Fabrication of a superhydrophobic ZnO nanorod array film on cotton fabrics via a wet chemical route and hydrophobic modification

A superhydrophobic ZnO nanorod array film on cotton substrate was fabricated via a wet chemical route and subsequent modification with a layer of n-dodecyltrimethoxysilane (DTMS). The as-obtained cotton sample was characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), scanning probe microscope (SPM) and X-ray photoelectron spectroscopy (XPS), respectively. The wettability of the cotton fabric sample was also studied by contact angle measurements. The modified cotton fabrics exhibited superhydrophobicity with a contact angle of 161° for 8 μL water droplet and a roll-off angle of 9° for 40 μL water droplet. It was shown that the proper surface roughness and the lower surface energy both played important roles in creating the superhydrophobic surface, in which the Cassie state dominated.     

A novel method to fabricate superhydrophobic surfaces based on well-defined mulberry-like particles and self-assembly of polydimethylsiloxane

A superhydrophobic surface was obtained by combining application of CaCO₃/SiO₂ mulberry-like composite particles, which originated from violent stirring and surface modification, and self-assembly of polydimethylsiloxane. Water contact angle and sliding angle of the superhydrophobic surface were measured to be about 164 ± 2.5° and 5°, respectively. The excellent hydrophobicity is attributed to the synergistic effect of micro-submicro-nano-meter scale roughness (fabricated by composite particles) and the low surface energy (provided by polydimethylsiloxane). This procedure makes it possible for widespread applications of superhydrophobic film due to its simplicity and practicability.     

Room temperature synthesis of water repellent silica coatings by the dip coat technique

The present paper describes the room temperature synthesis of dip coated water repellent silica coatings onto stainless steel substrates using 1,1,1,3,3,3-hexamethyldisilazane as a surface modifying agent. The hydrophobic property of the silica coating was enhanced by increasing its surface roughness, which was achieved by a proper control over the MeOH/TMOS molar ratio (S) during the synthesis. The contact angle of a water droplet (10 μl) increased from 72° to 145° with an increase in the S value from 9.1 to 36.4. The silica coating showed a minimum sliding angle of 15° for a water droplet of 10 μl. The water repellent silica coatings are thermally stable up to a temperature of 340 °C. The results have been discussed by taking into consideration the contact angle measurements, surface morphology and sol-gel parameters.     

Preparation of superhydrophobic films on titanium as effective corrosion barriers

Stable superhydrophobic films were prepared on the electrochemical oxidized titania/titanium substrate by a simple immersion technique into a methanol solution of hydrolyzed 1H,1H,2H,2H-perfluorooctyltriethoxysilane [CF₃(CF₂)₅(CH₂)₂Si(OCH₂CH₃)₃, PTES] for 1 h at room temperature followed by a short annealing at 140 °C in air for 1 h. The surface morphologies and chemical composition of the film were characterized by means of water contact angle (CA), field emission scanning electron microscopy (FESEM), atomic force microscope (AFM) and X-ray photoelectron spectroscopy (XPS). The water contact angle on the surface of this film was measured to be as high as 160°. SEM images showed that the resulting surfaces exhibited special hierarchical structure. The special hierarchical structure along with the low surface energy leads to the high surface superhydrophobicity. The corrosion resistance ability and durance property of the superhydrophobic film in 3.5 wt.% NaCl solution was evaluated by the electrochemical impedance spectroscopy (EIS). The anticorrosion properties of the superhydrophobic film are compared to those of unmodified pure titanium and titania/titanium substrates. The results showed that the superhydrophobic film provides an effective corrosion resistant coating for the titanium metal even with immersion periods up to 90 d in the 3.5 wt.% NaCl solution, pointing to promising future applications.     

Fabrication of superhydrophobic cotton fabrics by silica hydrosol and hydrophobization

Superhydrophobic cotton fabrics were prepared by the incorporation of silica nanoparticles and subsequent hydrophobization with hexadecyltrimethoxysilane (HDTMS). The silica nanoparticles were synthesized via sol-gel reaction with methyl trimethoxy silane (MTMS) as the precursor in the presence of the base catalyst and surfactant in aqueous solution. As for the resulting products, characterization by particle size analyzer, scanning electron microscopy (SEM), scanning probe microscopy (SPM), X-ray photoelectron spectroscopy (XPS), and thermal gravimetric analysis (TGA) were performed respectively. The size of SiO₂ nanoparticles can be controlled by adjusting the catalyst and surfactant concentrations. The wettability of cotton textiles was evaluated by the water contact angle (WCA) and water shedding angle (WSA) measurements. The results showed that the treated cotton sample displayed remarkable water repellency with a WCA of 151.9° for a 5 μL water droplet and a WSA of 13° for a 15 μL water droplet.     

