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.     

A simple solution-immersion process for the fabrication of superhydrophobic cupric stearate surface with easy repairable property

The present work reports a simple and time-saving method to fabricate cupric stearate film on zinc substrate by a solution-immersion process. Superhydrophobic surfaces are conventionally prepared employing two steps: roughening a surface and lowering its surface energy. The fabrication of superhydrophobic cupric stearate surface is reported using a one-step process by immersing a zinc plate coated with copper into the stearic acid solution, simplifying the complexity of two different steps involved in the conventional methods. The surface of the zinc plate coated with copper is found to be covered with low surface energy cupric stearate film providing the water contact angle of 160 ± 1° with the rolling off properties. In addition, the damaged superhydrophobic surface can restore superhydrophobicity property by immersing the surface into the stearic acid solution again.     

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.     

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.     

Fabrication of superhydrophobic copper surface with ultra-low water roll angle

Binary geometric structures at the micro- and nano-scale are fabricated on copper surfaces via simple sandblasting and surface oxidation process. The rough surfaces show excellent superhydrophobicity and ultra-low water roll angle (RA) after fluorination. The structure effect is deduced by comparing it with those of a single micro- or nano-scale structure. Such superhydrophobic copper surfaces can be widely used in many fields such as corrosion protection, liquid transportation without loss. Such a facile technique is expected to offer a feasible avenue for the industrial fabrication of superhydrophobic surfaces.     

Facile fabrication of large-scale stable superhydrophobic surfaces with carbon sphere films by burning rapeseed oil

Stable anti-corrosive superhydrophobic surfaces were successfully prepared with the carbon nanosphere films by means of depositing the soot of burning rapeseed oil. The method is extremely cheap, facile, time-saving and avoided any of the special equipments, special reagents and complex process control. The method is suitable for the large-scale preparation of superhydrophobic surface and the substrate can be easily changed. The as-prepared surfaces showed stable superhydrophobicity and anti-corrosive property even in many corrosive solutions, such as acidic or basic solutions over a wide pH range. The as-prepared superhydrophobic surface was carefully characterized by the field emission scanning electron microscopy and transmission electron microscope to confirm the synergistic binary geometric structures at micro- and nanometer scale. This result will open a new avenue in the superhydrophobic paint research with these easily obtained carbon nanospheres in the near future.     

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°.     

A simple method for the preparation of superhydrophobic PVDF-HMFS hybrid composite coatings

A superhydrophobic surface was obtained by embedding hydrophobically modified fumed silica (HMFS) particles in polyvinylidene fluoride (PVDF) matrix. The water contact angle (WCA) on the PVDF-HMFS hybrid composite coating is influenced by the content and nature of silica particles in the coating. As the silica concentration in PVDF matrix was increased from 33.3% to 71.4%, WCA increased from 117° to 168° and the sliding angle decreased from 90° to <1°. Surface topography of the coating was examined using scanning electron microscopy. An irregular rough surface structure composed of microcavities and nanofilaments 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 of different substrates.     

Facile fabrication of superhydrophobic polytetrafluoroethylene surface by cold pressing and sintering

A series of superhydrophobic polytetrafluoroethylene (PTFE) surfaces were prepared by a facile cold pressing and sintering method, and their microstructures and wetting behaviors could be artificially tailored by altering sintering temperature and using different masks. Specifically, the microstructures mainly depended on the sintering temperature, whereas the wetting behaviors, water contact angle (WCA) and sliding angle (SA), greatly hinged on both the sintering temperature and mask. Then a preferable superhydrophobic surface with WCA of 162 ± 2° and SA of 7° could be obtained when the sintering temperature was 360 °C and the 1000 grit abrasive paper was used as a mask. In addition, it was worth noting that the as-prepared surfaces exhibited excellent stability under UV illumination, which was the most key factor for them toward practical applications.     

Superhydrophobic silica films by sol–gel co-precursor method

Wetting phenomena of water droplets on solid are of crucial concern in our daily life as well as in engineering and science. The present paper describes the room temperature synthesis of superhydrophobic silica films on glass substrates using trimethylethoxysilane (TMES) as a co-precursor. The coating sol was prepared by keeping the molar ratio of tetraethoxysilane (TEOS) precursor, methanol (MeOH) solvent, water (H₂O) constant at 1:38.6:8.68, respectively, with 2 M NH₄OH throughout the experiments and the TMES/TEOS molar ratio (M) was varied from 0 to 1.1. It was found that with an increase in M value, the hydrophobicity of the films increased, however the optical transmission decreased from 88% to 82% in the visible range. The hydrophobic silica films retained their hydrophobicity up to a temperature of 275 °C and above this temperature the films became superhydrophilic. The hydrophobic silica films were characterized by Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), Fourier Transform Infrared (FT-IR) spectroscopy, percentage of optical transmission, humidity test and static and dynamic contact angle measurements.     

Preparation of lotus-like superhydrophobic fluoropolymer films

Styrene and 2,2,3,4,4,4-hexafluorobutyl methacrylate copolymers were synthesized by bulk polymerization, and the superhydrophobic copolymer films were prepared subsequently using phase separation technique. The copolymer was dissolved in tetrahydrofuran, and then added ethanol into the solution thereafter, to induce phase separation. The microstructures of the polymer films were controlled by the degree of phase separation, which was enhanced properly by the concentration of ethanol. The surface morphology of the films, observed by environmental scanning electron microscope, is similar to that of the lotus leaf. The contact angle and sliding angle were measured as 154.3° and 5.8°, respectively. The excellent superhydrophobic property demonstrated that the phase separation technique is useful for preparing lotus-like fluoropolymer films.     

