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.     

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.     

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°.     

Investigation into the photo-induced change in wettability of hydrophobized TiO2 films

The photo-induced change in wettability of hydrophobized TiO₂ films has been investigated for steel coated with acidic TiO₂ nanosols containing varying concentrations of dispersed nanocrystalline titania, such as Degussa P25. The photo-induced change in wettability was evaluated by measuring the time-dependent drop of water contact angle (WCA) after samples had been soaked in either n-octyltriethoxysilane (OTS) or decanoic acid (DA). TiO₂ films treated in this way exhibit superhydrophobic behaviour, with WCA greater than 160°. After radiation with UV (black light), the superhydrophobic properties are transformed into superhydrophilic properties, with WCA of almost 0°. As P25 content and layer thickness increase, high rates of photo-induced change are found, but a moderate calcination regime is required. On the other hand, hardness and E modulus pass through a maximum at 25 wt% P25, so that a P25 content between 25 and 50 wt% is the optimum for practical uses. With such stable coatings, wettability can be controlled over a wide range, and the switch between hydrophobic and hydrophilic states can be carried out repeatedly when DA is used as the hydrophobizing agent. Use of a low calcination temperature (450 °C) for the intermediate annealing of the single layers in multilayer coatings and a short final sintering step at a relatively high temperature (e.g. 630 °C for 10 min) allow the preparation of relatively thin TiO₂ films on steel with a high photoactivity.     

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.     

Preparation of superhydrophobic surface with a novel sol-gel system

Sol-gel method is a simple and cheap way to prepare superhydrophobic coatings or films, however, most of the researches on sol-gel focus on silica or ZnO sol-gel. The present paper proposes a novel sol-gel which is made from hydrolysis and condensation of the by-product of polymethylhydrosiloxane (PMHS) reacting with γ-aminopropyltriethoxysilane (KH550). The mechanism of formation of the by-product and the sol-gel is discussed and the by-product is characterized by FT-IR. The mass ratio of KH550/PMHS of the sol-gel influences the water contact angle (WCA) and water sliding angle (WSA) of the film made of spraying the sol-gel to microscope glass. When the mass ratio of KH550/PMHS of the sol-gel reaches 0.25, WCA of the corresponding film is 157° and WSA of it is less than 1°. The mechanism of formation of the sol-gel is discussed, and the size of the sol-gel is characterized by polarization microscope as well. The morphology of the film made of the sol-gel is analyzed by means of scanning electron microscope (SEM). It was found that the diameter of the particle of the superhydrophobic film is about 40 μm, nevertheless, from the larger magnification picture, the particle is found to be composed of micro-balls whose diameter is about 2 μm, and the micro-ball is composed of nano-sphere whose diameter is less than 200 nm.     

Surface modification on a glass surface with a combination technique of sol-gel and air brushing processes

This study fabricated the large area and optically transparent superhydrophobic silica based films on glass surface with optimized hardness. A silane coupling agent, tetraethoxysilane (TEOS), effectively bonds silica particles onto the glass substrate. Desired surface roughness was obtained by adjusting nano silica particles concentration of the precursors prepared by the sol-gel process. Silica suspension was coated onto the glass substrate by the air brushing methods. This method can deposit a uniform, transparent coating on the glass substrate efficiently. Diluting the precursor by adding ethanol or a mixture of D.I. water and ethanol further improved the transmittance and superhydrophobicity efficiency. The results showed that as the silica particle concentration and the thickness of the coating were increased, the surface roughness was enhanced. Rougher surface displayed a higher superhydrophobicity and lower transmittance. Therefore, the concentration of silica particle, volume of coatings, and the ratio of ethanol and D.I. water are of great importance to deposit a transparent, superhydrophobic coating on glass.     

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.     

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.     

Erosion of polyimide modified by amorphous silica sol in the stream of oxygen plasma

Polymeric coatings derived from Kapton H polyimide, thermoplastic polyimide (PI), and a composite with amorphous silica sol (PI-SS) were irradiated in a magnetoplasma dynamic accelerator of oxygen plasma simulating the action of atomic oxygen (AO). The volumetric erosion coefficients of polymers were calculated, and the comparative analysis of the stability of coatings was performed. The changes in morphology of polymer surfaces before and after irradiation were studied by means of scanning electron microscopy. It was shown that the PI-SS composite has increased resistance to atomic oxygen. The composition of the PI-SS composite was found at which the particles of silica sol are uniformly dispersed over the polymer volume that explains a better resistance of PI-SS polymeric-inorganic compositions to the action of atomic oxygen. The lowest stability was registered for the coating based on Kapton H polyimide. The surfaces of all coatings after irradiation were found to possess a carpetlike morphology. Each polymer featured a number of distinctive peculiarities of the surface structure caused by the differences in the chemical structure of the polymides under investigation.     