Transparent Superhydrophobic silica coatings on glass by sol-gel method

Wetting behavior of solid surfaces is a key concern in our daily life as well as in engineering and science. In the present study, we demonstrate a simple dip coating method for the preparation of Thermally stable, transparent superhydrophobic silica films on glass substrates at room temperature by sol-gel process. The coating alcosol was prepared by keeping the molar ratio of methyltriethoxysilane (MTES), trimethylmethoxysilane (TMMS), methanol (MeOH), water (H₂O) constant at 1:0.09:12.71:3.58, respectively with 13 M NH₄OH throughout the experiments and the films were prepared with different deposition time varied from 5 to 25 h. In order to improve the hydrophobicity of as deposited silica films, the films were derivatized with 10% trimethylchlorosilane (TMCS) as a silylating agent in hexane solvent for 24 h. Enhancement in wetting behavior was observed for surface derivatized silica films which showed a maximum static water contact angle (172°) and minimum sliding angle (2°) for 25 h of deposition time. The superhydrophobic silica films retained their superhydrophobicity up to a temperature of 550 °C. The silica films were characterized by field emission scanning electron microscopy (FE-SEM), surface profilometer, Fourier transform infrared (FT-IR) spectroscopy, thermo-gravimetric and differential thermal analysis (TG-DTA), percentage of optical transmission, water contact angle measurements. The imperviousness behavior of the films was tested with various acids.     

Thermal effect on superhydrophobic performance of stearic acid modified ZnO nanotowers

The thermal desorption of stearic acid on superhydrophobic zinc oxide nanotowers has been investigated. The stearic acid passivated zinc oxide nanotowers provide a very high contact angle of ∼173 ± 1.1° with a very low hysteresis of ∼1.4 ± 0.5° due to the presence of a binary structure composed of several nanosteps on each nanotower of height ∼700 nm that eventually reduces the area of contact between the drop and the nanotowers and trapping more air as revealed by the field emission scanning electron microscopy images. The superhydrophobic performance of these nanotowers, however, declines following annealing at elevated temperatures. Fourier transform infrared spectra show a reduction in the intensity of stearic acid -CH_n peaks at elevated temperatures revealing the cause of the decrease in contact angle and confirming the occurrence of thermal desorption at 184 °C. The corresponding activation energy for desorption determined from our data is 0.34 ± 0.05 eV. It is found that the stearic acid has completely disappeared at 350 °C, making the sample hydrophilic.     

Mechanically stable and corrosion resistant superhydrophobic sol-gel coatings on copper substrate

Development of the anticorrosion coatings on metals having both passive matrix functionality and active response to changes in the aggressive environment has raised tremendous interest in material science. Using a sol-gel deposition method, superhydrophobic copper substrate could be obtained. The best hydrophobic coating sol was prepared with methyltriethoxysilane (MTES), methanol (MeOH), and water (as 7 M NH₄OH) at a molar ratio of 1:19.1:4.31 respectively. The surface morphological study showed the ball like silica particles distributed on the copper substrate with particle sizes ranging from 8 to 12 μm. The coatings showed the static water contact angle as high as 155° and the water sliding angle as low as 7°. The superhydrophobic nature was maintained even though the deposited copper substrate was soaked for 100 h in 50% of HCl solution. The coatings are stable against humidity and showed superhydrophobic behavior even after 90 days of exposure. The coatings are mechanically stable and water drops maintained the spherical shape on the bent copper substrate, which was bent more than 90°.     

Preparation and properties of ZnS superhydrophobic surface with hierarchical structure

A novel ZnS hierarchical structure composed of nanorod arrays with branched nanosheets and nanowires grown on their upside walls, was synthesized over Au-coated silicon substrate via chemical vapor deposition technique. Contact angle and sliding angle of this hierarchical film with no surface modification were measured to be about 153.8° and 9.1° for 5 μl water droplets. Self-cleaning behavior and dynamic water-repelling performance were clearly demonstrated. In addition, electrowetting transition phenomenon from superhydrophobic to hydrophilic state happened when a critical bias ∼7.0 V was applied. Below this threshold voltage, the contact angle change is little. This work for the first time reports the creation of ZnS superhydrophobic surface and could enrich its research field as surface functional materials.     

