The corrosion resistance of 316L stainless steel coated with a silane hybrid nanocomposite coating

The present work aims at evaluating the corrosion resistance of 316L stainless steel pre-treated with an organic–inorganic silane hybrid coating. The latter was prepared via a sol–gel process using 3-glycidoxypropyl-trimethoxysilane as a precursor and bisphenol A as a cross-linking agent. The corrosion resistance of the pre-treated substrates was evaluated by neutral salt spray tests, linear sweep voltammetry and electrochemical impedance spectroscopy techniques during immersion in a 3.5% NaCl solution. In addition, the effect of the drying method as an effective parameter on the microscopic features of the hybrid coatings was studied using Fourier transform infrared spectroscopy and scanning electron microscopy. Results show that the silane hybrid coatings provide a good coverage and an additional corrosion protection of the 316L substrate.     

Effect of functional groups (methyl,phenyl) on organic–inorganic hybrid sol–gel silica coatings on surface modified SS 316

Organic–inorganic hybrid sol–gel based silica coatings derived from hydrolysis and condensation of organically modified silane precursors like phenyltrimethoxysilane and methyltriethoxysilane along with tetraethoxysilane were deposited on different surface pre-treated (as-cleaned, plasma-treated, shot-blasted) SS 316 grade stainless steel substrate, using dip coating technique. The coatings were heat treated at 150 °C for 2 h in air. The pre-treated surfaces were characterized using X-ray Photoelectron Spectroscopy and Scanning Electron Microscopy. The water content of the sols was determined by Karl Fischer titration to evaluate the degree of completion of hydrolysis and condensation reactions. Cured coatings were characterized to evaluate thickness, water contact angle, pencil scratch hardness, gloss, and shrinkage in coating thickness. Impact test was carried out on pigmented coatings derived from sols synthesized using the two silane precursors. The corrosion resistance and water durability tests were carried out to compare the coatings derived from using different precursors and different surface pre-treatments. The corrosion tests were carried out for 1 h and 24 h exposure to a 3.5% NaCl solution by electrochemical polarization measurements. It was found that coatings from methyl substituted organically modified alkoxysilane exhibited better hydrophobicity, scratch hardness, impact resistance and barrier properties with respect to corrosion, when compared to those derived from phenyl substituted trialkoxysilane. The difference in performance of coatings was explained on the basis of difference in hydrolysis and condensation rates between the two organically modified silane precursors used for the sol synthesis.     

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.     

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.     

Silica based organic–inorganic hybrid nanocomposite coatings for corrosion protection

Silica based organic–inorganic hybrid nanocomposite coatings have been developed for corrosion protection of 1050 aluminum alloys by dip coatings technique. The hybrid sols were prepared by hydrolysis and condensation of 3-glycidoxypropyl-trimethoxysilane (GPTMS) and tetramethoxy silane (TMOS) in the presence of an acidic catalyst and bisphenol A (BPA) as cross-linking agent. Such prepared hybrid coatings were found to be relatively dense, uniform and defect free. Structural characterization of the hybrid coatings were performed using optical microscopy, scanning electron microscopy (SEM) and attenuated total reflectance-infrared (ATR-IR) spectroscopy. Corrosion resistance properties of the hybrid sol–gel coatings were studied by potentiodynamic scanning (PDS) and salt spray testing methods. The results indicate excellent barrier protection performance of the coatings. In addition, the effect of molar ratio of GPTMS–BPA (silane content) on corrosion resistance of the coatings was investigated. The PDS results demonstrated that the corrosion resistance of hybrid coatings improved by decreasing of silane content.     

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.     

Corrosion protection by zirconia-based thin films deposited by a sol–gel spin coating method

This paper focuses on the structure and corrosion behavior of 316L stainless steel coated by inorganic ZrO₂, hybrid ZrO₂–PMMA, and combined inorganic–hybrid films. The coatings were deposited by a particulate sol–gel spin-coating route, using carboxymethyl cellulose as a nanoparticle dispersant. The electrochemical evaluations were conducted in a simulated body fluid, via potentiodynamic polarization and impedance spectroscopic experiments. According to the results, the hybrid coating presented a better corrosion protection compared to the inorganic coating, due to a lesser density of structural defects. However, the best corrosion resistance was found for a combined coating which consists of an inorganic bottom layer and a hybrid top layer, due to a desirable compromise of good adhesion and low defect density.     

