Bonding and corrosion protection mechanisms of γ-APS and BTSE silane films on aluminum substrates

Films of γ-aminopropyltriethoxysilane (γ-APS), 1,2-bis[triethoxysilyl] ethane (BTSE) and their mixtures adsorbed onto pure aluminum from aqueous solutions were characterized by means of ellipsometry, infrared spectroscopy (IR) and X-ray photoelectron spectroscopy (XPS). It was found that after hydrolysis in water the silanes were readily adsorbed onto aluminum oxide surfaces initially forming hydrogen bonds. Upon curing, such bonds are replaced by metallosiloxane bonds, Si - O - Al. The remaining silanol groups in the film condense and form Si - O - Si bonds. As the Si - O - Al bonds are known to hydrolyze, the corrosion protection is related to the hydrophobicity of the siloxane films formed on the metal substrate. BTSE films are acidic as they contain free silanol groups, therefore these are compatible with some paints but not with others. Electrochemical impedance spectroscopy (EIS) results, salt spray test results and filiform corrosion test results showed that some silane treatments, such as two-step γ-APS/BTSE and BTSE only, provided better corrosion protection on aluminum substrates as compared with a chromate treatment. Mechanisms of adhesion and corrosion protection of these silane films on aluminum substrates are proposed.     

Deposition of hybrid 3-GPTMS's film on AA2024-T3: Dependence of film morphology and protectiveness performance on coating conditions

This paper describes the elaboration of 3-glycidoxypropyltrimethoxysilane (3-GPTMS) films onto AA2024-T3 aluminum alloy for corrosion protection.The dependence of sol–gel morphology on both precipitation under cathodic polarization and nitrate incorporation was investigated via scanning electron microscopy (SEM).Once added into silanization solution, sodium nitrate promoted the reaction of silane condensation and enhanced the film compactness.Electrochemical impedance spectroscopy results (EIS) indicated that doping silane film with NaNO₃ ameliorated its barrier property and protectiveness. Silane films applied onto AA2024-T3 surface by using potentiostatic method, exhibited obviously higher corrosion resistance than those obtained by conventional “dip-coating” method. The resistance of coating is accentuated when not very negative potential was applied.     

Photogenerated cathodic protection and invalidation of silane/TiO<Subscript>2</Subscript> hybrid coatings

Silane/TiO₂ hybrid coatings were prepared on 304 stainless steel (304 SS) by a simple dipping method, where the silane is d-γ-methylacryloxy propyl trimethoxyl silane (CH₂=C(CH₃)COO(CH₂)₃Si(OCH₃)₃, MPMS). The photogenerated cathodic protection and invalidation of the hybrid coatings were evaluated by microstructure and electrochemical characterization. The coupling agent MPMS reduced the agglomeration of the nanosized TiO₂ powders and promoted the adhesion of the coatings. Barrier protection of the coupled metal was promoted for the hybrid coatings in a short corrosion time. However, MPMS decreased the carrier concentration of the TiO₂ electrode due to the large interface resistance. As a result, the corrosion potential shifted positively and the photogenerated cathodic protection decreased. In long-time corrosion, the hybrid coatings became invalid because of the accumulation of electropositive holes that may weaken the Ti–O bond and destroy the barrier effect.     

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.     

黄铜表面硅烷自组装膜在氯化钠溶液中的耐蚀性

采用自组装技术在黄铜表面分别制备γ-巯基丙基三甲氧基硅烷(PropS-SH)、十二烷基三甲氧基硅烷(DTMS)、氨基丙基三甲氧基硅烷(APS)和γ-氯丙基三甲氧基硅烷(CPTMS)自组装膜,并分别采用电化学极化法、接触角测试和傅里叶红外光谱研究硅烷膜的耐蚀性、疏水生和结构.结果表明:经PropS-SH、DTMS和CPT...     

