Preparation and characterization of slice-like Cu2(OH)3NO3 superhydrophobic structure on copper foil

Superhydrophobic structure was prepared on copper foil via a facile solution-immersion method. Thus slice-like Cu₂(OH)₃NO₃ crystal was prepared on the surface of the copper foil by sequential immersing in an aqueous solution of sodium hydroxide and cupric nitrate. And the superhydrophobic structure was obtained by modifying the slice-like Cu₂(OH)₃NO₃ crystal with 1H,1H,2H,2H-perfluorodecyltriethoxysilane (FAS-17). The morphologies, chemical compositions and states, and hydrophobicity of the surface-modifying films on the copper foil substrates were analyzed by means of scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and water contact angle measurement. Moreover, the thermal stability of the slice-like structure was also evaluated using thermogravimetric analysis (TGA). It was found that roughening of the copper foil surface helped to increase the hydrophobicity to some extent, but no superhydrophobicity was obtained unless the slice-like Cu₂(OH)₃NO₃ crystal formed on the Cu substrate was modified with 1H,1H,2H,2H-perfluorodecyltriethoxysilane. Besides, the superhydrophobicity of the FAS-17-modified slice-like Cu₂(OH)₃NO₃ structure was closely related to the surface morphology. And this hydrophobic structure retained good superhydrophobic stability at elevated temperature and in long-term storage as well, which should be critical to the application of Cu-matrix materials in engineering.     

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.     

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.     

Facile preparation of superhydrophobic copper surface by HNO3 etching technique with the assistance of CTAB and ultrasonication

Superhydrophobic rough structure was prepared on copper wafer via HNO₃ etching technique with the assistance of Cetyltrimethyl Ammonium Bromide (CTAB) and ultrasonication. After modification of 1H,1H,2H,2H-perfluorodecyltriethoxysilane (FDTES), the copper wafer showed stable superhydrophobicity. The morphologies, chemical compositions and hydrophobicity of the substrates were analyzed by scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and water contact angle measurement. Dense and spherical micropits appeared on copper wafer after it was etched by 5 M nitric acid with 1.2 mM CTAB under ultrasonication for 20 min. The SEM results indicated that the joint action of CTAB and ultrasonication caused the formation of dense and spherical micropits.     

Thermal stability of HfO2 nanotube arrays

Thermal stability of highly ordered hafnium oxide (HfO₂) nanotube arrays prepared through an electrochemical anodization method in the presence of ammonium fluoride is investigated in a temperature range of room temperature to 900 °C in flowing argon atmosphere. The formation of the HfO₂ nanotube arrays was monitored by current density transient characteristics during anodization of hafnium metal foil. Morphologies of the as-grown and post-annealed HfO₂ nanotube arrays were analyzed by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Although monoclinic HfO₂ is thermally stable up to 2000 K in bulk, the morphology of HfO₂ nanotube arrays degraded at 900 °C. A detailed X-ray photoelectron spectroscopy (XPS) study revealed that the thermal treatment significantly impacted the composition and the chemical environment of the core elements (Hf and O), as well as F content coming from the electrolyte. Possible reasons for the degradation of the nanotube at high temperature were discussed based on XPS study and possible future improvements have also been suggested. Moreover, dielectric measurements were carried out on both the as-grown amorphous film and 500 °C post-annealed crystalline film. This study will help us to understand the temperature impact on the morphology of nanotube arrays, which is important to its further applications at elevated temperatures.     

Fabrication and surface characterization of biomimic superhydrophobic copper surface by solution-immersion and self-assembly

Biomimic superhydrophobic surfaces with contact angle greater than 150° and low sliding angle on copper substrate were fabricated by means of a facile solution immersion and surface self-assembly method. The scanning electron microscopy showed a nanoneedle structure copper surface with sporadic flower-like aggregates after treatment with sodium hydroxide and potassium persulfate solution. X-ray photoelectron spectroscopy and X-ray diffraction results confirmed that the formed nanoneedles were crystallized Cu(OH)₂. And the hydrophilic Cu(OH)₂ surface can be further modified into superhydrophobic through surface self-assembly with dodecanoic acid.     

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 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.     

Rapid fabrication of superhydrophobic surfaces on copper substrates by electrochemical machining

Hierarchical micrometer-nanometer-scale binary rough structures were fabricated on copper substrates by electrochemical machining in a neutral NaCl electrolyte. The rough structures are composed of the micrometer scale potato-like structures and the nanometer scale cube-like structures. After modified by the fluoroalkylsilane, the copper surfaces reached superhydrophobicity with a water contact angle of 164.3° and a water tilting angle less than 9°. This method has a high processing efficiency which can take just 3 s to fabricate the roughness required by the superhydrophobic surface. The effect of the processing time on wettability of the copper surfaces was investigated in this paper. The possible mechanism of the formation of the hierarchical roughness was also proposed, and the wettability of the copper surfaces was discussed on the basis of the Cassie-Baxter theory.     