Preparation of transparent BN films with superhydrophobic surface

A novel approach was investigated to obtain the superhydrophobicity on surfaces of boron nitride films. In this method boron nitride films were deposited firstly on Si(1 0 0) and quartz substrate using a radio frequency (RF) magnetron sputtering system, and then using CF₄ plasma treatment, the topmost surface area can be modified systematically. The results have shown that the water contact angle on such surfaces can be tuned from 67° to 159°. The films were observed to be uniform. The surfaces of films consist of micro-features, which were confirmed by Atomic Force Micrograph. The chemical bond states of the films were determined by Fourier Transform Infrared (FTIR) Spectroscopy, which indicate the dominance of B-N binding. According to the X-ray Photoelectron Spectroscopy analysis, the surface of film is mainly in BN phase. The micro-feature induced surface roughness is responsible for the observed superhydrophobic nature. The water contact angles measured on these surfaces can be modeled by the Cassie's formulation.     

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.     

Fabrication of superhydrophobic polyaniline films with rapidly switchable wettability

A superhydrophobic polyaniline (PANI) film has been fabricated by using a facile one-step spraying method. The PANI was synthesized via in situ doping polymerization in the presence of perfluorooctanoic acid (PFOA) as the dopant. The water contact angle of this superhydrophobic surface reaches to 156°. Both the surface chemical compositions and morphological structures were analyzed. A granular morphology of PANI with a moderate amount of nanofibers was obtained. Moreover, a rapid surface wettability transition between superhydrophobicity and superhydrophilicity can be observed when it is doped with PFOA and de-doped with base. The mechanism for this tunable wettability has been discussed in detail.     

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.     

Imparting superhydrophobic and biocidal functionalities to a polymeric substrate by the sonochemical method

Multifunctional substrates with superhydrophobic and biocidal properties are gaining interest for a wide range of applications; however, the production of such surfaces remains challenging. Here, the sonochemical method is utilized to impart superhydrophobicity and antimicrobial properties to a polyethylene (PE) sheet. This is achieved by sonochemically depositing nanoparticles (NPs) of a hydrophobic fluoro-polymer (FP) on the PE sheets. The polymer is a flexible, transparent fluoroplastic composed of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride in the form of a powder. The NPs of polymers are generated and deposited on the surface of the PE using ultrasound irradiation. Optimizing the process results in a homogeneous distribution of 110–200 nm of NPs on the PE surface. The coated surface displays a water-contact angle of 160°, indicating excellent superhydrophobicity. This superhydrophobic surface shows high stability under outdoor conditions for two months, which is essential for various applications. In addition, metal-oxide nanoparticles (CuO or ZnO NPs) were integrated into the polymer coating to achieve antibacterial properties and increase the surface roughness. The metal oxides were also deposited sonochemically. The antibacterial activity of the FP@ZnO and FP@CuO PE composites was tested against the bacterium Staphylococcus aureus, and the results show that the FP@CuO PE can effectively eradicate the bacteria. This study highlights the feasibility of using the sonochemical method to deposit two separate functions, opening up new possibilities for producing “smart” novel surfaces.     

Separating small amount of water and hydrophobic solvents by novel superhydrophobic copper meshes

A novel filtration device for the separation of small amount of water and hydrophobic solvents was proposed, and its separation efficiency was also quantitatively studied for the first time. This goal was achieved by a copper mesh with superhydrophobic and superoleophilic properties, which was fabricated by simply immersing in aqueous solution of NaOH and K₂S₂O₈, and subsequent modification with n-dodecanethiol. The results demonstrated that a slightly tilted copper mesh could separate small amount of hydrophobic solvents and water with high efficiency. This finding provides a new strategy to the development of functional filtration devices that may have many potential applications in the field such as biomedicine, microanalysis, purification, etc.     

Fabrication of superhydrophobic wood surface by a sol-gel process

The superhydrophobic wood surface was fabricated via a sol-gel process followed by a fluorination treatment of 1H, 1H, 2H, 2H- perfluoroalkyltriethoxysilanes (POTS) reagent. The crystallization type of silica nanoparticles on wood surface was characterized using X-ray diffraction (XRD), the microstructure and chemical composition of the superhydrophobic wood surface were described by scanning electron microscope (SEM) and energy dispersive spectrometer (EDS), the bonding force between the silica nanoparticles and POTS reagent was analyzed by Fourier transform infrared spectroscopy (FT-IR) and the superhydrophobic property of the treated sample was measured by contact angle (CA) measurements. An analytical characterization revealed that nanoscale silica spheres stacked uniformly over the wood surface, and with the combination of the high surface roughness of silica nanoparticles and the low surface free energy film of POTS on wood surface, the wood surface has turned its wetting property from hydrophilic into superhydrophobic with a water contact angle of 164° and sliding angle less than 3°.     

One-step electrodeposition process to fabricate cathodic superhydrophobic surface

In this work, a rapid one-step process is developed to fabricate superhydrophobic cathodic surface by electrodepositing copper plate in an electrolyte solution containing manganese chloride (MnCl₂·4H₂O), myristic acid (CH₃(CH₂)₁₂COOH) and ethanol. The superhydrophobic surfaces were characterized by means of scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The shortest electrolysis time for fabricating a superhydrophobic surface is about 1 min, the measured maximum contact angle is 163° and rolling angle is less than 3°. Furthermore, this method can be easily extended to other conductive materials. The approach is time-saving and cheap, and it is supposed to have a promising future in industrial fields.     

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.