The effect of ceramic nanoparticles on tribological properties of alumina sol–gel thin coatings

Thin alumina coatings containing zirconia or alumina nanoparticles having diameter of ～20–30 nm were deposited by the sol–gel dip-coating process on silicon wafers. The mass content of nanoparticles in the alumina coating was fixed at 15% in relation to the theoretical mass of alumina matrix resulted from the amount of the applied precursor. Atomic force microscopy (AFM) was used to image the surface topography of as-made coatings and find out the wear level after frictional tests. Tribological tests were performed with the use of a microtribometer operating in the load range of 30–100 mN. It was found that the presence of α-alumina (corundum) or zirconia nanoparticles enhances the tribological performance of alumina layers annealed at 100 °C by decreasing the average wear rate by 20% and 63% for zirconia and corundum nanoparticles, respectively. No wear was observed for samples containing both types of nanoparticles annealed at 500 °C.     

Preparation and dielectric properties of dense and amorphous alumina film by sol–gel technology

Dense and crack-free aluminum oxide films were fabricated by sol–gel spin-coating technology. Aluminum nitrate (Al(NO₃)₃.9H₂O) was used as the precursor material. X-ray diffraction shows that the fabricated films are amorphous. X-ray photoelectron spectroscopy confirms that the thin films are alumina (Al₂O₃). Field-emission scanning electron microscopy images of the films reveal that the films are compact with a dense cross section. Dielectric measurements were carried out on samples with a metal–insulator–metal structure. The electrical characteristics of the films were affected by the thermal sintering temperature of the films. The leakage current density of the films decreases with the increase in the sintering temperature and increases with the increase in the measuring temperature. The leakage current shows a linear dependence on the voltage in the low-electric field-regime. The current density ascends to higher values due to the effect of space charges in the high-electric-field regime. The ionization energy of the top-electrode metals (Au, Pt or Ti–Au) has a strong effect on the leakage current.     

Corrosion resistance performance of cerium doped silica sol–gel coatings on 304L stainless steel

The aim of this work is the synthesis and investigation of silane based organic–inorganic hybrid coatings, which can be used to improve the corrosion performance of steel structures subjected to a marine environment. The silane based sol–gel coatings were prepared by dip coating 304L stainless steel in a solution of organically modified silica sol made through hydrolysis and condensation of 3-glycidoxypropyl-trimethoxysilane (GPTMS) as precursor and bisphenol A (BPA) as a cross-linking agent in an acid catalyzed condition. The influence of the addition of cerium and the use of bisphenol A as a cross-linking agent on the microscopic features and morphology as well as on the corrosion resistance of the coatings were examined using Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), neutral salt spray tests, potentiodynamic polarization and electrochemical impedance techniques. Results show that cerium modified nano-hybrid coatings exhibit a superior corrosion inhibition performance to that displayed by silica hybrid coatings. Additionally, data showed that the bisphenol A as a cross-linking agent has a significant effect on the morphology and corrosion resistance of the cerium doped silica coating. Omitting the use of bisphenol A causes the creation of defects/cracks in the coating, thereby promoting diffusion of the aggressive electrolyte toward the substrate and decreasing the corrosion resistance of the coating.     

Deposition of alumina coatings on monocrystalline diamonds by sol–gel techniques

Machining of steel or iron-based alloys with diamond tools leads to rapid tool failure — probably due to chemical wear. The use of monocrystalline diamond tools has, up to now, been obligatory for precision machining. Coating the diamonds with a thin but hard and chemically inert alumina film may overcome the problem. Alumina coatings were deposited by sol–gel techniques. It was shown that a very thin TiN intermediate layer, deposited by reactive sputtering, results in a good adhesion of the alumina coatings to the monocrystalline diamonds. The microstructure of the coatings was characterized by field-emission scanning electron microscopy (FE-SEM) and by transmission electron microscopy (TEM). The deposited coatings showed a nanocrystalline, dense microstructure. The hardness of the coatings was investigated by ultramicrohardness measurements (UMH).     