Organic-inorganic hybrid superhydrophobic surfaces using methyltriethoxysilane and tetraethoxysilane sol-gel derived materials in emulsion

By applying alkaline-catalyzed co-hydrolysis and copolycondensation reactions of tetraethoxysilane (TEOS) and methyltriethoxysilane (MTES) in organic siloxane modified polyacrylate emulsion (OSPA emulsion), we are able to demonstrate the potential for developing a sol-gel derived organic-inorganic hybrid emulsion for a superhydrophobic surface research. TEOS and MTES derived sol-gel moieties can be designed for a physical roughness and hydrophobic characteristic (Si-CH₃) of the hybrid superhydrophobic surface, while OSPA emulsion can be endowed for good film-forming property. The effect of formulation parameters on superhydrophobicity and film-forming property was analyzed. The water contact angle (WCA) on the sol-gel derived hybrid film is determined to be 156°, and the contact angle hysteresis is 5° by keeping the mole ratio of TEOS:MTES:C₂H₅OH:NH₃·H₂O:AMP-95 at 1:4:30:10:0.63 and the mass percentage of OSPA emulsion at 25%. The nanoparticle-based silica rough surface is observed as the mole ratio of MTES/TEOS at 4:1. The sol-gel derived organic-inorganic hybrid emulsion shows remarkable film-forming property when the mole ratio of MTES/TEOS reaches or exceeds 4:1. With the primer coating, the performance of superhydrophobic film achieve actual use standard. It reveals that this new procedure is an effective shortcut to obtain a superhydrophobic surface with potential applications.     

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.     

Enhancement in hydrophobicity of silica films using metal acetylacetonate and heat treatment

Water is one of the most affecting chemicals that can cause damage to the solid surface. To protect the surface due to the action of water, the surface should be made hydrophobic. In the present study, the improvement in hydrophobicity of silica films using metal acetylacetonate (M-acac) by employing heat treatment to methyltrimethoxy silane (MTMS) based silica coatings is reported as a novel attempt. Instead of following the established trends of the surface derivatization or co-precursor method, iron acetylacetonate Fe(acac)₃, copper acetylacetonate Cu(acac)₂ and heat treatment were used to incorporate hydrophobicity with silica coatings. As M-acac is readily soluble in organic solvents, Fe(acac)₃ and Cu(acac)₂ were dissolved in methanol (MeOH) and their concentration was varied from 0 to 0.025 M. The coating solution was prepared by optimizing molar ratio of MTMS:MeOH:basic H₂O to 1:7.15:6.34, respectively. Gelation time (t_g) for Cu(acac)₂ containing silica sol and that containing Fe(acac)₃ were noted to be 30 and 55 min, respectively. The substrates were taken out after gelation and heat treated at 150 °C for 2 h. The heat treated films showed a dramatic increase in the static water contact angle from 82° to as high as 142°.     

Chemical synthesis of nanocrystalline SnO2 thin films for supercapacitor application

Nanocrystalline SnO₂ thin films were deposited by simple and inexpensive chemical route. The films were characterized for their structural, morphological, wettability and electrochemical properties using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy techniques (SEM), transmission electron microscopy (TEM), contact angle measurement, and cyclic voltammetry techniques. The XRD study revealed the deposited films were nanocrystalline with tetragonal rutile structure of SnO₂. The FT-IR studies confirmed the formation of SnO₂ with the characteristic vibrational mode of Sn-O. The SEM studies showed formation of loosely connected agglomerates with average size of 5-10 nm as observed from TEM studies. The surface wettability showed the hydrophilic nature of SnO₂ thin film (water contact angle 9°). The SnO₂ showed a maximum specific capacitance of 66 F g⁻¹ in 0.5 Na₂SO₄ electrolyte at 10 mV s⁻¹ scan rate.     