High-throughput characterization of BixY3−xFe5O12 combinatorial thin films by magneto-optical imaging technique

Bi_xY_3−xFe₅O₁₂ thin films have been grown on GGG (Gd₃Ga₅O₁₂) (1 1 1) substrates by the combinatorial composition-spread techniques under substrate temperature (T_sub) ranging from 410 to 700 °C and O₂ pressure of 200 mTorr. In order to study the effect of substrates on the deposition of Bi_xY_3−xFe₅O₁₂ thin films, garnet substrates annealed at 1300 °C for 3 h were also used. Magneto-optical properties were characterized by our home-designed magneto-optical imaging system. From the maps of Faraday rotation angle θ_F, it was evident that the Faraday effect appears only when T_sub = 430-630 °C. θ_F reaches to the maximum value (∼6°/μm, λ = 632 nm) at 500 °C, and is proportional to the Bi contents. XRD and EPMA analyses showed that Bi ions are easier to substitute for Y sites and better crystallinity is obtained for annealed substrates than for commercial ones.     

Superhydrophobicity of polytetrafluoroethylene thin film fabricated by pulsed laser deposition

Superhydrophobic polytetrafluoroethylene (PTFE) thin films were obtained by pulsed laser deposition (PLD) technique carried out with KrF excimer laser (λ = 248 nm) of about 1 J/cm² at a pressure of 1.33 Pa. The samples exhibit high water contact angle of about 170° and the sliding angle smaller than 2°. From studying the surface morphology of the prepared films, it is believed that the nano-scale surface roughness has enhanced the hydrophobic property of the PTFE. The increase of trapping air and reducing liquid-solid contact area due to the rough surface, as suggested by the Cassie-Baxter's model, should be responsible for superhydrophobicity of the PLD prepared films. This study thus provides a convenient one-step method without using wet-process to produce a superhydrophobic surface with good self-cleaning properties.     

Superhydrophobic surfaces based on dandelion-like ZnO microspheres

This study presents a simple method to fabricate superhydrophobic surface based on ZnO nanoneedles. ZnO nanoneedles had been constructed on zinc layers by immersing in an aqueous NH₄OH solution at 80 °C. The ZnO films were characterized by X-ray diffraction, scanning electron microscopy and X-ray photoelectron spectroscopy. The ZnO films exhibited excellent superhydrophilicity (contact angle for water was 0°), while they changed wettability to superhydrophobicity with a water contact angle greater than 150° after further chemical modification with n-dodecanoic acid. The procedure reported here only needs readily available reagents and laboratory equipments, which can be applied to various substrates of any size and shape.     

Roles of oleic acid during micropore dispersing preparation of nano-calcium carbonate particles

In the present work, nano-calcium carbonate powder was prepared by micropore dispersion method with assistance of oleic acid as surfactant. CO₂ gas was dispersed into the Ca(OH)₂/H₂O slurry via a glass micropore-plate with the diameter of micropore about 20 μm. To investigate the effect of oleic acid on the size of CaCO₃ particles, different amount of oleic acid was added in Ca(OH)₂/H₂O slurry at 5 °C and 25 °C, respectively. XRD patterns show that cubic calcite is the only crystalline phase in all cases. ZPA data and TEM photo indicate that the average particle size synthesized at 5 °C without oleic acid is of about 40 nm, slightly smaller than that of prepared at 25 °C, and that the dispersity of sample prepared at 5 °C is better than that of 25 °C. When oleic acid is added in both temperatures, the average particle size decreases a little. FT-IR spectra demonstrate that oleic acid interacts with Ca²⁺ and carbon-carbon double bond existed on the surface of particle. Consequently, two opposite roles of oleic acid during the process of preparation of nano-CaCO₃ were proposed, namely preventing nanoparticles from growing during reaction and making nanoparticles reunite to a certain extent after reaction.     

Design and fabrication of a TiO2/nano-silicon composite visible light photocatalyst

Nano-silicon (nc-Si) was utilized as the charges generator to promote the photocatalytic and super-hydrophilic reactivity of TiO₂ film under visible light irradiation. The photocatalytic ability of TiO₂/nc-Si composite photocatalyst was evaluated by a set of experiments to photodecompose 100 ppm methylene blue (MB) in aqueous solution. And the super-hydrophilic property was characterized by measuring the water droplet contacts angle, under visible light irradiation in atmospheric air and at room temperature. Under 100 mW/cm² visible light irradiation, the droplet contact angles were reduced to 0° within 4 h with nc-Si charge generator. Additionally, the rate constant of MB photo-degradation was promoted 6.6 times.     

Fabrication of superhydrophobic surfaces on zinc substrates

Stable superhydrophobic surfaces were fabricated on the zinc substrates through simple silver replacement deposition process with the modification of octadecyl mercaptan. The effects of reaction conditions on the surface morphology and wettability of the prepared surfaces were carefully studied. The results show that the fabrication of a best superhydrophobic surface depends largely on the moderate reactant concentration. When the concentration of AgNO₃ solution was 2 mmol/L, the zinc substrate was covered by a dendritic outline structure. Aggregated silver nanoparticles were formed on the substrate in accordance with some certain laws, exhibiting great surface roughness. The typical hierarchical micro-nanostructures, flower-like structures and porous structures also could be found from the SEM images. The maximal water contact angle (CA) value of about 161 ± 2°, and the minimal sliding angle (SA) of about 2° were obtained under the same reaction condition.     

