Fabrication and characterization of a cotton candy like surface with superhydrophobicity

Superhydrophobic thin films were prepared on glass by air-brushing the in situ polymerization compositions of D₅/SiO₂. The wettability and morphology were investigated by contact angle measurement and scanning electron microscopy. The most superhydrophobic samples prepared had a static water contact angle of 157° for a 5 μl droplet and a sliding angle of ∼1° for 10 μl droplet. Thermal stability analysis showed that the surface maintained superhydrophobic at temperature up to 450 °C. Air trapping and capillary force on superhydrophobic behavior were evaluated.     

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.     

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.     

Optically transparent, superhydrophobic methyltrimethoxysilane based silica coatings without silylating reagent

The superhydrophobic surfaces have drawn lot of interest, in both academic and industries because of optically transparent, adherent and self-cleaning behavior. Surface chemical composition and morphology plays an important role in determining the superhydrophobic nature of coating surface. Such concert of non-wettability can be achieved, using surface modifying reagents or co-precursor method in sol-gel process. Attempts have been made to increase the hydrophobicity and optical transparency of methyltrimethoxysilane (MTMS) based silica coatings using polymethylmethacrylate (PMMA) instead of formal routes like surface modification using silylating reagents. The optically transparent, superhydrophobic uniform coatings were obtained by simple dip coating method. The molar ratio of MTMS:MeOH:H₂O was kept constant at 1:5.63:1.58, respectively with 0.5 M NH₄F as a catalyst and the weight percent of PMMA varied from 1 to 8. The hydrophobicity of silica coatings was analyzed by FTIR and contact angle measurements. These substrates exhibited 91% optical transmittance as compared to glass and water drop contact angle as high as 171 ± 1°. The effect of humidity on hydrophobic nature of coating has been studied by exposing these films at relative humidity of 90% at constant temperature of 30 °C for a period of 45 days. The micro-structural studies carried out by transmission electron microscopy (TEM).     

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 stable superhydrophobic polyphenylsilsesquioxane/nanosilica composite coatings

The superhydrophobic polyphenylsilsesquioxane (PPSQ)/nanosilica composite coatings were prepared by spray coating method with nano fumed silica (NFS) particles embedded in PPSQ matrix. The water contact angle (WCA) increased from 92.9° to 152.5° and the sliding angle (SA) decreased from more than 60° to 3.9° as the NFS content increased. The superhydrophobicity retained up to 500 °C, sustained by the hierarchical micro-nano structures and excellent thermal stability of PPSQ. A superhydrophobic PPSQ coating with WCA of 152.6° and SA of 7.8° was obtained by solvent-nonsolvent method for comparison as well. However, it gradually lost superhydrophobicity at 200 °C because of the elimination of nanostructures by the thermal softening of PPSQ.     

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.     

A stable superhydrophobic and superoleophilic Cu mesh based on copper hydroxide nanoneedle arrays

A superhydrophobic and superoleophilic copper mesh was prepared via a simple electrochemical route. Copper substrates were anodized in a 1 mol/L NaOH aqueous solution to produce a rough thin film of Cu(OH)₂ nanoneedle arrays and then the film was reacted with 1H,1H,2H,2H-perfluorooctyltriethoxysilane to form a very thin and stable hydrophobic coating layer. X-ray photoelectron spectroscopy (XPS) data revealed the coordination of silicon atoms with cuprate (CuO) molecules present on the anodized substrate. The water contact angle of the perfluoroalkylsilane-modified nanoneedle surface was approximately 170°. Furthermore, the superhydrophobicity was maintained after wet treatments in aqueous solutions with a wide pH range of 2−14 and after a long storage time of 4 months. This excellent durability and long-term reliability, which was unattainable in comparable samples modified with n-dodecanethiol or n-dodecanoic acid, could be interpreted with the formation of a stable and dense surface modification layer via a condensation reaction between -SiOEt and -CuOH and subsequent polymerization among the ethoxysilane adsorbates. Preliminary studies of the dynamic permeation behaviors of water and non-polar solvents exhibited a potential use of the hybrid copper mesh as a filtering layer for oil and water separation.     

Investigation into the photo-induced change in wettability of hydrophobized TiO2 films

The photo-induced change in wettability of hydrophobized TiO₂ films has been investigated for steel coated with acidic TiO₂ nanosols containing varying concentrations of dispersed nanocrystalline titania, such as Degussa P25. The photo-induced change in wettability was evaluated by measuring the time-dependent drop of water contact angle (WCA) after samples had been soaked in either n-octyltriethoxysilane (OTS) or decanoic acid (DA). TiO₂ films treated in this way exhibit superhydrophobic behaviour, with WCA greater than 160°. After radiation with UV (black light), the superhydrophobic properties are transformed into superhydrophilic properties, with WCA of almost 0°. As P25 content and layer thickness increase, high rates of photo-induced change are found, but a moderate calcination regime is required. On the other hand, hardness and E modulus pass through a maximum at 25 wt% P25, so that a P25 content between 25 and 50 wt% is the optimum for practical uses. With such stable coatings, wettability can be controlled over a wide range, and the switch between hydrophobic and hydrophilic states can be carried out repeatedly when DA is used as the hydrophobizing agent. Use of a low calcination temperature (450 °C) for the intermediate annealing of the single layers in multilayer coatings and a short final sintering step at a relatively high temperature (e.g. 630 °C for 10 min) allow the preparation of relatively thin TiO₂ films on steel with a high photoactivity.     