Fabrication and characterization of superhydrophobic thin films based on TEOS/RF hybrid

Preparation of superhydrophobic silica-based thin film by adjusting different concentration of reverse (W/O) emulsion of resorcinol formaldehyde resin (re-RF) which was hybridised with silica sol has been developed. The hybrid films were coated by the mixing solution which included precursor solution (sol-gel process) and re-RF (sol-gel process). Rough surfaces were obtained by removing the organic polymer at high temperature and then the hydrophobic groups bonded onto the films were obtained by the reaction with trimethylchlorosilane (TMCS). Characteristic properties of the as-prepared cross-section and surface of the films were analyzed by scanning electron microscopy (SEM) and atom force microscopy (AFM). The experimental parameters are mainly varied the weight ratio of re-RF to silica sol from 0.2 to 4.0. The result showed that the contact angle of the modified silica film was greater than 160° when the weight ratio of re-RF to silica sol was 2.0.     

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).     

The influence of gas flow rate on the structural,mechanical, optical and wettability of diamond-like carbon thin films

In this research, diamond-like carbon (DLC) thin films were deposited on silicon substrates by radio-frequency plasma enhanced chemical vapor deposition method using gas mixture of CH₄ and Ar. The effect of different CH₄/Ar gas ratio on the structure, refractive index, transmission and hardness of the DLC thin films were investigated by means of Raman spectroscopy, ellipsometry, Fourier transform Infrared Spectroscopy and nano-indentation methods, respectively. Nuclear resonant reaction analysis was used to measure the amount of hydrogen and carbon in the thin films. Furthermore, wettability of the thin films was achieved by measuring of water contact angle (WCA). The results indicated that the structural properties of the diamond-like carbon thin films are strongly dependent on the composition of gas mixture. Based on ellipsometry results, refractive index of the thin films varied in the range of 1.89–2.06 at 550 nm. FTIR results determined that deposition of DLC thin films on silicon substrate led to an increase of the light transmission in IR region and these films have the potential to be used in silicon optics as the antireflective coatings in this region. Nano-indentation analysis showed that the thin films hardness changed in the range of 7.5–11 GPa. On the other hand hydrogen content and fraction of C?H bonds in the samples increased by an increase in the gas ratio of CH₄/Ar. Also, WCA measurements indicated that WCA for thin films with gas ratio of 3/7 is the most and equal to 79°.     

Acrylic coatings exhibiting improved hardness, solvent resistance and glossiness by using silica nano-composites

To prepare nano-composite emulsion acrylic resins with improved surface hardness and solvent resistance, nano-silica particles were treated with surfactants. The monomers of methyl methacrylate/butylacrylate were co-polymerized on the surface of dispersed silica particles. Several emulsions with different silica contents and copolymer mole fractions were prepared. Finally the emulsions were modified to water-based acrylic coatings and improved properties such as surface hardness, solvent resistance and glossiness were determined. The study of coatings was directed to find the improved resin by optimum surface properties. Size distribution and morphology of latexes were characterized by Fourier transform infrared spectroscopy, dynamic light scattering, transmission electron microscopy and scanning electron microscopy. The glass transition temperature of nano-composites was measured and discussed its relation with silica contents, monomer mole fractions and improved properties of coatings. The optimum pendulum hardness of coatings was on 0.46 methyl methacrylate mole fraction and 120 g silica content. An increase in pendulum hardness of nano-composites with the addition of modified silica was observed. DLS and TEM studies indicate that silica particles were dispersed homogenously through the polymer matrix.     

Fabrication of superhydrophobic surfaces based on ZnO-PDMS nanocomposite coatings and study of its wetting behaviour

Superhydrophobic surfaces based on ZnO-PDMS nanocomposite coatings are demonstrated by a simple, facile, time-saving, wet chemical route. ZnO nanopowders with average particle size of 14 nm were synthesized by a low temperature solution combustion method. Powder X-ray diffraction results confirm that the nanopowders exhibit hexagonal wurtzite structure and belong to space group P63mc. Field emission scanning electron micrographs reveal that the nanoparticles are connected to each other to make large network systems consisting of hierarchical structure. The as formed ZnO coating exhibits wetting behaviour with Water Contact Angle (WCA) of ∼108°, however on modification with polydimethylsiloxane (PDMS), it transforms to superhydrophobic surface with measured contact and sliding angles for water at 155° and less than 5° respectively. The surface properties such as surface free energy (γ_p), interfacial free energy (γ_pw), and the adhesive work (W_pw) were evaluated. Electron paramagnetic resonance (EPR) studies on superhydrophobic coatings revealed that the surface defects play a major role on the wetting behaviour. Advantages of the present method include the cheap and fluorine-free raw materials, environmentally benign solvents, and feasibility for applying on large area of different substrates.     

