIC) method. Two functionalized SiO₂-NPs using dodecyl triethoxysilane and hexadecyl trimethoxysilane as coupling agents denoted as E-NPs and F-NPs, respectively were fabricated by a sol–gel process to promote the hydrophobicity properties of the synthesized SiO₂-NPs. New hybrid composites denoted as P_y and T_y(y = 1, 2, and 3) were fabricated by incorporating 1, 3, and 5 wt% of the functionalized SiO₂-NPs (E-NPs or F-NPs) into the Z3-copolymers matrix, respectively. The chemical structures of the synthesized copolymers, unfunctionalized SiO₂-NPs, and the hybrid composites were elucidated by FTIR and ¹HNMR spectroscopes. The surface wettability and topography of the glass-surface coated by synthesized (styrene/vinyl acetate) copolymers and the silica hybrid composites were analyzed using water contact angle, scanning electron, and atomic force microscopes. The results showed that a highly superhydrophobic coated hybrid composite with a contact angle of 161.48° was achieved by Z3-copolymer/F5-NPs denoted as T3-composite at F5-NPs concentration of 5 wt%.     

Facile preparation of superhydrophobic and high oleophobic polymer composite coatings with self-cleaning,heat-resistance and wear-resistance

Superhydrophobic and high oleophobic PPS-matrix composite coatings with excellent self-cleaning, bending/heat/wear-resistance have been successfully prepared by a simple spray method through designing hierarchical structures and modifying with low surface energy groups in this work. The test results showed that the polyphenylene sulfide (PPS)/ 43 wt.% fluorinated ethylene propylene (FEP)/ polyetheretherketone (PEEK)/ 1 wt.% polydimethylsiloxane (PDMS) composite coatings exhibited superhydrophobic and high oleophobic simultaneously, with the highest contact angles of water, glycerine, ethylene glycol, crude oil and oil-water mixture up to 173 ± 1.5°, 156 ± 1.3°, 153 ± 1.3°, 151 ± 1.3° and 155 ± 1.3°, respectively. The wear life of the coating was recorded to be the longest reaching about 30 h without any surface damage until the wear test is terminated, which was 10 times of the PPS/PEEK coating. The intrinsic brittleness of PPS/PEEK coating can be avoided by the addition of FEP. Moreover, the coating can also keep superhydrophobic after immersing in strong acid and base solutions for 15 days. Under the condition of 200 °C for 1 h, the weight losses of the coatings were less than 3 % of the coating, showing outstanding heat-resistance. Under the condition of dirty, the coating also demonstrated the excellent self-cleaning effect, protecting substrates from pollution in practical applications. It is believed that our research provides a new approach to extending the life span of superhydrophobic coatings for petroleum pipeline.     

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.