Electrochemical behavior of (Cr,W, Al,Ti, Si)N multilayer coating on nitrided AISI 316L steel in natural seawater

AISI 316L steel is often used in materials applied toward nuclear power but are subjected to pitting corrosion in a marine environment. In this study, (Cr, W, Al, Ti, Si)N multilayer coatings were deposited using multi-arc ion plating on the surface of non-nitrided and nitrided AISI 316L steel. The microstructure and corrosion resistance of four different systems were investigated, namely, (i) untreated AISI 316L steel, (ii) plasma nitrided (PN), (iii) coated on an untreated matrix (coating) only, and (iv) coated on nitrided (hybrid) specimens. The phase structures, morphologies, and compositions of the different specimens were characterized using X-ray diffraction, transmission electron microscope, Atomic Force Microscope, scanning electron microscope, X-ray photoelectron spectroscopy, and energy dispersive x-ray spectroscopy. The results show that a thin CrWAlTiSiN multilayer coating, approximately 2.3 μm in thickness, is deposited on the surface of an ~12 μm nitrided layer. Potentio-dynamic polarization and electrochemical impedance spectroscopy were used to evaluate the assessment of the electrochemical behavior in the natural seawater of China's Yellow Sea. The hybrid specimens exhibited excellent corrosion resistance compared to both the nitrided and coated specimens.     

类金刚石薄膜在模拟体液中的电化学阻抗

利用双放电腔微波等离子体源全方位离子注入设备,分别采用等离子体增强化学气相沉积技术、等离子体源离子注入和等离子体增强化学气相沉积复合技术两种工艺对医用3161,不锈钢进行类会刚石薄膜表面改性。利用电化学阻抗谱法考察了两种工艺制备的类金刚石薄膜在模拟体液中的抗腐蚀性能。结果表明：与采用等离子体增强化学气相沉积技术制备的类金刚石薄膜相比,在72h的浸泡时间内,采用等离子体源离子注入和等离子体增强化学气相沉积复合技术制备的类金刚石薄膜防腐蚀性能明显增高,腐蚀阻抗较高,碳注入层可有效抑制溶液渗入薄膜和基体之间的界面,起到了腐蚀防护层的作用。动电位极化测试表明：采用复合技术制备的类金刚石薄膜在模拟体液中的腐蚀倾向性更低,钝态稳定性更好。     

A comparative study on the corrosion resistance of AA2024-T3 substrates pre-treated with different silane solutions: Composition of the films formed

This work reports a comparative study on the corrosion resistance of AA2024-T3 pre-treated with three different silane solutions. The silanes used for the pre-treatments of the AA2024-T3 panels were: 1,2-bis(triethoxysilyl)ethane (BTSE), bis-[triethoxysilylpropyl]tetrasulfide (BTESPT) and γ-mercaptopropyltrimethoxysilane (γ-MPS). The analytical characterisation of the silane films was performed by Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). The corrosion performance of the pre-treated substrates was evaluated by electrochemical impedance spectroscopy (EIS). The results show that the pre-treatments based on silanes provide good corrosion protection of unpainted AA2024-T3. Painted substrates, previously pre-treated with the silane solutions also revealed improved corrosion resistance and good adhesion properties. Fatigue tests show that the silane pre-treatments do not affect the fatigue behaviour of the AA2024-T3. The work also discusses the formation of the protective silane films.     

Chemical composition and corrosion protection of silane films modified with CeO2 nanoparticles

The present work aims at understanding the role of CeO₂ nanoparticles (with and without activation in cerium(III) solutions) used as fillers for hybrid silane coatings applied on galvanized steel substrates.The work reports the improved corrosion protection performance of the modified silane films and discusses the chemistry of the cerium-activated nanoparticles, the mechanisms involved in the formation of the surface coatings and its corrosion inhibition ability.The anti-corrosion performance was investigated using electrochemical impedance spectroscopy (EIS), the scanning vibrating electrode technique (SVET) and d.c. potentiodynamic polarization. The chemical composition of silanised nanoparticles and the chemical changes of the silane solutions due to the presence of additives were studied using X-ray photoelectron spectroscopy (XPS) and nuclear magnetic resonance spectroscopy (NMR), respectively.The NMR and XPS data revealed that the modified silane solutions and respective coatings have enhanced cross-linking and that silane-cerium bonds are likely to occur.Electrochemical impedance spectroscopy showed that the modified coatings have improved barrier properties and the SVET measurements highlight the corrosion inhibition effect of ceria nanoparticles activated with Ce(III) ions. Potentiodynamic polarization curves demonstrate an enhanced passive domain for zinc, in the presence of nanoparticles, in solutions simulating the cathodic environment.     

