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.     

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.     

Effect of cerium concentration on microstructure,morphology and corrosion resistance of cerium–silica hybrid coatings on magnesium alloy AZ91D

The aim of this work was to investigate the effect of cerium concentration on microstructure, morphology and anticorrosion performance of cerium–silica hybrid coatings on magnesium alloy AZ91D. Vinyltriethoxysilane (VETO) and γ-glycidoxypropyltrimethoxysilane (GPTMS) were employed as precursors to prepare sol–gel based silica coating. Cerium nitrate hexahydrate as dopant in five different concentrations was added into the silica coatings. Fourier transform infrared (FT-IR) spectrum analysis, viscosity measurements and scanning electron microscopy (SEM) were employed to characterize the microstructure and morphology of these coatings. It was found that with the increase of cerium concentration, the degree of decomposition of silane chains in the coating network increased. The corrosion resistance of the cerium–silica hybrid coatings was estimated by electrochemical impedance spectroscopy (EIS) measurements and potentiodynamic polarization tests. The results demonstrated that corrosion resistance of coatings initially increases and then decreases as cerium concentration goes up. When the cerium concentration is 0.01 M, corrosion resistance reaches its maximum.     

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 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.     

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.     

The effect of zirconia ions on corrosion performance of sol–gel coated galvanized steel

Currently, galvanized steel is treated with hexavalent chrome passivation. Sol–gel coating has been found to be a potential replacement for the hazardous hexavalent chrome passivation treatment. The aim of this work is to study the effect of zirconyl nitrate on corrosion behavior of sol–gel coating. Aminopropyl-trimethoxysilane and 3-glycidoxypropyltrimethoxysilane were employed as precursors to prepare the sol–gel-based silane coating. The sol–gel film was deposited on galvanized steel sheet by dip coating method. The chemical properties of sol–gel solution and coated films were analyzed by infrared spectroscopy. Morphology of the film was characterized by scanning electron microscope. The corrosion resistance of the coated samples was evaluated by electrochemical impedance spectroscopy, potentiodynamic polarization curve, and salt spray test. The results indicated that zirconia-doped coatings have better corrosion resistance in comparison with their undoped counterparts. The coating doped with 0.5% zirconyl nitrate provides better corrosion protection due to the inhibitive action of zirconia ion.     

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.     

Effect of chloride concentration range on the corrosion resistance of Cu–xNi alloys

The anodic behaviour of Cu–xNi alloys and Cu and Ni metals was studied in slightly alkaline solutions containing Cl–-ions in the concentration range from 0.01 to 2.0moldm–3. The morphology and composition of the surface films formed by anodic polarization were analysed by scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). On the basis of quasi-potentiodynamic polarization data, Ec against cNaCl diagrams were constructed, where Ec is the critical pitting potential. These diagrams allow the determination of areas where the materials are susceptible to localized pitting attack. A critical chloride concentration (ccrit) exists below which the resistance to localized corrosion increases with decreasing nickel content and above which it increases with increasing nickel content. This effect is connected with the change in the corrosion resistance observed for the pure metal constituents, i.e., copper and nickel as a function of chloride concentration. The kinetic parameters of pitting corrosion of Cu–xNi alloys reflect the specific properties of both elements and suggest that an increase in Ni content above 40% would not have a significant effect on the corrosion resistance of Cu–xNi alloys.     

Effect of SiC on the corrosion resistance of electroless Cu–P–SiC composite coating

In this work, Cu–P–SiC composite coatings were deposited via electroless plating with the addition of sodium hypophoshite (NaH₂PO₂) as a reducing agent. The coating compositions deposited were determined by using energy dispersive X-ray spectroscopy (EDX). The surface morphology of the coatings that were analyzed using scanning electron microscopy (SEM) showed that SiC particles were uniformly distributed by virtue of surfactant addition and mechanical stirring. The anti-corrosion properties of Cu–P and Cu–P–SiC coatings in NaCl and HCl solutions were investigated by the weight loss and potentiodynamic polarization techniques. The results showed that the corrosion resistance of Cu–P–SiC coatings was superior to that of electroless Cu–P coatings and carbon steel substrates in various concentrations of NaCl and HCl solutions.     