Reactive SPS for sol–gel alumina samples: Structure,sintering behavior,and mechanical properties

This work presents a fast and direct controlled routine for the fabrication of fully dense alumina based on the reactive spark plasma sintering (reactive-SPS) of boehmite (γ-AlOOH) nano-powders obtained by the sol–gel technique. The evolution of the transition aluminas during sintering has been studied. Some boehmite powders were seeded with α-Al₂O₃ particles prior to the gelation. Boehmite seeded powders exhibited a direct transition to α-Al₂O₃ at 1070 °C, enhancing the transformation kinetics and lowering the required temperature by more than 100 °C. For comparison, other samples were prepared by previously annealing the seeded and unseeded boehmite powders. Thus, α-Al₂O₃ powders were obtained and were sintered by standard-SPS. A detailed structural and mechanical characterization is presented, comparing the hardness and indentation fracture resistance for different grain sizes and porosities. Both the reactive-SPSed samples and the standard-SPSed samples showed a high hardness (18–20 GPa), whereas the reactive-SPSed samples exhibited a lower indentation fracture resistance due to a large grain size (～10 μm). Improvements of this procedure for obtaining smaller grain size are discussed. In summary, the presented technique brings a revolutionary fast method for the fabrication of fully dense alumina, as this process reduces the time and temperature required for alumina densification.     

Effect of cerium concentration on corrosion resistance and polymerization of hybrid sol–gel coating on martensitic stainless steel

Stainless steels are increasingly used in the aeronautics field for the manufacture of structural parts. One of them, the X13VD martensitic stainless steel (X12CrNiMoV12-3), known for its good mechanical properties, has a poor corrosion resistance in confined or severe environments. In the past years, Cr(VI) based pre-treatments have been currently used for corrosion protection of different metals, however, they are toxic and due to environmental regulations, they will be definitely banned in a near future. Alternatives to replace Cr(VI) show advantages and drawbacks considering key properties such as: corrosion resistance, adhesion of coatings, fatigue resistance, durability and reliability. However, some of their possible alternatives show high potential.     

Processing and properties of sol gel derived alumina–carbon nano tube composites

High purity alumina–carbon nano tube (CNT) composites were prepared by an aqueous sol–gel processing route. CNTs were dispersed in alumina sol containing appropriate amount of MgO precursor. Aqueous slurry of alumina was seeded into the sol followed by gelation, drying and calcination at 1000 °C for 1 h. The calcined powder consisting of alumina-coated CNTs and alumina was milled, sieved, dried, pressed and pressureless sintered at 1400–1600 °C for 1 h in nitrogen atmosphere. Sintered samples were further isostatically hot pressed at 1300 °C and the properties were compared with the pressureless sintered samples. Phase formation was followed by XRD study, CNT retention was confirmed by Raman studies and the samples were further characterized for mechanical and microstructural properties.     

Preparation of hybrid silica sol–gel coatings on mild steel surfaces and evaluation of their corrosion resistance

Hybrid silica sol–gel coatings were prepared on mild steel substrate by dip coating technique. The coatings were subsequently heat treated at 200 °C in order to improve their corrosion properties. The coating sols were synthesized using Glycidoxypropyltrimethoxysilane (glymo) and Aminopropylethoxysilane (ameo) as precursor materials. Potentiodynamic polarization curves were derived and Electrochemical Impedance Spectroscopy (EIS) measurements were made in NaCl solution. The surface and cross-section morphology of coated specimens were characterized by scanning electron microscopy (SEM). Fourier transformed infrared (FTIR) analysis was used to identify the presence of various functional groups in the coating solutions. A comparison of the corrosion resistance of the coated and uncoated mild steel was presented. The results indicated that the corrosion resistance of the coated mild steel was improved considerably.     

Antireflective coatings prepared by sol–gel processing: Principles and applications

Sol–gel processing is a powerful tool to prepare antireflective (AR) coatings on optical surfaces. In this paper the different strategies to obtain antireflective properties are reviewed: porous λ/4 layers, multilayer interference-type films and index-gradient materials such as “moth eye” structures. The processing of the respective films is described and evaluated; references to respective commercial products on glass substrates are given.AR coatings may have a particularly high importance for transparent ceramics as their index of refraction is significantly higher than that of common glass types. Reflective losses therefore are higher which is especially unpleasant for materials with a yet improvable intrinsic transparency.Recent studies indicate that specific porous λ/4 layers may exhibit pronounced anti-soiling features. Laboratory experiments as well as outdoor exposure tests were used to demonstrate the dust-repellant properties.     