Electrochemical investigation of high-performance silane sol–gel films containing clay nanoparticles

Silane sol–gel coatings are widely used as adhesion promoters between inorganic substrates, such as metals, and organic coatings. The aim of these pre-treatments is to enhance the corrosion protection performance of the organic coating improving the adhesion to the substrate and acting as a barrier against water and aggressive ions diffusion. It is a matter of fact that the silane sol–gel pre-treatments do not provide an active protection against corrosion processes except for the partial inhibition of the cathodic reaction. Inorganic pigments can improve the barrier properties of the silane sol–gel film, enhancing the resistance against corrosion. In this study, different amounts of montmorillonite nanoparticles were added to a water based silanes mixture in order to improve the barrier properties of the sol–gel coating. Hot dip galvanized steel was used as substrate. The sol–gel film consists of a combination of three different silanes, GPS, TEOS and MTES. The clay nanoparticles used in this study were mainly neat montmorillonite. The proper concentration of filler inside the sol–gel films was determined comparing the corrosion resistance of silane layers with different nanoparticles contents. Additionally, the effect of CeO₂ and Ce₂O₃ enriched montmorillonite particles. The EIS analysis and the polarization measurements demonstrated that the optimal amount of neat montmorillonite nanoparticles is about 1000 ppm. The same electrochemical techniques highlighted the limited effect of the cerium oxides grafted to the clay nanoparticles on the corrosion resistance of the silane sol–gel film. The TEM analysis proved the presence of a nano-crystalline structure inside the silane sol–gel film due to the formation of crystalline silica domains.     

Silane sol–gel film as pretreatment for improvement of barrier properties and filiform corrosion resistance of 6016 aluminium alloy covered by cataphoretic coating

The aim of this study is to develop a newly silane sol–gel pretreatment on the barrier properties and filiform corrosion resistance of 6016 aluminium alloy covered by cataphoretic coating. The sol–gel coatings are used as coupling agent between aluminium substrate and cataphoretic paint. The pretreatment is an aqueous solution of three different silane compounds (glycidyloxypropyltrimethoxysilane (GPS), tetraethoxysilane (TEOS) and methyltriethoxysilane (MTES)) hydrolysed at two different pH (2 and 3.5). A system without pretreatment was studied as reference. The electrocoatings were cured between 155 °C and 195 °C in order to modify their mechanical properties.Polarisation curves, EIS and FT-IR measurements were used in order to characterize the silane layers. EIS measurements were used to follow the barrier properties and the water uptake evolution on intact coatings.The filiform corrosion protection of the coating was also evaluated by a normalized filiform corrosion test.     

Effect of sub-layer temperature during HFCVD process on morphology and corrosion behavior of tungsten carbide coating

WC coating was deposited on the polished and cleaned 316L stainless steel by Hot Filament Chemical Vapor Deposition (HFCVD) technique at 400°C and 500°C. Field Emission Gun Scanning Electron Microscope (FEG-SEM) was used to study the corrosion morphology of the WC coatings. Energy dispersive spectroscopy (EDS) was used to analyze the chemical composition of the coatings. Coating porosity was measured by immersion in water. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques were used to study the corrosion behavior of the coating in the solution of 1 mol/L H₂SO₄. Results showed that the WC coatings have a honeycomb microstructure where its porosity was increased at higher temperature of the sub-layer. Also, the WC coating significantly increases the corrosion resistance of 316L stainless steel. And increasing the sub-layer temperature in the HFCVD method reduces the corrosion resistance of the WC coating. Corrosion morphology was indicative of pitting corrosion of the WC coating.     

Development of new processes to protect zinc against corrosion,suitable for on-site use

Protection against corrosion of metals is well known as an important issue in numerous fields. In all cases, the improvement of durability of these metals has to be connected to the development of environmentally friendly processes. Sol–gel protective coatings have shown excellent chemical stability and enhanced corrosion resistance for zinc substrates. Further, the sol–gel method, used as technique of surface protection, showed the potential for the replacement of toxic pre-treatments. This paper highlights the recent developments and applications of silane based sol–gel coatings on zinc substrates. Then, the challenges for industrial transfer of the developed process are also discussed because this process presents a disadvantage for on-site use, which is the too time-consuming thermal treatment. So, the goal of this study was to determine the convenient experimental conditions to reduce the duration of heat treatment of the hybrid sol–gel layer, compatible with the severe industrial requirements, without reducing the protection against corrosion. To reach this objective, a correlation between the results of chemical analyses and the protection against corrosion efficiency was established.     

