Optimization of hybrid sol–gel coatings by combination of layers with complementary properties for corrosion protection of AA2024

The coating system usually employed for corrosion protection of metal substrates consists of different layers which can be constituted of a chemical conversion coating applied on the metal surface followed by a number of organic layers. Hybrid films prepared by the sol–gel method provide a good approach as protective layers on metallic surfaces, although it is necessary to combine the barrier functionality with an active protection mechanism to avoid corrosion when the coating is damaged. Previous works have shown that it is very difficult to reach this result in a mono-layer sol–gel because the amount of inhibitors incorporated tends to increase significantly the porosity of the coating and reduces drastically the barrier properties. This work presents the characterization of a multi-layer sol–gel hybrid inorganic–organic coating system with a structure composed of an intermediate cerium inhibited layer deposited between two un-doped layers on AA2024 alloy. The comparison between the inhibited system and a bi-layer non-inhibited one has allowed to assess the migration of the cerium ions into the hybrid coating towards the substrate corresponding to the improvement of the corrosion properties. The combination of the physical barrier and the active protection enables to obtain an effective protective system.     

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.     

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.     

Inhibiting effect of 8-hydroxyquinoline on the corrosion of silane-based sol–gel coatings on AA 2024-T3

This work presents the silane-based sol–gel coatings that prepared by in situ doping 8-hydroxyquinoline as corrosion inhibitor for the protection of AA 2024-T3. The morphology and thickness of the sol–gel coatings were observed by scanning electron microscope (SEM). Immersion tests and electrochemical impedance spectroscopy (EIS) were used to study the corrosion resistance of the blank and 8-hydroxyquinoline doped sol–gel coatings. The results indicate that the addition of 8-hydroxyquinoline effectively improved the corrosion resistance of the sol–gel coatings. The self-healing effect of 8-hydroxyquinoline on the corrosion in the defects of sol–gel coating was assessed by scanning vibrating electrode technique (SVET) and proved by the results of energy-dispersive X-ray spectroscopy (EDS) mapping.     

Characterization of hybrid sol–gel coatings doped with hydrotalcite-like compounds to improve corrosion resistance of AA2024-T3 alloys

The inhibition effect of hydrotalcite addition to hybrid sol–gel coatings applied on AA2024-T3 alloy was evaluated. Hydrotalcite belongs to the anionic clay family with wide applications, most of them based on its anion exchange capacity due to its double layered structure. In this work hydrotalcite (HT) powder was prepared by the classical co-precipitation method using magnesium and aluminum nitrates as precursors. Different weight percentages (1, 5 and 10%, w/w) of hydrotalcite with Mg/Al ratio of 2.5 were added to hybrid sols prepared by copolymerization of 3-Glycydoxypropyltrimethoxysilane (GPTMS) and tetra-n-propoxyzirconium (TPOZ). The sol–gel coatings were deposited by dip-coating method on AA2024-T3 substrate. Scanning electron microscopy (SEM) and mechanical profilometry measurements revealed the heterogeneous particle sizes and the distribution of the agglomerates. Hydrotalcite additions significantly increased the bond strength between metal and coating, according to pull-off test results.The corrosion performance was evaluated by the salt spray fog chamber test and by Electrochemical Impedance Spectroscopy (EIS). The results showed a marked improvement of the corrosion resistance on the aluminum alloy when HT was added to the hybrid sol–gel coating. This positive effect was more evident at higher weight percentages of hydrotalcite.     

Preparation of scratch resistant superhydrophobic hybrid coatings by sol–gel process

Organic–inorganic hybrid coatings on glass substrates with superhydrophobic properties and with improved scratch resistance were obtained by means of applying a multilayer approach including multiple sol–gel processes. The coatings exhibited a water contact angle (WCA) higher than 150°. Ultraviolet (UV)-curable vinyl ester resins and vinyltriethoxysilane (VTEOS) as coupling agent were employed to increase the adhesion between substrate and the inorganic layers. The surfaces were characterized by means of dynamic contact angle and roughness measurements. Indeed, the occurrence of superhydrophobic behavior was observed. The scratch resistance of the hybrid coatings was tested to evaluate the adhesion of the coatings to the glass substrate. The proposed preparation method for scratch resistant, mechanically stable, superhydrophobic coatings is simple and can be applied on large areas of different kinds of substrates.     