Effect of curing process on simulated antisoiling properties of sol–gel coating on pine sapwood

Recently, inorganic–organic hybrid coatings produced by the sol–gel route have proven to be a potential protective treatment for wooden surfaces. In this study, the effect of curing process on simulated antisoiling properties of sol–gel coating was investigated. The sol–gel coating was spray-coated on pine sapwood and cured with different temperature and time combinations. The antisoiling properties were studied by measuring the water contact angle of the coating after different curing processes. In addition, abrasion resistance and contact angle of oleic acid were measured. An optical profilometer was used to investigate surface roughness of the coating. Sufficient hydro- and oleophobicity were obtained with all of the curing parameters. The comparison between curing parameters showed that lower temperature and 1–3 h curing time leads to significant improvement in the durability of the water and oil repellent properties of the coating.     

Enhancement of hybrid sol–gel coating and industrial application on polished porcelain stoneware tiles and investigation of the performance

The aim of this study was to improve stain resistance and cleanability of polished porcelain tiles by sealing the micro-pores on the tile surface with hybrid sol–gel solution. For this purpose, solutions of a hybrid system based on sol–gel technology were prepared. The obtained solution were applied to polished unglazed tiles and subsequently spread with soft tissue thereon. To achieve complete sealing, both organic and inorganic particles of different sizes were mixed with obtained sol–gel hybrid systems. Coated surfaces were investigated by means of a scanning electron microscope. The stain resistance and the cleanability of the tile surface were tested according to ISO-10545-2014 standard. It has been shown that prepared sealing material permanently prevents formation of stains such as olive oil, green staining paste, iodine solution on the surface of polished porcelain tiles. The remains of stains on the surface can easily be removed from it with a cleaning agent.     

Enhancement of corrosion protection of 3-glycidoxypropyltrimethoxysilane-based sol–gel coating through methylthiourea doping

Protection of aluminum metal and its alloys from corrosion is a key requirement for many engineering applications. Nowadays, sol–gel coating technology is recognized as the ideal replacement for chromate conversion coatings. The present work makes use of 3-glycidoxypropyltrimethoxysilane (GPTMS) as a precursor for sol–gel coating. GPTMS was subjected to hydrolysis and subsequent condensation reaction to get a three-dimensional network and methylthiourea (MTU) was incorporated into the sol–gel matrix. MTU-doped GPTMS-based sol–gel coatings were applied over aluminum metal by dip coating method. The resultant coating was studied by FTIR, XRD and SEM. MTU-doped GPTMS-based sol–gel coatings increased the hydrophobic nature of the coating and were stable up to a temperature of 450°C. The protective nature of the coatings was evaluated in a 1% NaCl environment using electrochemical impedance and polarization studies. The study has revealed that doping of MTU enhanced the protection ability of doped GPTMS-based sol–gel coating to a significant extent.     

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.     

Tough hybrid hydrogels based on simultaneous dual in situ sol–gel technique and radical polymerization

A tough hybrid hydrogel has been developed by dual in situ sol–gel reaction of γ-ethacryloxypropyltrimethoxysilane (MPTMS) and tetrabutyl titanate, as well as in situ radical polymerization of acrylamide (AM) and MPTMS. In this hydrogel, covalently bonded SiO₂ and TiO₂ nanoparticles were used as inorganic filler and multifunctional crosslinker. Nano-TiO₂ was bonded onto the surface of SiO₂ by forming Ti O Si bonds and SiO₂ bonded with polymer chains by the formation of C O Si bonds, which were confirmed by Fourier transform infrared and X-ray photoelectron spectroscopy technology. Transmission electron microscopy images revealed that SiO₂ and TiO₂ tended to construct a distinct rod-like structure in poly(AM) matrix. This specific microstructure enhanced the mechanical properties of hydrogel. The compressive stress of the gel reached up to 9.49 MPa, and the compressive fracture energy was as high as 5307.73 J m⁻². This strategy provided a probable method for the preparation of tough soft materials with potential applications in chemical machinery and actuators. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47742.     