Effect of silica/PVC composite coatings on steel-substrate corrosion protection

In this paper we focus on the preparation of thin polymer coatings synthetized from 30-nm and 600-nm silica particles dispersed in polyvinyl chloride (PVC) and deposited on two different steel substrates: duplex DSS 2205 and austenitic AISI 316L steel. We show that a silica surface modification with silane IO₇T₇(OH)₃ (trisilanol isooctyl polyhedral oligomeric silsesquioxane, POSS) significantly improves its dispersion properties when mixed with PVC. For comparison, the surface morphology and surface roughness of PVC coatings filled with both silanated and as-received (non-silanated) silica fillers were analyzed with scanning electron microscopy (SEM) and atomic force microscopy (AFM) when sprayed on the steel surface. The effect of the silica silanization is later on reflected in a decreased average surface roughness in the silanated, compared to non-silanated, silica/PVC-coatings. The wetting properties of the silanated and non-silanated silica/PVC-coatings on DSS 2205 and AISI 316L were investigated using contact-angle and surface-energy measurements, indicating an increased surface hydrophilicity in terms of a decreased static water contact angle and an increased total surface energy compared to the uncoated specimens. Finally, the beneficial corrosion resistance of the silica/PVC coatings was confirmed with potentiodynamic polarization spectroscopy in a 3.5% NaCl solution.     

Application of a repellent urea–siloxane hybrid coating in the oil industry

Urea–siloxane hybrid coatings were prepared by the sol–gel method from a dipodal diurea silane and methyltriethoxysilane. The coatings combine corrosion protection and scratch and solvent resistance in one layer and enable the incorporation of polydimethylsiloxane (PDMS) to achieve repellent properties. PDMS of different molecular weights were investigated with a molecular weight of 2000–3500 g/mol providing a repellent surface with the best durability. The coating was applied on plate heat exchangers mounted on North Sea oil platforms to prevent crude-oil derived fouling. While the uncoated heat exchangers get clogged by waxy substances and require costly maintenance in regular intervals, the coated heat exchanger significantly prolongs the service interval by at least a factor of 3.     

Analytical characterization of silane films modified with cerium activated nanoparticles and its relation with the corrosion protection of galvanised steel substrates

Galvanised steel substrates were pre-treated in bis-1,2-[triethoxysilyilpropyl]tetrasulphide silane solutions containing SiO₂ or CeO₂ nanoparticles activated with cerium ions. The surface composition was investigated by infrared spectroscopy. The film thickness was determined by scanning electron microscopy. The results showed that the barrier properties of silane films modified with nanoparticles depend upon the concentration of nanoparticles. The results also showed that the silane film thickness increases when the nanoparticles are activated with cerium ions. The anti-corrosion behaviour of the cerium activated nanoparticles was also investigated at the microscale level, in artificial induced defects, using the scanning vibrating electrode technique (SVET). The substrates treated with the silane coating modified with CeO₂ nanoparticles revealed improved corrosion behaviour comparatively to the coatings modified with SiO₂ nanoparticles. X-ray photoelectron spectroscopy and Auger electron spectroscopy experiments carried out on the defects after immersion in NaCl solutions revealed the presence of a surface film containing zinc corrosion products and cerium/ceria compounds.     

Corrosion protection of Mg alloys by cathodic electrodeposition coating pretreated with silane

The corrosion resistance characteristics of three coatings on magnesium alloy AZ31—conventional paint with phosphate film, cathodic electrodeposition coating (E-coating), and E-coating pretreated with silane (Mg/silane/E-coating)—have been studied by means of electrochemical impedance spectroscopy (EIS) in a 3.5 wt% NaCl neutral aqueous solution and salt spray test using ASTM B117. Silane film was obtained by dipping AZ31 specimens in diluted hydroalcoholic silanic solutions and successively curing. It was found that the corrosion resistance of the Mg alloy with E-coating was superior to conventional paint and could be further enhanced with silane pretreatment as an interfacial film. The results of water volume fraction (Φ_saturation) and diffusion coefficient (D) also indicated that the Mg/silane/E-coating possessed excellent compactness and corrosion resistance. A model of the corrosion mechanism for Mg/silane/E-coating has been presented through EIS analysis.     

Hierarchical polymer nanocomposite coating material for 316L SS implants: Surface and electrochemical aspects of PPy/f-CNTs coatings

Biocompatible nanocomposite coatings can be synthesized to offer improved surface properties for biomaterials and biomedical implants. Nanocomposite coatings containing polypyrrole (PPy) matrix reinforced with functionalized multi-wall carbon nanotubes (f-CNTs) were deposited on 316L SS substrates using electrochemical route. FT-IR, XRD, SEM, and TEM were employed to characterize the nanocomposite microstructure. High resolution imaging showed relatively uniform dispersion of the CNTs in the nanocomposite with a typical tubular structure. Micro-indentation tests revealed improvement in the hardness of the PPy/CNTs coatings. Measurement of the contact angle indicated enhanced surface wettability of the nanocomposite coatings. The corrosion behavior of 316L SS samples coated with PPy/CNTs was studied in SBF medium. The corrosion potential and the breakdown potential of coated 316L SS substrates shifted to more noble values as compared to uncoated 316L SS samples. The results suggest that incorporating CNTs as reinforcements in PPy coatings can provide enhanced properties in terms of surface hardness, biocompatibility, and corrosion resistance.