Superhydrophobic surfaces prepared from water glass and non-fluorinated alkylsilane on cotton substrates

Superhydrophobic surfaces have been successfully prepared by sol-gel method using water glass as starting material. Such surfaces were obtained first by dip-coating the silica hydrosols prepared via hydrolysis and condensation of water glass onto cotton substrates, then the surface of the silica coating was modified with a non-fluoro compound, hexadecyltrimethoxysilane (HDTMS), to gain a thin film through self-assembly, superhydrophobicity with a water contact angle higher than 151° can be achieved. The morphology and surface roughness were characterized by SEM and AFM.     

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.     

Preparation of durable hydrophobic cellulose fabric from water glass and mixed organosilanes

Durable superhydrophobic cellulose fabric was prepared from water glass and n-octadecyltriethoxysilane (ODTES) with 3-glycidyloxypropyltrimethoxysilane (GPTMS) as crosslinker by sol-gel method. The result showed that the addition of GPTMS could result in a better fixation of silica coating from water glass on cellulose fabric. The silanization of hydrolyzed ODTES at different temperatures and times was studied and optimized. The results showed that silanization time was more important than temperature in forming durable hydrophobic surface. The durability of superhydrophobicity treatment was analyzed by XPS. As a result, the superhydrophobic cotton treated under the optimal condition still remained hydrophobic properties after 50 washing cycles.     

Controlled fabrication of transparent and superhydrophobic coating on a glass matrix via a Green method

A facile, green method was explored for the organic-inorganic complex coating with superhydrophobic and transparent property on glass matrix. The glass surface was firstly treated with polyethylene glycol (PEG) and SiO₂ organic-inorganic solution and then modified with a layer of 1,1,1,3,3,3-Hexamethyldisilazane (HMDS). The glass samples were characterized by scanning electron microscopy (SEM), water contact angle (CA) measurement, and UV–Vis spectrophotometry. The results showed that the optical transmission over the visible range up to 89 % (in reference to 100 % transmission defined by bare glass substrate), and the water CA of the film reached 168^°. Superhydrophobic coatings with excellent optical transmittance will have potential applications in our daily life.     

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.     

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.     

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).     

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.     

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.     

Formation of hierarchical ZnO nanostructure on tinfoil substrate and the application on wetting repellency

Hierarchical ZnO (zinc oxide) nanostructures composed with nano-sheet and micro-flower structures (made from the nano-sheet) have been generated on tinfoil substrate via a chemical bath deposition process. Benefiting from an inherent distinct lattice constant compared with commonly used glass or other kinds of substrate, the tinfoil substrate played an important role on the formation of the hierarchical ZnO nanostructures. The resulting hierarchical ZnO surface shows excellent superhydrophobicity and extremely low water rolling angle after being modified with spin coating Teflon. The flexible and superhydrophobic characteristics of such fabricated substrate will be beneficial for applications requiring bendable and lightweight superhydrophobic substrates. In addition, the multifunctional properties of ZnO nanostructures are expected to broaden the applications to electronic and optical applications.     

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.     

有机/无机杂化纳米粒子制备多孔增透膜

以甲基丙烯酸四氟丙酯-co-γ-甲基丙烯酰氧丙基三甲氧基硅烷[P(TFPMA-co-TMSPMA)]共聚物和聚苯乙烯(PS)二元混合乳液旋涂成膜,再采用环己烷选择性溶解除去PS纳米粒子的方法制备了多孔有机/无机杂化纳米基光学增透膜。研究了二元混合乳液固含量、旋涂速度及纳米粒子粒径等参数对增透膜性能的影响。通过选用不同固含量的混合乳液以及改变成膜转速,可制得膜厚在109～208nm之间,折射率nf在1.22～1.25之间,在400～1100nm波段均获得最大透射率高于99.1%的增透膜;此外,研究发现膜的粗糙度及透射率对纳米粒子粒径有较强的依赖性,减小成膜乳液粒子粒径可有效降低膜的粗糙度。     

The bond strength of Al-Si coating on mild steel by kinetic spraying deposition

Kinetic spraying (or cold gas dynamic spraying) works by accelerating small solid particles to supersonic velocities, and then impacting them onto a substrate. These high impact velocities, and low particle temperatures are the principal attributes of kinetic spraying technology. However, only recently has this technology's interfacial behavior, due to particle/substrate impaction, become well understood. In order to investigate the particle/substrate bond behavior, Al-Si feedstock was deposited onto mild steel, over a range of particle velocities; next, their respective coating bond strengths were measured by the stud pull coating adherence test. The effects of the particle velocity and the substrate surface roughness on the coating bond strength were presented, and a model of the particle/substrate bond generation was discussed in an effort to estimate the bond strength.     