Effect of thermal treatments on sputtered silver nanocluster/silica composite coatings on soda-lime glasses: ionic exchange and antibacterial activity

Silver nanocluster/silica composite coatings were deposited on both soda-lime and silica glasses by radio frequency (RF) co-sputtering. The effect of thermal treatments on the microstructure in the range of 150?C450?°C were examined by UV?Cvisible spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and Time of Flight-Elastic Recoil Detection Analysis. Sodium/silver ionic exchange was evidenced for coatings sputtered on soda-lime substrates after heating at 450?°C; presence of silver ions and/or silver nanoclusters, nanocluster size and their position inside the sputtered layers will be discussed for as-deposited and heated coatings on both substrates. The antibacterial activity of all coatings was determined against Staphylococcus aureus and Candida albicans by disk diffusion method and colonies forming units count; in agreement with microstructural results, the antibacterial activity present on all coatings was slightly reduced after heating at 450?°C. All coatings have been submitted to humidity plus UV ageing and sterilization by autoclave, gamma ray and ethylene oxide gas. Tape resistance (ASTM D3359-97) tests have been done on each coating before and after ageing and sterilizations, revealing a good adhesion on soda-lime substrates, except for those aged in humidity plus UV and sterilized by autoclave. Scratch tests and nanoindentation tests have been done on each coating, as-deposited and after heating at 450?°C. The coating hardness was improved by heating only when coatings were deposited on silica. The heating of coatings deposited on soda-lime substrates gave opposite effect on their hardness.     

Microstructure and properties of Ni-Co/nano-Al2O3 composite coatings by pulse reversal current electrodeposition

Ni-Co/nano-Al₂O₃ (Ni-Co/Al₂O₃) composite coatings were prepared under pulse reversal current (PRC) and direct current (dc) methods respectively. The microstructure of coatings was characterized by means of XRD, SEM and TEM. Both the Ni-Co alloy and composite coatings exhibit single phase of Ni matrix with face-centered cubic (fcc) crystal structure, and the crystal orientation of the Ni-Co/Al₂O₃ composite coating was transformed from crystal face (2 0 0) to (1 1 1) compared with alloy coatings. The hardness, anti-wear property and macro-residual stress were also investigated. The results showed that the microstructure and performance of the coatings were greatly affected by Al₂O₃ content and the electrodeposition methods. With the increasing of Al₂O₃ content, the hardness and wear resistance of the composite coatings enhanced. The PRC composite coatings exhibited compact surface, high hardness, better wear resistance and lower macro-residual stress compared with that of the dc composite coatings.     

A simple method for preparation of transparent hydrophobic silica-based coatings on different substrates

A facile, inexpensive, and general approach is explored for the fabrication of transparent silica/organic silicon hybrid sol, which could form transparent hydrophobic coatings on different substrates conveniently. The sol was prepared by using hexamethyldisilazane (HMDS) as a surface-modifying agent and the source of base catalyst required for the hydrolysis of tetraethoxysilane (TEOS). The resulting silica-based coatings on glass slide have shown an optical transmission over the visible range up to 89% (in reference to 100% transmission defined by a plain glass substrate) and high thermal stability. The water contact angle of the film reached 152^○. Hydrophobic coatings with excellent optical transmittance were also successfully formed on writing paper and aluminum foils. The transparent hydrophobic silica-based hybrid sol will have potential applications in creating outdoor building glass, protecting paper files from moisture and preventing metals from corrosion.     

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.     

Effect of the dispersibility of ZrO2 nanoparticles in Ni-ZrO2 electroplated nanocomposite coatings on the mechanical properties of nanocomposite coatings

ZrO₂ nanoparticles was uniformly co-deposited into a nickel matrix by electroplating of nickel from a Watts bath containing particles in suspension which were monodispersed with dispersant under DC electrodeposition condition. It was found that morphology, orientation and hardness of the nanocomposite coatings with monodispersed ZrO₂ nanoparticles had lots of difference from the nanocomposite coatings with agglomerated ZrO₂ nanoparticles and pure nickel coatings. Especially, the result of hardness showed that only a very low volume percent (less than 1 wt.%) of monodispered ZrO₂ nanoparticles in Ni-ZrO₂ nanocomposite coatings would result in higher hardness of the coatings. The hardness of Ni-ZrO₂ nanocomposite coatings with monodispersed and agglomerated ZrO₂ nanoparticles were 529 and 393 HV, respectively. The hardness value of the former composite coatings was over 1.3 times higher than that of the later. All these composite coatings were two-three times higher than that of pure nickel plating (207 HV) prepared under the same condition. The strengthening mechanisms of the Ni-ZrO₂ nanocomposite coatings based on a combination of grain refinement strengthening from nickel matrix grain refining and dispersion strengthening from dispersion state of ZrO₂ nanoparticles in the coatings.