Corrosion resistance of aluminum oxide film and electrolytically coloured film in sodium chloride solution

The main interest of this study is to compare the corrosion resistance of aluminum anodic oxide film anodized in sulfuric acid bath with that of preanodized and electrolytically coloured film.Examinations have been carried out referring to (1) potentiostatted polarization curves shown on the specimens in 0.5 M sodium chloride solution, (2) impedance diagrams of the specimens and barrier thickness by Hunter's method and (3) optical metallographical observations of the aspects of pitting corrosion which took place on these specimens, and dipping test in corrosive solution.The results obtained are summarized as follows: (1) Typical difference was observed in regard to the potentiostatted polarization curves (i-t curves) between the two types of specimens in 0.5 M sodium chloride solution. The corrosion current caused by pitting corrosion of the electrolytically coloured specimens was smaller than that of anodized ones on the measurement by i-t curves. (2) The survey through the interfacial impedance diagrams of the specimens made clear that the impedance of the electrolytically coloured film was larger than that of uncoloured anodic oxide film, especially this greater increasing part of impedance was achieved in 15 s. This tendency was similar for the measurement of barrier thickness by Hunter's method. (3) The optical metallographical observations have demonstrated that there were far more advanced pitting corrosion on the anodic oxide film than on the electrolytically coloured film. In the dipping test, uncoloured anodized aluminum showed high extent of pitting corrosion, while electrolytically coloured aluminum performed well during colouring. So the total result of above examinations reveals that electrolytically coloured films are definitely more resistive to corrosion than anodic oxide films and this is due to the thick barrier layer of the former films.     

7075铝合金表面硅烷化处理的研究

对7075铝合金进行了硅烷化处理,并对硅烷膜的厚度、吸水率、成分、形貌及耐蚀性等进行了分析。硅烷处理液通过水解和缩合反应形成Si-O-A1共价键,覆盖在铝合金表面形成硅烷膜。结果表明:硅烷膜表面均匀、致密,吸水率仅为0.763%。,厚度约为4um;铝合金经过硅烷化处理后,膜电阻至少增加了两个数量级,自腐蚀电位正移一0・331 V,自腐蚀电流密度降低了近两个数量级,耐蚀性明显提高。     

Corrosion protection properties of silica coatings formed by sol–gel method on Al: The effects of acidity,withdrawal speed,and annealing temperature

In this research, silica films were coated onto aluminum sheets using the sol–gel dip-coating method from acidic and basic solutions containing (C₂H₅O)₄Si, C₂H₅OH, H₂O, and catalysts. NH₃ and HNO₃ were used as catalysts in the acidic and basic solutions, respectively. The characteristics of the films were investigated as a function of the sol catalyst, withdrawal rate, and heat treatment temperature. Morphology of the coatings was studied by scanning electron microscopy (SEM). Corrosion behavior of coated and uncoated aluminum sheets was measured in 0.1 M NaCl. Findings indicated that SiO₂ coatings can offer proper protective properties against corrosive environments. Results also showed that conditions used to prepare the coatings significantly affect the morphology and thus, the corrosion protection of the silica films.     

Adhesion performance of an epoxy clear coat on aluminum alloy in the presence of vinyl and amino-silane primers

The influence of amino and vinyl-silane-based treatments on the performance of an epoxy coated AA 1050 aluminum has been studied. The surface energy of the silane treated samples was determined using static contact angle measurement. Chemical interactions between the silane layer and aluminum substrates were also examined using FTIR-ATR spectroscopy. Pull-off adhesion was used under wet, dry and recovery conditions. The contact angle measurements showed a relative increase in the surface free energy of the silane treated specimens. For specimens treated with silane solutions below the IEP of aluminum, adhesion strengths were higher than those for pHs higher than IEP. This may suggest that an acid–base interaction occurs between the negatively charged silanol species and the positively charged AA surface. FTIR revealed two modes of interaction, one between silane and Al³⁺ (Si–O–Al), and the other indicative of a siloxane network (Si–O–Si). Thickness measurement showed that the silane layer is 100–200 nm thick indicating that the silane formed at the surface is not a monomolecular layer. Direct pull-off adhesion measurements of silane treated samples showed a significant improvement in initial bond strength compared with degreased aluminum substrates. However, those silane solutions having pHs higher than 8.4 showed inferior adhesion in comparison to those having lower pHs. The adhesion improvement was maintained, to some extent, after exposure to salt spray cabinet. In spite of good dry, wet and recovery adhesion, silane treated surfaces are not comparable with chromated AA aluminum in terms corrosion resistance.     