Silicon nanowire and polyethylene superhydrophobic surfaces for discrete magnetic microfluidics

A microfluidic method to manipulate small drops of water is studied on two different superhydrophobic surfaces. Using this digital magnetofluidic method, water drops containing paramagnetic carbonyl-iron microparticles were displaced on silicon nanowire (Si NW) and low-density polyethylene (LDPE) superhydrophobic surfaces using magnetic fields. Horizontal, vertical, or upside-down drop movement is made possible by the action of capillary forces induced by paramagnetic particles aligning and following a magnetic field, indicating that three-dimensional digital microfluidics is possible. Also, both Si NW and LDPE superhydrophobic surfaces combine surface chemistry with nano and microscale surface roughness to make drop movement possible. Si NW superhydrophobic surfaces were prepared using vapor-liquid-solid growth systems followed by coating with a perfluorinated hydrocarbon. LDPE superhydrophobic surfaces were prepared by growing polyethylene crystals on a polyethylene substrate through careful rate control.     

Fabrication of superhydrophobic surfaces on zinc substrates and their application as effective corrosion barriers

Stable superhydrophobic surfaces have been effectively fabricated on the zinc substrates through one-step platinum replacement deposition process without the further modification or any other post processing procedures. The effect of reaction temperatures on the surface morphology and wettability was studied by using SEM and water contact angle (CA) analysis. Under room temperature, the composite structure formed on the zinc substrate was consisted of microscale hexagonal cavities, densely packed nanoparticles layer and micro/nanoscale structures like the flowers. The structure has exhibited great surface roughness and porosity contributing to the superhydrophobicity where the contact angle could reach an ultra high value of around 170°. Under reaction temperature of 80 °C, the composite structure, on the other hand, was hierarchical structure containing lots of nanoscale flowers and some large bushes and showed certain surface roughness (maximum CA value of about 150°). In addition, an optimal superhydrophobic platinum surface was able to provide an effective anticorrosive coating to the zinc substrate when it was immersed into an aqueous solution of sodium chloride (3% NaCl) for up to 20 days. The corrosion process was monitored through electrochemical means and the results are compared with those of unprotected zinc plates.     

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°.     

Nanosphere dispersion on a large glass substrate by low dose ion implantation for localized surface plasmon resonance

Dispersing nanospheres on a large glass substrate is the key to fabricate noble metal nanostructures for localized surface plasmon resonance through dispersed nanosphere lithography. This article reports that by modifying the glass surface with low dose ion implantation and successively dip coating the surface with poly(diallyldimethyl ammonium chloride) (PDDA), polystyrene or silica nanospheres can be dispersed on a large glass substrate. Investigation shows that several kinds of ions, such as silicon, boron, argon, and arsenic, can improve the nanosphere dispersion on glass, attributed to the ion bombardment-caused silicon increment. Ion implantation imposes no surface roughness or optical loss to the glass substrate, thus this method is suitable for localized surface plasmon resonance application. Experiments show silicon ion implantation can best disperse the nanospheres. For the gold nanostructures obtained by obliquely evaporating 30 nm of gold film onto the polystyrene nanospheres, which are dispersed on a silicon ion implanted glass substrate, a localized surface plasmon resonance sensitivity of 242 nm/RIU is achieved.     

Fabrication and characterization of transparent superhydrophobic thin films based on silica nanoparticles

A simple method, which was based on self-assemble of silica nanoparticles and heptadecafluorodecyl trimethoxysilane, was used to fabricate a transparent superhydrophobic thin film with a water contact angle higher than 146°. The film has a uniform thickness of about 200 nm and a certain surface roughness about 20 nm, which makes it both transparent and superhydrophobic. PACS 06.60.Ei; 81.07.Pr; 81.16.Dn; 81.20.Fw; 81.65.-Ps     

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°.     

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.