Wetting and superhydrophobic properties of PECVD grown hydrocarbon and fluorinated-hydrocarbon coatings

Wetting characteristics of micro-nanorough substrates of aluminum and smooth silicon substrates have been studied and compared by depositing hydrocarbon and fluorinated-hydrocarbon coatings via plasma enhanced chemical vapor deposition (PECVD) technique using a mixture of Ar, CH₄ and C₂F₆ gases. The water contact angles on the hydrocarbon and fluorinated-hydrocarbon coatings deposited on silicon substrates were found to be 72° and 105°, respectively. However, the micro-nanorough aluminum substrates demonstrated superhydrophobic properties upon coatings with fluorinated-hydrocarbon providing a water contact angle of ∼165° and contact angle hysteresis below 2° with water drops rolling off from those surfaces while the same substrates showed contact angle of 135° with water drops sticking on those surfaces. The superhydrophobic properties is due to the high fluorine content in the fluorinated-hydrocarbon coatings of ∼36 at.%, as investigated by X-ray photoelectron spectroscopy (XPS), by lowering the surface energy of the micro-nanorough aluminum substrates.     

Superhydrophobic sol-gel nanocomposite coatings with enhanced hardness

Sol-gel superhydrophobic coatings with improved hardness were prepared by embedding fumed silica nanoparticles in a partially condensed hybrid sol of methyltriethoxysilane (MTEOS) and colloidal silica. Fumed silica particles of size 25-30 nm were incorporated in the sol and the mixture was spray-coated on glass substrate. Water contact angle (WCA) of the composite coating increased with increase in silica content of the sol mixture. The concentration of silica in the sol mixture was optimized to obtain robust superhydrophobic coatings with a WCA of 162.5° and a pencil hardness of 5H. The wetting state of water droplet on the sol-gel composite coatings was analysed with both Wenzel and Cassie-Baxter models.     

Superhydrophobic brocades modified with aligned ZnO nanorods

A superhydrophobic ZnO oriented nanorods coating on brocade substrate was prepared by a low-temperature wet chemical route, and the corresponding waterproof properties were evaluated. From wetting measurement, the modified brocades have a water contact angle of ∼152° and roll-off angle of 9° to a 10 μL water-droplet. A direct immersion of the modified brocades in water gives a strongly water-repellent behavior. The obtained waterproof brocades offer an opportunity for fabricating some special and protective drygoods.     

Superhydrophobic cotton fabric fabricated by electrostatic assembly of silica nanoparticles and its remarkable buoyancy

Highly hydrophilic cotton fabrics were rendered superhydrophobic via electrostatic layer-by-layer assembly of polyelectrolyte/silica nanoparticle multilayers on cotton fibers, followed with a fluoroalkylsilane treatment. The surface morphology of the silica nanoparticle-coated fibers, which results in the variety of the hydrophobicity, can be tailored by controlling the multilayer number. Although with the static contact angle larger than 150°, in the case of 1 or 3 multilayers, the fabrics showed sticky property with a high contact angle hysteresis (>45°). For the cotton fabrics assembled with 5 multilayers or more, slippery superhydrophobicity with a contact angle hysteresis lower than 10° was achieved. The buoyancy of the superhydrophobic fabric was examined by using a miniature boat made with the fabric. The superhydrophobic fabric boat exhibited a remarkable loading capacity; for a boat with a volume of 8.0 cm³, the maximum loading was 11.6 or 12.2 g when the boat weight is included. Moreover, the superhydrophobic cotton fabric showed a reasonable durability to withstand at least 30 machine washing cycles.     

Fabrication of superhydrophobic binary nanoparticles/PMMA composite coating with reversible switching of adhesion and anticorrosive property

Ag-TiO₂-Thiol/Poly(methyl methacrylate) (PMMA) coating has been prepared via adsorbed-layer nanoreactor technique and self-assembling method. The composite coating shows a superhydrophobic property with reversible switching of adhesion. In the UV-vis spectra, absorption appeared in ultraviolet region of 229-293 nm (UVC region) and 320-370 nm (UVA region). Additionally, the stability of the superhydrophobic surface was tested under the following conditions: (1) in basic solution (pH = 14); (2) in acid solution (pH = 1); (3) in artificial seawater. The coating shows stability since the contact angle of the sample still remained higher than 150° in the above conditions. The corrosion resistance of the superhydrophobic surfaces was investigated by electrochemical measurements and the results revealed that the superhydrophobic coatings are anticorrosive well.