Preparation and characterization of phosphine oxide containing organosilica hybrid coatings by photopolymerization and sol–gel process

A series of UV-cured organic–inorganic hybrid coating materials containing up to 20 wt.% silica were prepared by sol–gel method from tetraethoxy silane (TEOS) which is used as the primary inorganic precursor, and diallylphenylphosphine oxide monomer (DAPPO), aliphatic urethane diacrylate resin (Ebecryl 210) are employed as the source of the organic components. In addition, methacryloxypropyltrimethoxy silane (MAPTMS) was used as both a secondary inorganic source and a silane-coupling agent to improve the compatibility of the organic and inorganic phases. The DAPPO content in all the coating formulations were from 0 to 20 wt.%. The physical and mechanical properties such as gel content, hardness, adhesion, gloss, contact angle as well as tensile strength were measured. These measurements revealed that all the properties of the hybrid coatings improved effectively, in case of adding the sol–gel precursor and DAPPO monomer content in the hybrid systems. The photo-calorimetric-DSC studies showed that the double bond conversion of the hybrid coatings was faster than the coating materials without silica. The thermal stabilities of the UV-cured hybrid materials were investigated by thermogravimetric analysis. The results showed that the addition of sol–gel precursor and DAPPO into the organic network also improves the thermal-oxidative stability of the hybrid coating materials. The surface morphology was also characterized by scanning electron microscopy (SEM). SEM studies indicated that inorganic particles were dispersed homogenously throughout the organic matrix.     

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.     

The electrochemical behaviour of sol–gel hybrid coatings applied on AA2024-T3 alloy: Effect of the metallic surface treatment

The effect of surface pre-treatments on the electrochemical behaviour of sol–gel coated AA2024-T3 alloys was studied in this work. Three different cleaning procedures were employed: degreasing, mechanical polishing, and chemical etching. The surface morphology was different depending on the pre-treatment. The smoothest surface corresponded to polished samples while the chemically etched ones had the highest roughness, even though the sol–gel film covered all the cavities. The hybrid sol–gel film was prepared by copolymerisation of two different sols, tetra-n-propoxyzirconium (TPOZ) as inorganic precursor and 3-glycydoxypropyltrimethoxysilane (GPTMS) as organic precursor. The corrosion resistance was evaluated using accelerated test (salt spray) and electrochemical measurements under continuous immersion. Both experiments indicated that degreased samples had better anticorrosive properties.     

Preparation and corrosion resistance of nanostructured PVC/ZnO–polyaniline hybrid coating

ZnO–polyaniline nanocomposite with core–shell nanostructure was prepared by in situ polymerization of aniline monomer in the presence of ZnO nanoparticles. Fourier transform infrared spectroscopy, X-ray diffraction patterns, field emission scanning electron microscopy and transmission electron microscopy techniques were used to characterize the composition and structure of ZnO–polyaniline nanocomposite. d.c. electrical conductivity measurement showed that the electrical conductivity of ZnO–polyaniline nanocomposite pellets is higher than that of pristine polyaniline and ZnO nanoparticles pellets. The addition of ZnO nanoparticles causes to the increasing of polyaniline electrical conductivity. ZnO–polyaniline nanocomposite was mixed with polyvinyl chloride (PVC) through a solution mixing method and the three components PVC/ZnO–polyaniline hybrid material was applied as coating on iron coupon by the solution casting method. Corrosion protection efficiency of PVC/ZnO–polyaniline hybrid coating on iron coupons was studied by open circuit potential and Tafel techniques in 3.5% NaCl solution as corrosive environment. According to the results, PVC/ZnO–polyaniline hybrid nanocomposite coating showed dramatically increased corrosion protection effect on iron samples compared to that of uncoated iron coupon and pure polyaniline anticorrosive coating. It was found that ZnO nanoparticles improve the barrier and electrochemical anticorrosive properties of polyaniline and the addition of polyvinyl chloride increases the barrier effect of polyaniline coating.     

