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°.     

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).     

Control on wetting properties of spin-deposited silica films by surface silylation method

Control on the wettability of solid materials by liquid is a classical and key issue in surface engineering. Optically transparent water-repellent silica films have been spin-deposited on glass substrates at room temperature (∼27 °C). The wetting behavior of silica films was controlled by surface silylation method using dimethylchlorosilane (DMCS) as a silylating reagent. A coating sol was prepared by keeping the molar ratio of methyltrimethoxysilane (MTMS) precursor, methanol (MeOH) solvent, water (H₂O) constant at 1:8.8:2.64 respectively, with 4 M NH₄OH as a catalyst throughout the experiments and the amount of DMCS in hexane was varied from 0 to 12 vol.%. It was found that with an increase in vol.% of DMCS, the water contact angle values of the films increased from 78° to 136°. At 12 vol.% of DMCS, the film shows static water contact angle as high as 136° and water sliding angle as low as 18°. The hydrophobic silica films retained their water repellency up to a temperature 295 °C and above this temperature the films show superhydrophilic behavior. These results are compared with our earlier research work done on silylation of silica surface using hexamethyldisilazane (HMDZ) and trimethylchlorosilane (TMCS). The hydrophobic silica films were characterized by taking into consideration the Fourier transform infrared (FT-IR) spectroscopy, thermo gravimetric-differential thermal (TG-DT) analyses, scanning electron microscopy (SEM), atomic force microscopy (AFM), % of optical transmission, thermal and chemical aging tests, humidity tests, static and dynamic water contact angle measurements.     

Sliding behavior of water drops on sol-gel derived hydrophobic silica films

Control on the wettability of solid state materials is a classical and key issue in surface engineering. Optically transparent methyltriethoxysilane (MTES)-based silica films with water sliding angle as low as 9° were successfully prepared by two-step sol-gel co-precursor method. The emphasis is given to the effect of trimethylethoxysilane (TMES) as a co-precursor on water sliding behavior of silica films. The coating sol was prepared with molar ratio of methyltriethoxysilane (MTES), methanol (MeOH), acidic water (0.01 M, oxalic acid) and basic water (12 M, NH₄OH) kept constant at 1:12.73:3.58:3.58 respectively, and the molar ratio of TMES/MTES (M) was varied from 0 to 0.22. The static water contact angle as high as 120° and the water sliding angle as low as 9° was obtained by keeping the molar ratio (M) of TMES/MTES at 0.22. When the modified films were cured at temperature higher than 280 °C, the films became superhydrophilic. Further, the humidity study was carried out at a relative humidity of 90% at 30 °C over 60 days. We characterized the water repellent silica films by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), % of optical transmission, humidity tests and static and dynamic water contact angle (CA) measurements.     

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.     

Transparent water repellent silica films by sol-gel process

Non-wettable surfaces with high contact angles and facile sliding angle of water droplets have received tremendous attention in recent years. The present paper describes the room temperature (∼27 °C) synthesis of dip coated water repellent silica coatings on glass substrates using iso-butyltrimethoxysilane (iso-BTMS) as a co-precursor. Emphasis is given to the influence of the hydrophobic reagent (iso-BTMS) on the water repellent properties of the silica films. Silica sol was prepared by keeping the molar ratio of tetraethoxysilane (TEOS) precursor, methanol (MeOH) solvent, water (H₂O) constant at 1:16.53:8.26 respectively, with 0.01 M NH₄F throughout the experiment and the molar ratio of iso-BTMS/TEOS (M) was varied from 0 to 0.965. The effect of M on the surface structure and hydrophobicity has been researched. The static water contact angle values of the silica films increased from 65° to 140° and water sliding angle values decreased from 42° to 16° with an increase in the M value from 0 to 0.965. The water repellent silica films are thermally stable up to a temperature of 280 °C and above this temperature the film shows hydrophilic behavior. The water repellent silica films were characterized by the Fourier Transform Infrared (FT-IR) Spectroscopy, Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), % of optical transmission, thermal and chemical aging tests, humidity tests, static and dynamic water contact angle measurements.     

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.     

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.     

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.     

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 hierarchical surfaces fabricated by anodizing of oblique angle deposited Al-Nb alloy columnar films

A combined process of oblique angle magnetron sputtering and anodizing has been developed to tailor superhydrophobic surfaces with hierarchical morphology. Isolated submicron columns of single-phase Al-Nb alloys are deposited by magnetron sputtering at several oblique deposition angles on a scalloped substrate surface, with the gaps between columns increasing with an increase in the deposition angle from 70° to 110°. Then, the columnar films have been anodized in hot phosphate-glycerol electrolyte to form a nanoporous anodic oxide layer on each column. Such surfaces with submicron-/nano-porous structure have been coated with a fluoroalkyl phosphate layer to reduce the surface energy. The porous surface before coating is superhydrophilic with a contact angle for water is less than 10°, while after coating the contact angles are larger than 150°, being superhydrophobic. The beneficial effect of dual-scale porosity to enhance the water repellency is found from the comparison of the contact angles of the submicron columnar films with and without nanoporous oxide layers. The larger submicron gaps between columns are also preferable to increase the water repellency.     

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.     

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.     

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 cotton fabric coating based on a complex layer of silica nanoparticles and perfluorooctylated quaternary ammonium silane coupling agent

A superhydrophobic complex coating for cotton fabrics based on silica nanoparticles and perfluorooctylated quaternary ammonium silane coupling agent (PFSC) was reported in this article. The complex thin film was prepared through a sol-gel process using cotton fabrics as a substrate. Silica nanoparticles in the coating made the textile surface much rougher, and perfluorooctylated quaternary ammonium silane coupling agent on the top layer of the surface lowered the surface free energy. Textiles coated with this coating showed excellent water repellent property, and water contact angle (CA) increased from 133° on cotton fabrics treated with pure PFSC without silica sol pretreatment up to 145°. The oil repellency was also improved and the contact angle of CH₂I₂ droplet on the fabric surface reached to 131°. In contrast, the contact angle of CH₂I₂ on the fabric surface treated with pure PFSC was only 125°.     

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.     

Deposition of superhydrophobic nanostructured Teflon-like coating using expanding plasma arc

A novel approach was used to grow nanostructured Teflon-like superhydrophobic coatings on stainless steel (SS). In this method Teflon tailings were pyrolyzed to generate fluorocarbon precursor molecules, and an expanding plasma arc (EPA) was used to polymerize these precursors to deposit Teflon-like coating. The coating shows super hydrophobic behavior with water contact angle (WCA) of 165°. The coating was observed to be uniform. It consists of nanostructured (∼80-200 nm) features, which were confirmed by scanning electron microscopy. The chemical bond state of the film was determined by XPS and FTIR, which indicate the dominance of -CF₂ groups in the deposited coating. The combination of nanofeature induced surface roughness and the low surface energy imparted by Teflon-like coating is responsible for the observed superhydrophobic nature.     

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.     

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.     

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.