Preparation and corrosion protective properties of nanostructured titania-containing hybrid sol–gel coatings on AA2024

Titania-containing organic–inorganic hybrid sol–gel films have been developed as an alternative to chromate-based coatings for surface pretreatment of aluminium alloys. Stable hybrid sols were prepared by hydrolysis of 3-glycidoxypropyltrimethoxysilane and different titanium organic compounds in 2-propanol solution in the presence of small amounts of acidified water. Different diketones were used as complexing agents in this synthesis for controllable hydrolysis of titanium organics. The properties of the obtained coatings were compared with those of zirconia-containing films. Electrochemical impedance spectroscopy (EIS) measurements and standard salt spray tests were performed to investigate the corrosion protection performance of the hybrid coatings. It was revealed that their protective properties depend significantly on the nature of metalorganic precursors and complexing agents used in the process of sol preparation. The best anticorrosive protection of AA2024 in chloride solutions is provided by the titania-containing sol–gel films prepared with titanium(IV) tetrapropoxide and acetylacetone as starting materials. In the case of zirconia-containing films, better protective properties were found when applying ethylacetoacetate as a complexing agent.     

Investigation of the mechanical and thermal fatigue properties of hybrid sol–gel coatings applied to AA2024 substrates

This research article reports on the response of various hybrid sol–gel materials when applied as coatings to pre-treated bare AA2024 substrates, to mechanical indentation and cyclic thermal stimuli, in order to determine their usefulness in aeronautical applications. Three groups of hybrid sol–gel-coated samples were prepared using various organosilanes and transition metal oxides. The characterization of the materials revealed that the presence of the organic functionalities, especially the methacrylate group, has a noticeable effect on the mechanical response of the hybrid coatings, in particular their flexibility. The presence of methacrylate group in the cured material gives it ability to flex which influenced the thermal fatigue characteristics of the coatings which are able to withstand the cyclic temperature regimes of 82 ± 3 to ?37 ± 3°C over 25 2 h cycles. This capability to maintain substrate protection is reflected in the corrosion resistance of the coatings as measured using electrochemical impedance spectroscopy and accelerated exposure testing. This result is important, as it shows that hybrid sol–gel materials can be used in applications where protecting a metal or ally substrate is paramount, especially in thermally volatile environments.     

Effect of p-aminobenzoic acid on synthesizing ordered mesoporous alumina via the sol–gel method

Ordered mesoporous alumina (OMA) samples were prepared via the sol–gel method. The triblock copolymer P123 and aluminum isopropoxide were chose as the template and aluminum source, respectively. The p-aminobenzoic acid (PABA) worked as both the interfacial protector and the assisted template. Different techniques, including X-ray diffractions, N₂ physisorption measurement and transmission electron microscope, were employed to study the structural properties of the prepared samples. The results showed that the mesostructure ordering and specific surface area of the samples highly depend on the quantity of the added PABA. The samples after calcinated at 800 °C with the n(PABA)/n(Al³⁺) molar ratio lying in 0.30 exhibited high specific surface areas (301 m² g^?1) and retained an ordered mesostructures. It was indicated that the carboxyl groups of PABA have multiple functions in the formation of OMA with a long-range ordering and high specific surface area. The carboxyl groups of PABA can slow down the hydrolysis-condensation reaction of aluminum isopropoxide, reduce the influence of chloride ions on self-assembly process. The amino groups of PABA can also react with the hydrogen ions to form quaternary ammonium salt, which can neutralize the charges of the chloride ions, protect the balance of inorganic–organic interface, further to improve the mesostructure ordering and specific surface area of the prepared OMA.     