Corrosion protection performance of sol–gel coatings doped with red mud applied on AA2024-T3

This paper studies the effect of 5 wt% red mud particles addition to sol–gel films applied on AA2024-T3 aluminium alloy. The red mud powder was dried or calcined, previously to added to the sol–gel film, in order to analyzed the effect of the thermal activation. The RM particles were characterized using several techniques; x-ray diffraction (XRD), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The results confirm that the thermal treatment leads to several phase transformations which affect to gibbsite, Al(OH)₃, boehmite, AlO(OH), and goethite, FeO(OH), species.     

Corrosion behaviour of sol–gel treated and painted AA2024 aluminium alloy

Design, development and scale-up of environmentally friendly coatings are very important in order to replace chromate based coatings for aluminium alloys. Barrier properties, paint adhesion and possibly self-healing ability are relevant aspects for replacement of chromate-based pre-treatments. Sol–gel materials are candidates for use in protective coating applications, as it is possible to form highly adherent and chemically inert oxide films on metal substrates.     

Bond strength of hybrid sol–gel coatings with different additives

The hybrid sol–gel coating on Al 2024-T3 was modified by adding polyaniline, TiO₂, or γ-Al₂O₃ nanoparticles in the formulation separately. The coating was then used as an adhesive to bond Al 2024-T3 alloys, forming a single lap joint. The bond strength of the sol–gel coating was investigated using a universal tensile test machine. The lap shear strength of the original sol–gel coating was about 1.38 MPa and it was increased up to 2.26 MPa after the modification by adding 0.05 wt% PANI microparticles in the sol–gel coating. The small increase in strength was attributed to an improvement in its adhesive flexibility because of incorporation of the long-chain organic polymer in its structure. Furthermore, the addition of different amounts of TiO₂ nanoparticles in the unmodified sol–gel coating also led to an increase in shear strength compared to the undoped sol–gel coating. Typically, a sol–gel coating containing 2.0 wt% of TiO₂ recorded the highest adhesive strength of about 4.0 MPa. A similar increase in strength was observed when doping γ-Al₂O₃ nanoparticles into the original hybrid sol–gel coating. Adding 0.5 wt% of γ-Al₂O₃ in the sol–gel coating increased the adhesive bonding strength up to 4.48 MPa. The fracture surface of the specimen was separately observed by SEM and Optical Microscopy in order to examine potential evidences of mechanism and nature of failure. The reason why the adhesive strength increased after the modification of the sol–gel coating is discussed in this article.     

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.     

Sol–gel processing of hybrid nanocomposite protective coatings using experimental design

Environmentally friendly hybrid nanocomposite sol–gel coatings as substitutes for chromate conversion coatings have attracted a great deal of attention recently. The coatings derived from hydrolysis and condensation of polymerizable silane precursors tetraethylorthosilicate (TEOS) and 3-glycidoxypropyltrimethoxysilane (GPTMS) were deposited onAA5083 substrates by a dip coating technique. Statistical design of experimental (DoE) methodology based on Taguchi orthogonal design has been used to study and optimize compositional and process parameters using multifactor analysis of variance (ANOVA) analysis method and the adhesion strength of coatings to the substrate as per pull off test has been used as a response. Adhesive strength of sol–gel coatings to the substrate was evaluated using pull off and tape tests. Bending, impact resistance and pencil scratch tests were employed to characterize mechanical properties of different coatings. The surface morphology and chemical composition of the hybrid films were studied by atomic force microscopy (AFM) and Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy (ATR/FTIR), respectively. Optical microscopy (OM) and field emission scanning electron microscopy (FE-SEM) were used to investigate structure of the coatings. The results show an increase of the hydrolysis water content at a constant organic/inorganic molar ratio and other variable parameters increases adhesion of coatings to substrate, and optimum coatings exhibit excellent mechanical properties as well as adhesive to the substrate.     

