Fabrication of superhydrophobic nanostructured surface on aluminum alloy

A superhydrophobic surface was prepared by consecutive immersion in boiling water and sputtering of polytetrafluoroethylene (PTFE or Teflon®) on the surface of an aluminum alloy substrate. Immersion in boiling water was used to create a micro-nanostructure on the alloy substrate. Then, the rough surface was coated with RF-sputtered Teflon film. The immersion time in boiling water plays an important role in surface morphology and water repellency of the deposited Teflon coating. Scanning electron microscopy images showed a “flower-like” structure in first few minutes of immersion. And as the immersion time lengthened, a “cornflake” structure appeared. FTIR analyses of Teflon-like coating deposited on water treated aluminum alloy surfaces showed fluorinated groups, which effectively reduce surface energy. The Teflon-like coating deposited on a rough surface achieved with five-minute immersion in boiling water provided a high static contact angle (～164°) and low contact angle hysteresis (～4°).     

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.     

Deposition of thick and adherent Teflon-like coating on industrial scale stainless steel shell using pulsed dc and RF PECVD

A unique combination of pulsed dc and radio frequency (RF) discharge deposition was used to deposit thick (∼5 μm) and adherent (2-4 MPa) Teflon-like coatings on a stainless steel (SS) shell of 2 m diameter size, through plasma enhanced chemical vapor deposition (PECVD). The details of deposition on such a big industrial scale component are reported for the first time. In this method, highly adherent thin interface layers were grown on SS shell that was electrically grounded, using pulsed dc discharge, followed by RF discharge deposition to build up the required coating thickness. The fluorocarbon precursor molecules, required for the deposition of Teflon-like coating, are generated indigenously by pyrolyzing the Teflon powder. The deposited coating was studied for its chemical bond state, surface roughness (Ra), morphology, thickness, and adhesive strength. These studies were carried out by using XPS, AFM, SEM, etc. The adhesive strength of the coating was measured by pin-pull test as per ASTM D4541 standard test. The coatings deposited with pulsed dc discharge were observed to have higher adhesive strength when compared with those deposited with RF discharge.     

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.     

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.     

Anti-icing performance of superhydrophobic surfaces

This article studies the anti-ice performance of several micro/nano-rough hydrophobic coatings with different surface chemistry and topography. The coatings were prepared by spin-coating or dip coating and used organosilane, fluoropolymer or silicone rubber as a top layer. Artificially created glaze ice, similar to the naturally accreted one, was deposited on the nanostructured surfaces by spraying supercooled water microdroplets (average size ∼80 μm) in a wind tunnel at subzero temperature (−10 °C). The ice adhesion strength was evaluated by spinning the samples in a centrifuge at constantly increasing speed until ice delamination occurred. The results show that the anti-icing properties of the tested materials deteriorate, as their surface asperities seem to be gradually broken during icing/de-icing cycles. Therefore, the durability of anti-icing properties appears to be an important point for further research. It is also shown that the anti-icing efficiency of the tested superhydrophobic surfaces is significantly lower in a humid atmosphere, as water condensation both on top and between surface asperities takes place, leading to high values of ice adhesion strength. This implies that superhydrophobic surfaces may not always be ice-phobic in the presence of humidity, which can limit their wide use as anti-icing materials.     

Facile method to prepare stable superhydrophobic Co3O4 surface

A facile and novel method was developed to fabricate rough Co₃O₄ surface with hierarchical micro- and nanostructures by the combination of simple solid state reactions and coating process. After modification with stearic acid, a superhydrophobic surface with water contact angle of 155 ± 1.8° and sliding angle of 2° was obtained. The superhydrophobic Co₃O₄ surface remained superhydrophobic property in a wide pH range from 3 to 14. The superhydrophobic Co₃O₄ surface also showed excellent self-cleaning property and high stability in ambient environments.     

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 of superhydrophobic wood surfaces via a solution-immersion process

Superhydrophobic wood surfaces were fabricated from potassium methyl siliconate (PMS) through a convenient solution-immersion method. The reaction involves a hydrogen bond assembly and a polycondensation process. The silanol was formed by reacting PMS aqueous solution with CO₂, which was assembled on the wood surface via hydrogen bonds with the wood surface -OH groups. The polymethylsilsesquioxane coating was obtained through the polycondensation reaction of the hydroxyl between wood and silanol. The morphology of products were characterized using a scanning electron microscope (SEM), the surface chemical composition was determined using energy dispersive X-ray analysis (EDXA), Fourier transform infrared spectroscopy (FT-IR), thermogravimetry (TGA) and contact angle measurement. Analytical results revealed that rough protuberances uniformly covered the wood surface, thus transforming the wood surface from hydrophilic to superhydrophobic. The water contact angle of the superhydrophobic wood surface was about 153° and a sliding angle was 4.6°.     