Fabrication and characterization of hybrid coating on Mg–Zn–Ca Mg alloy for enhanced corrosion and degradation resistance as medical implant

Magnesium (Mg)-based alloys have appealing properties as promising implants for medical applications. However, their clinical applications are hindered due to the rapid corrosion and degradation rate in the physiological environment. In this investigation, we reported a novel interfacial engineering approach for the fabrication of polymer/ceramic hybrid coating on Mg–Zn–Ca Mg alloy. Firstly, hydroxyapatite (HA) coating was fabricated on the Mg–Zn–Ca sample followed by an alkali treatment that was performed in 1 M NaOH solution at 60 °C. Finally, polycaprolactone (PCL) coating was synthesized using a dip-coating approach on the top of the HA-coated Mg–Zn–Ca specimen. Microhardness test and adhesion test revealed that PCL/HA hybrid coating significantly improved mechanical properties and enhanced biointerface property between the substrate and coating. The immersion tests showed that the hybrid coating considerably slowed down the degradation in the simulated body fluid (SBF) solution. In addition, in vitro electrochemical investigations confirmed that PCL/HA coating significantly improved corrosion resistance and greatly reduced corrosion rate by about 10 times compared to HA coating and about 900 times to untreated Mg–Zn–Ca sample. Moreover, cytotoxicity assessment exhibited PCL/HA hybrid coating enhanced biocompatibility and bioactivity due to adopting a suitable interfacial engineering approach.     

Impact of hybrid self-assembled nanophase particle-based sol–gel coatings on the localized corrosion behavior of modified 9Cr–1Mo steel in chloride medium

Corrosion protection coatings were developed based on a hybrid self-assembled nanophase particle process (HSNAP) for the localized corrosion resistance of modified 9Cr–1Mo steel in 0.05 M NaCl solution. The coating sol was prepared using silane-zirconia precursors and a polymeric crosslinking agent. Scanning electron microscopy and X-ray photoelectron spectroscopy were used to study the morphology and composition of the coated specimens, respectively. The thickness of the coatings was determined by a thickness gauge meter and Raman imaging analysis. The corrosion resistance of coated specimens was analyzed using electrochemical impedance spectroscopy, and it was observed that HSNAP-coated specimens showed superior resistance to localized corrosion than the as-received specimens in chloride medium.     

Structure characterisation and mechanical properties of crystalline alumina coatings on stainless steel fabricated via sol–gel technology and fibre laser processing

The surface modification of stainless steel by coating with alumina (Al₂O₃) was carried out using sol–gel coating technology in combination with laser processing. Alumina coatings have been synthesised via a sol–gel route and deposited on stainless steel substrates by dip coating. The coated substrates were then treated with pulsed ytterbium fibre laser radiation (λ = 1064 nm) in continuous wave mode with different specific energies. The composition and structure of the coated surfaces after laser processing were characterised by ATR-FTIR, XRD, SEM and contact angle measurements, whilst the mechanical properties of modified surfaces were determined using nano-indentation. The results showed that the alumina xerogel films coated on the substrates are successfully converted into crystalline alumina ceramic coatings by the laser irradiation, the structure of resulting coatings being dependent on the irradiation conditions, with increase of laser specific energy leading to the formation of initially γ-Al₂O₃ with increasing amounts of α-Al₂O₃ at higher energy. Nano-indentation results reveal that the laser processing results in significant improvement in hardness and Young's modulus of the alumina-coated surface and, at optimum, can achieve the mechanical properties at the same level as pure α-alumina ceramic, much higher than those of the as-dried xerogel coating.     

Preparation of multi-coating PZT thick films by sol–gel method onto stainless steel substrates

PbZr_0.45Ti_0.55O₃ ferroelectric films have been prepared by sol–gel method, using alkoxide precursor compounds and multi-layer technique. The gel films were deposited by spin-coating onto stainless steel substrates. In order to obtain crystallization in the perovskite phase, the samples were annealed at 600–700°C for 1 min. The dependence of the electric properties on the heat-treatment temperature is studied, and the coercive electric field as a function of the material thickness is determined. By SEM photography, the microstructure of the films could be shown to be homogeneous.     

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.