Corrosion study of hybrid sol–gel coatings containing boehmite nanoparticles loaded with cerium nitrate corrosion inhibitor

To improve the corrosion protection of sol–gel derived hybrid silica/epoxy coatings containing boehmite nanoparticles, inorganic corrosion inhibitor was introduced into the coating via encapsulation in the nanoparticles. The morphology and chemical structure of the deposited films were studied by Scanning Electron Microscopy (SEM) and Fourier Transformed Infra-red Spectroscopy (FT-IR). The anticorrosion and self-healing properties of the coatings were evaluated by Electrochemical Impedance Spectroscopy (EIS). The high corrosion resistance performance of such coatings is due to the presence of encapsulated cerium nitrate corrosion inhibitor that can be released at the defects within the coating, hindering the corrosion reactions at defective sites.     

Corrosion study of hybrid sol–gel coatings containing boehmite nanoparticles loaded with cerium nitrate corrosion inhibitor

To improve the corrosion protection of sol–gel derived hybrid silica/epoxy coatings containing boehmite nanoparticles, inorganic corrosion inhibitor was introduced into the coating via encapsulation in the nanoparticles. The morphology and chemical structure of the deposited films were studied by Scanning Electron Microscopy (SEM) and Fourier Transformed Infra-red Spectroscopy (FT-IR). The anticorrosion and self-healing properties of the coatings were evaluated by Electrochemical Impedance Spectroscopy (EIS). The high corrosion resistance performance of such coatings is due to the presence of encapsulated cerium nitrate corrosion inhibitor that can be released at the defects within the coating, hindering the corrosion reactions at defective sites.     

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.     

Study of the degradation of hybrid sol–gel coatings in aqueous medium

The design and development of suitable multilayered functional coatings for delaying corrosion advance in metals and become controlled-release vehicles requires that the properties of the coatings are known. Coatings prepared by the sol–gel method provide a good approach as protective layers on metallic surfaces. This kind of coating can be prepared from pure chemical reagents at room temperature and atmospheric pressure, with compositions in a very wide range of environmentally non-aggressive precursors. Sol–gel coatings based on siloxane bonded units were prepared, starting with an organic–inorganic hybrid system. Synthesis procedures included acid-catalysed hydrolysis, sol preparation, and the subsequent gelation and drying. The alkoxide precursors used were methyl-triethoxysilane (MTMOS) and tetraethyl-orthosilicate (TEOS) in molar ratios of 10:0, 9:1, 8:2 and 7:3. After determination of the optimal synthesis parameters, the materials were characterised by solid ²⁹Si nuclear magnetic resonance (²⁹Si NMR), Fourier transform infrared spectroscopy (FTIR), contact angle measurement and electrochemical impedance spectroscopy (EIS) test. Finally, the materials were assayed by controlling their weight in contact with water, to determine their ability to degrade by hydrolysis. Electrochemical analysis reveals the formation of pores and water uptake during the degradation. The quantity of TEOS is one of the principal parameters that determine the kinetics of degradation. There is a correlation between the degradation process obtained for long periods and the electrochemical parameters obtained by EIS in short times. The study tries to incorporate knowledge that can be used for designing the degradation process of the functional coatings and to control their properties in short times.     

Preparation of nano-AlN powder by sol–gel foaming and its sintering properties

Uniformly dispersed nano-sized aluminum nitride powders were prepared by the sol–gel foaming method using aluminum nitrate as the aluminum source, sucrose as the carbon source, and ammonium chloride as the foaming agent. The effects of ammonium chloride content on the particle size and the sintering properties of aluminum nitride were investigated. The results showed that when the molar ratio of ammonium chloride to aluminum nitrate was .5, the colloidal foams were uniform, large, and fluffy, and amorphous alumina precursors with uniform particles could be prepared. Aluminum nitride powder with a particle size of 22–27 nm can be obtained by calcining these precursors in nitrogen atmosphere at 1400°C for 2 h. At the same time, aluminum nitride bulk material with a relative density of 95% can be obtained by sintering the compact samples in nitrogen atmosphere at 1700°C for 2 h.