Highly ordered anodic TiO2 nanotube arrays and their stabilities as photo(electro)catalysts

Highly ordered TiO₂ nanotube arrays with an average diameter of 230 nm, a wall thickness of 30 nm and a length of 1.8 μm were fabricated within a large domain by electrochemically anodizing of a titanium foil in a mixed solution of glycerol and NH₄F aqueous electrolyte. The TiO₂ nanotubes exhibit an anatase structure after annealing at 450 °C in air for 3 h. The direct photolysis (DP), photocatalytic (PC), electrocatalytic (EC) and photoelectrocatalytic (PEC) activities of the TiO₂ nanotube arrays were investigated using methyl orange (MO) as the model pollutant. The degradation of MO in PC process is faster than that in DP process, which confirms the photocatalysis of TiO₂ nanotube arrays. The degradation rate in PEC process is much higher than those in EC and PC processes, which demonstrates the synergetic effect between PC and EC processes. The synergetic factor is 4.1, which suggests that the synergetic effect is strong. Moreover, the stabilities of morphology, structure and photo(electro)catalytic degradation performance of the TiO₂ nanotube arrays were studied in order to evaluate their applicability as photo(electro)catalysts. The photo(electro)catalytic experiments bring neither morphological nor structural modifications to the nanotube arrays. The photo(electro)catalytic degradation rates of the TiO₂ nanotube arrays maintain stable in 10 cycles, which indicates that the TiO₂ nanotube arrays are appropriate to be applied as photo(electro)catalysts.     

Super-hydrophobicity and oleophobicity of silicone rubber modified by CF4 radio frequency plasma

Owing to excellent electric properties, silicone rubber (SIR) has been widely employed in outdoor insulator. For further improving its hydrophobicity and service life, the SIR samples are treated by CF₄ radio frequency (RF) capacitively coupled plasma. The hydrophobic and oleophobic properties are characterized by static contact angle method. The surface morphology of modified SIR is observed by atom force microscope (AFM). X-ray photoelectron spectroscopy (XPS) is used to test the variation of the functional groups on the SIR surface due to the treatment by CF₄ plasma. The results indicate that the static contact angle of SIR surface is improved from 100.7° to 150.2° via the CF₄ plasma modification, and the super-hydrophobic surface of modified SIR, which the corresponding static contact angle is 150.2°, appears at RF power of 200 W for a 5 min treatment time. It is found that the super-hydrophobic surface ascribes to the coaction of the increase of roughness created by the ablation action and the formation of [-SiF_x(CH₃)_2−x-O-]_n (x = 1, 2) structure produced by F atoms replacement methyl groups reaction, more importantly, the formation of [-SiF₂-O-]_n structure is the major factor for super-hydrophobic surface, and it is different from the previous studies, which proposed the fluorocarbon species such as C-F, C-F₂, C-F₃, CF-CF_n, and C-CF_n, were largely introduced to the polymer surface and responsible for the formation of low surface energy.     

Controlled growth of superhydrophobic films by sol-gel method on aluminum substrate

Superhydrophobic surface was prepared by sol-gel method on aluminum substrate via immersing the clean pure aluminum substrate into the solution of zinc nitrate hexahydrate (Zn(NO₃)₂·6H₂O) and hexamethylenetetraamine (C₆H₁₂N₄) at different molar ratios and unchanged 0.04 mol/L total concentration, then heated at 95 °C in water bath for 1.5 h, subsequently modified with 18 alkanethiols or stearic acid. When the molar ratios of Zn(NO₃)₂·6H₂O and C₆H₁₂N₄ were changed from 10:1 to 1:1 the contact angle was higher than 150°. The best prepared surface had a high water contact angle of about 154.8°, as well as low angle hysteresis of about 3°. The surface of prepared films using Zn(NO₃)₂·6H₂O and C₆H₁₂N₄ composed of ZnO and Zn-Al LDH, and Al. SEM images of the film showed that the resulting surface exhibits different flower-shaped wurtzite zinc oxide microstructure and porous Zn-Al LDH. The special flowerlike and porous architecture, along with the low surface energy leads to the surface superhydrophobicity.     

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.     

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.     

Fabrication and characterizations of a polymer hybrid OA/MA/St-TiO2

A nano-hybrid composite of octadecyl acrylate/maleic anhydride/styrene (OA/MA/St) encapsulating nano-TiO₂ with an average particle size of 30-60 nm was fabricated based on chemical modification of nanotitania. The polymer hybrid OA/MA/St-TiO₂ and nano-TiO₂ were characterized by infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), static contact angle (CA) as well as transmission electron microscopy (TEM). FT-IR spectra and TGA results suggest that the copolymer OA/MA/St adheres on the surface of nano-TiO₂ through physical adsorption and chemical bonding. The calculated reacted OH surface density is about 0.6 OH/nm², and the modification efficiency is approximately 27.28%. In addition, when the molar ratio of OA/MA/St is 7:2:1, the hybrid shows the strongest hydrophobicity, and its static contact angle reaches as high as 146°. TEM image of the hybrid OA/MA/St-TiO₂ reveals that the modified particles have good dispersibility and compatibility with n-hexane.     

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.