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).     

A simple fabrication method for mechanically robust superhydrophobic surface by hierarchical aluminum hydroxide structures

Superhydrophobic surfaces with uniformly superhydrophobic surface where nano-scale structures were fabricated by alkali surface modification method and self-assembled monolayer coating. To enhance mechanical durability of the superhydrophobicity, we propose the fabrication process for dual-scale hierarchical structures combining both microstructure via sandblasting techniques and the nanostructured aluminum hydroxide layer. The superhydrophobic surfaces fabricated by both methods exhibited a high water contact angle and very low contact angle hysteresis. By forming the hierarchical structure, the mechanical durability of superhydrophobic aluminum hydroxide surface was improved. The resulting hierarchical structures are suitable for diverse applications of aluminum in various industrial areas, including self-cleaning, anti-frosting, and microfluidic devices for rigorous environments.     

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 surface on a wood substrate

A layer of lamellar superhydrophobic coating was fabricated on a wood surface through a wet chemical process. The superhydrophobic property of the wood surface was measured by contact angle (CA) measurements. The microstructure and chemical composition of the superhydrophobic coating were analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). An analytical characterization revealed that the microscale roughness of the lamellar particles was uniformly distributed on the wood surface and that a zinc stearate monolayer (with the hydrophobic groups oriented outward) formed on the ZnO surface as the result of the reaction between stearic acid and ZnO. This process transformed the wood surface from hydrophilic to superhydrophobic: the water contact angle of the surface was 151°, and the sliding angle was less than 5°.     

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.     

Synthesis and microstructure observation of titanium carbonitride nanostructured coatings using reactive plasma spraying in atmosphere

In the present study, nanostructured titanium carbonitride (TiCN) coatings were successfully deposited by reactive plasma spraying (RPS) technology using a self-designed gas tunnel mounted on a normal plasma spray torch. The phase composition and microstructure of the TiCN coatings were characterised by XRD, SEM and TEM. The results indicated that the main phase of the coatings was FCC TiC_0.2N_0.8 with a small amount of Ti₃O. The coating that was deposited using 35 kW displayed better microstructure and properties. The coating exhibited a typical nanostructure including 90 nm diamertrical equiaxed grains and 400 nm long columnar grains by TEM images. The SEM observation further revealed that the equiaxed grains in parallel direction to the substrate surface in TEM images were actually the columnar grains perpendicular to the substrate surface. The formation mechanism of the nanostructured coatings was also discussed. The measured microhardness value of the coating was approximately 1659 Hv_100 g, and the calculated crack extension force was about 34.9 J/m².     

Control of tribological properties of diamond-like carbon films with femtosecond-laser-induced nanostructuring

This paper reports tribological properties of diamond-like carbon (DLC) films nanostructured by femtosecond (fs) laser ablation. The nanostructure was formed in an area of more than 15 mm × 15 mm on the DLC surface, using a precise target-scan system developed for the fs-laser processing. The frictional properties of the DLC film are greatly improved by coating a MoS₂ layer on the nanostructured surface, while the friction coefficient can be increased by surface texturing of the nanostructured zone in a net-like patterning. The results demonstrate that the tribological properties of a DLC surface can be controlled using fs-laser-induced nanostructuring.     

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.     

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.     

Superhydrophobicity of polyvinylidene fluoride membrane fabricated by chemical vapor deposition from solution

Due to the chemical stability and flexibility, polyvinylidene fluoride (PVDF) membranes are widely used as the topcoat of architectural membrane structures, roof materials of vehicle, tent fabrics, and so on. Further modified PVDF membrane with superhydrophobic property may be even superior as the coating layer surface. The lotus flower is always considered to be a sacred plant, which can protect itself against water, dirt, and dust. The superhydrophobic surface of lotus leaf is rough, showing the micro- and nanometer scale morphology. In this work, the microreliefs of lotus leaf were mimicked using PVDF membrane and the nanometer scale peaks on the top of the microreliefs were obtained by the method of chemical vapor deposition from solution. The surface morphology of PVDF membrane was investigated by scanning electronic microscopy (SEM) and atomic force microscope (AFM). Elemental composition analysis by X-ray photoelectron spectroscopy (XPS) revealed that the material of the nanostructure of PVDF membrane was polymethylsiloxane. On the lotus-leaf-like PVDF membrane, the water contact angle and sliding angle were 155° and 4°, respectively, exhibiting superhydrophobic property.