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.     

Superhydrophobic and icephobic surfaces prepared by RF-sputtered polytetrafluoroethylene coatings

A superhydrophobic and icephobic surface were investigated on aluminum alloy substrate. Anodizing was used first to create a micro-nanostructured aluminum oxide underlayer on the alloy substrate. In a second step, the rough surface was coated with RF-sputtered polytetrafluoroethylene (PTFE or Teflon^®). Scanning electron microscopy images showed a “bird's nest”-like structure on the anodized surface. The RF-sputtered PTFE coating exhibited a high static contact angle of ∼165° with a very low contact angle hysteresis of ∼3°. X-ray photoelectron spectroscopy (XPS) results showed high quantities of CF₃ and CF₂ groups, which are responsible for the hydrophobic behavior of the coatings. The performance of this superhydrophobic film was studied under atmospheric icing conditions. These results showed that on superhydrophobic surfaces ice-adhesion strength was 3.5 times lower than on the polished aluminum substrate.     

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.     

Fabrication of superhydrophobic coating via a facile and versatile method based on nanoparticle aggregates

Herein, we report a facile and low cost method for the fabrication of superhydrophobic surface via spin coating the mixture of polydimethylsiloxane precursor (PDMS) and silicon dioxide (SiO₂) nanoparticles. The surface hydrophobicity can be well tuned by adjusting the weight percent of PDMS and SiO₂. The water contact angle (WCA) can increase from 106.8 ± 1.2° on PDMS film to 165.2 ± 2.3° on PDMS/SiO₂ coating, companying with a change from adhering to rolling which was observed from tilting angle (TA) characterization. Multi-scale physical structures with SiO₂ nanoparticle aggregates and networks of SiO₂ nanoparticle aggregates are characterized by scanning electron microscopy (SEM) and atomic force microscope (AFM), and they can be observed more clearly from the AFM images treated with software (WSxM). Then the relationship between surface hydrophobicity and structures is further discussed based on Wenzel and Cassie models, indicating that the appearance of networks of nanoparticle aggregates is important in the Cassie state. The superhydrophobic coating can keep the superhydrophobicity at least for one month under environment conditions and readily regenerate after mechanical damage. Additionally, the superhydrophobic coating can be fabricated using other methods including dip coating, spray coating and casting. Thus, a large area of superhydrophobic coatings can be easily fabricated. Therefore the range of possible applications for these facile and versatile methods can be expanded to various actual conditions.     

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 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.     

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.     

Preparation of hybrid film with superhydrophobic surfaces based on irregularly structure by emulsion polymerization

A superhydrophobic surface originated from quincunx-shape composite particles was obtained by utilizing the encapsulation and graft of silica particles to control the surface chemistry and morphology of the hybrid film. The composite particles make the surface of film form a composite interface with irregular binary structure to trap air between the substrate surface and the liquid droplets which plays an essential role in obtaining high water contact angle and low water contact angle hysteresis. The water contact angle on the hybrid film is determined to be 154 ± 2° and the contact angle hysteresis is less than 5°. This is expected to be a simple and practical method for preparing self-cleaning hydrophobic surfaces on large area.     

Comparative studies on p-type CuI grown on glass and copper substrate by SILAR method

Depending upon the method of synthesis and the nature of substrate surface, there is variation in the physico-chemical properties of the material. Cuprous iodide films are deposited at room temperature on the glass and copper substrates by a simple SILAR method and the obtained results are compared. The p-type material with optical band gap 2.88 eV is found to be possessing face-centered cubic crystal structure with lattice parameter 6.134 Å. We observed irregular particles for the CuI film on the glass substrate while patterned arrays of micro-rods with cabbage like tips on copper substrate, for the same preparative conditions. Also, the material deposited on copper is showing superhydrophobic nature (contact angle ∼156°) while that on glass it is hydrophilic (contact angle ∼88°). We have characterized the thin films by X-ray diffraction, scanning electron microscopy, surface roughness and contact angle measurement, thermoelectric power measurement and optical studies. This hydrophobic, p-type material with wide band gap will be helpful in the development of optoelectronic devices.     

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.     

Electrostatic powder spraying process for the fabrication of stable superhydrophobic surfaces

Nano-sized Al₂O₃ particles were modified by heptadecafluorodecyl trimethoxysilane and 2,3-epoxy propoxy propyl trimethoxysilicane to make it both hydrophobic and reactive. The reactive nano-particles were mixed with polyester resin containing curing agents and electrostatic sprayed on stainless steel substrates to obtain stable superhydrophobic coatings after curing. The water contact angle (WCA) on the hybrid coating is influenced by the content of Al₂O₃ particles in the coating. As the Al₂O₃ concentration in the coating was increased from 0% to 8%, WCA increased from 68° to 165°. Surface topography of the coatings was examined using scanning electron microscopy (SEM). Nano-particles covered on the coating surface formed continuous film with greatly enhanced roughness, which was found to be responsible for the superhydrophobicity. The method is simple and cost effective and can be used for preparing self-cleaning superhydrophobic coating on large areas.