Characterization of sol–gel coated 316L stainless steel for biomedical applications

Silica based organic–inorganic hybrid coatings were deposited on 316L stainless steel by sol–gel technique. The hybrid sols were prepared by hydrolysis and condensation of 3-methacryloxypropyltrimethoxysilane (TMSM) and tetraethylorthosilicate (TEOS) at different molar ratios. Electrochemical experiments were performed to evaluate the corrosion resistance properties of the coatings. Structural characterization of the coatings was performed using scanning electron microscopy (SEM) and Fourier transform infrared (FTIR) spectroscopy. Contact angle measurement and cell morphology assay were performed to investigate the hydrophilicity and in vitro cytotoxicity of the coatings, respectively. The results indicate formation of a crack-free and highly adherent film acting as a protective barrier against the physiological medium. Corrosion resistance of hybrid coatings was influenced by the molar ratios of TMSM:TEOS. The best corrosion protection was obtained at TMSM:TEOS molar ratio of 1:1. Sol–gel coatings enhanced the hydrophilicity of 316L steel surfaces. Also, these coatings showed non-toxicity for L929 cells.     

Effect of peptiser species on crystallisation of alumina gel produced by sol–gel process

The present work reports a study on the effect that a peptiser species has on the crystallisation of alumina gel produced by a sol–gel process to help develop a method for producing α-Al₂O₃ at low temperature. The white precipitate of aluminium hydroxide, which was prepared with a homogeneous precipitation method using aluminium nitrate and urea in an aqueous solution, was peptised using various peptisers at room temperature to form a transparent alumina sol. The alumina gel obtained from the alumina sol, which was produced using formic acid as the peptiser, was most dominantly crystallised into α-Al₂O₃ by annealing at 900°C. The optimal [peptiser]/[Al³⁺] (P/A) molar ratio for the crystallisation into α-Al₂O₃ was 0.2. The alumina gel began to crystallise into α-Al₂O₃ with annealing at as low as 500°C when formic acid and a P/A ratio of 0.2 were used.     

Electrophoretic deposition of bioactive wollastonite and porcelain–wollastonite coatings on 316L stainless steel

Wollastonite and porcelain–wollastonite coatings on stainless steel were obtained by electrophoretic deposition using acetone as dispersive medium. A direct electric current of 800 V for 3 min was used for obtaining the single wollastonite coating. A well-sintered layer was observed after heat treatment at 1050 °C for 1 h in air. The two-layer coating was obtained by depositing dental porcelain at 400 V for 30 s followed by the deposition of wollastonite at 400 V for 3 min. After forming the two layers, this complex coating was heat treated at 800 °C for 5 min. Under these conditions, strong bonds of both the interface wollastonite–porcelain and that of porcelain–metallic substrate were observed. The in vitro bioactivity assessment of the coatings was performed by immersing the deposited substrates in simulated body fluid (SBF) for 21 days. All the materials showed to be highly bioactive through the formation of a homogeneous apatite layer.     

Influence of silane structure on curing behavior and surface properties of sol–gel based UV-curable organic–inorganic hybrid coatings

In this study, three usual silane precursors, tetraethoxysilane (TEOS), vinyltrimethoxysilane (VTMS), and 3-methacryloxypropyltrimethoxysilane (MPS), and different binary and triplet blends of them were polymerized via a sol–gel method under acidic conditions. ²⁹Si NMR spectroscopy was used to characterize and quantify the degree of condensation of oligomers. The organic phase was based on a three-acrylate monomer trimethylolpropane triacrylate (TMPTA). The effect of prepared oligomers on the curing behavior of hybrid materials and the interaction between organic and inorganic phases were monitored via photo differential scanning calorimetry (Photo-DSC). Atomic force microscopy (AFM) was used to investigate the surface properties of UV-cured hybrid materials. Photo-DSC results showed that the addition of functionalized oligomers can increase both the photopolymerization rate and the final degree of conversion. They also indicated that oligomers containing MPS are more compatible with the organic phase than other oligomers. Topography and phase trace images of AFM showed that oligomers containing VTMS migrate to the surface of films and affect the water contact angle. In contrast to VTMS, the presence of MPS in oligomers causes the formation of covalent bonds between the organic and inorganic phases in the bulk of the film, and so the surface properties of the film remain unchanged.     

Characterization of wollastonite coatings prepared by sol–gel on Ti substrate

Wollastonite coatings were prepared by sol–gel on Ti substrate and their microstructures have been studied. The phase compositions and the surface morphologies of these coatings were examined by X-ray diffraction and scanning electron microscopy. Thermal behavior of dried gel was examined by differential scanning calorimetry (DSC) and thermogravimetry (TG). There are many cracks among coatings and particles with size about 200–300 nm distributing inside cracks. DSC and TG results show that the glass transformation temperature of dried gel is about 850°C. After calcined at temperature 900°C, the phase of coatings consists of wollastonite, SiO₂, and CaSi₂O₅.     

Synthesis of nanocrystalline gadolinium doped ceria via sol–gel combustion and sol–gel synthesis routes

Gadolinium doped ceria (GDC) has been investigated as a promising material for application as an electrolyte in intermediate temperature solid oxide fuel cells (IT-SOFC). In this work, 10GDC powders (Gd_0.1Ce_0.9O_1.95) were synthesized by sol–gel combustion and sol–gel synthesis routes using the same complexing agents in both procedures. The thermal behavior of Gd–Ce–O precursor gels was investigated by TG–DSC measurements. X-ray diffraction (XRD) analysis was used for the characterization of phase purity and crystallinity of synthesized samples. Scanning electron microscopy (SEM) was employed for the estimation of surface morphological features. Nitrogen adsorption–desorption (BET model) was used for evaluation of specific surface area. The surface composition was determined by X-ray photoelectron spectroscopy (XPS). Electrical properties of synthesized ceramic samples were studied by means of impedance spectroscopy.     

Mechanical properties of sol–gel prepared nanocomposite coatings in the presence of titania and alumina-derived nanoparticles

Hybrid nanocomposite coatings were prepared by sol–gel method using silica, titania and alumina nanoparticles derived from their alkoxides precursors; in the presence of 3-glycidoxypropyl-trimethoxysilane (GPTMS) and bisphenol A (BPA) on 1050 aluminium alloy substrate. The effect of type and ratio of nanoparticles on mechanical behaviour of the coatings were investigated by dynamic mechanical thermal analysis (DMA) and nanoindentation experiments. DMA results demonstrated that the values of the glass transition temperature (T_g) and the temperature at maximum tan (δ), (T_t) as well as the storage modulus of the hybrid samples depend mainly on the silane content and titania to alumina molar ratio of nanoparticles in the coating composition. In addition, nanoindentaion experiments were performed to study the mechanical properties such as hardness, elastic modulus and E/H ratio for the nanocomposite hybrid coatings. Nanoindentation results indicate that the homogenous reinforced structure was formed in the surface of nanocomposite coating with incorporation of titania and alumina-derived nanoparticles. The incorporation of TiO₂ in comparison with AlOOH nanoparticles in the GPTMS-based coatings showed an improving effect on E/H ratio.     

Preparation and characterisation of bioactive hydroxyapatite–silica composite nanopowders via sol–gel method for medical applications

Abstract

Abstract

This study focuses on preparation and characterisation of hydroxyapatite–silica composite nanopowders with different contents of silica. Hydroxyapatite–silica composite nanopowders with 10, 20, 30 and 40?wt‐% silica were prepared using a sol–gel method at 600°C with phosphoric pentoxide and calcium nitrate tetrahydrate as the source of hydroxyapatite, also tetraethylorthosilicate and methyltriethoxisilane as the source of silica. XRD, FTIR, SEM, EDAX and TEM techniques were used for characterisation and evaluation of the phase composition, crystallinity, crystallite size, functional groups, morphology and composition of the products. Dissolution behaviour of the products was evaluated at predetermined time periods by an atomic absorption spectrometer and a pH meter. Results indicated the presence of nanocrystalline hydroxyapatite phase and amorphous silica nanoparticles in composite nanopowders. Also, by increasing the content of silica in composite nanopowders, the crystallite size and crystallinity of hydroxyapatite phase decreased and the Ca ion release rate changed.