Improving the corrosion resistance of a-C:H film by a top a-C:H:Si:O layer

During the deposition of a-C:H film, defects (pinholes or discontinuities) caused by excessive stress will inevitably appear, which will reduce the corrosion resistance of the a-C:H film. In this study, top a-C:H:Si:O layers (thickness of approximately 0.3 μm) on the surface of a-C:H films were deposited on a large scale by PACVD technology using acetylene (C₂H₂) and/or hexamethyldisiloxane (HMDSO) as reactants, to improve the corrosion resistance of a-C:H films while ensuring the appropriate overall hardness of the films. The corrosion behaviors of the films were studied by electrochemical impedance spectroscopy (EIS) and Tafel polarization. We found that the a-C:H/a-C:H:Si:O films possess a lower electrolyte penetration rate due to their stronger capacitance characteristics. In addition, the corrosion current density of the a-C:H/a-C:H:Si:O films (10^?10 A cm^?2) were reduced by 2 orders of magnitude compared to the a-C:H film (10^?8 A cm^?2), and by 3 orders of magnitude compared to 316 stainless steel (10^?7 A cm^?2). The impedance results obtained by EIS were simulated using appropriate equivalent circuits, and the corresponding electrical parameters were used to further verify the electrochemical protection behavior of the top a-C:H:Si:O layer.     

Nanoparticle-filled silane films as chromate replacements for aluminum alloys

Silane surface treatments have been developed as an alternative for toxic and carcinogenic chromate-based treatments for years. It is consistently observed that ultra-thin silane films offer excellent corrosion protection as well as paint adhesion to metals. The silane performance is comparable to, or in some cases better than, that of chromate layers. The most recent studies also showed that the silane films can be thickened and strengthened by loading of a small amount of nanoparticles such as silica and alumina into the films resulting in enhanced corrosion protection of aluminum alloys.     

铝合金表面新型硅烷膜的制备及表面形貌研究

通过正交试验确定了铝合金表面硅烷膜技术的最佳工艺参数。在基础配方上制备了硅烷膜,利用硫酸铜点滴试验评价了工艺参数,结果表明,水解温度、硅烷浓度、醇水比及pH主要影响了硅烷溶液的水解与缩合反应。分析了硅烷膜的表面形貌、初步探讨了硅烷膜的耐腐蚀性能,结果表明,硅烷膜均匀、致密,具有比铬酸盐钝化更优的防护作用。     

铝合金表面GPTMS硅烷膜的制备及耐蚀性能研究

为提高铝合金耐腐蚀力,运用正交试验法研究在铝合金表面制备 γ-（2,3-环氧丙氧）丙基三甲氧基硅烷（GPTMS）自组装膜最佳工艺条件,利用极化曲线和扫描电子显微镜研究该硅烷膜在铝合金表面的耐腐蚀性能。研究表明：最佳工艺条件为 100 mL溶液中, pH＝4. 5,V（GPTMS）∶V（EtOH）∶V（H₂O）= 2∶7∶91,T_{1（水解温度）}＝25 ℃,t_{1（水解时间）}＝7 h,t_{2（浸涂时间）}＝10 min,t_{3（固化时间）}＝90 min,T_{2（固化温度）}＝120 ℃,该工艺条件下制备的硅烷膜具有优异的耐腐蚀性能。     

Corrosion protection of aluminum alloy substrate with nano-silica reinforced organic–inorganic hybrid coatings

Organic–inorganic hybrid (OIH) thin films derived from the sol–gel process have emerged as sustainable metal pretreatment alternatives to toxic heavy metal-based systems. In recent years, such OIH systems based on Si, Zr, and Ti have been successfully developed and commercialized for pretreatment of aluminum alloys, galvanized steel, cold-rolled steel, and many other metals and alloys, for improving adhesion and corrosion resistance performance. A variety of approaches are being used to further enhance performance of such OIH systems to match or surpass that obtained from chromate-based systems. In the present study, a novel bis-silane compound has been synthesized and used as a primary sol–gel precursor for OIH coatings. In order to further improve their mechanical and corrosion resistance performance, colloidal nanoparticles have been incorporated. The microstructure of the deposited films as a function of their composition and formation of Si–O–Si structural network has been studied by Confocal Raman spectroscopic technique. The chemical structure of the OIH films has been characterized by FTIR analysis. Electrochemical impedance spectroscopy, DC polarization measurements, and accelerated neutral salt-fog test (ASTM B117) have been used to evaluate corrosion resistance performance of coatings on industrial aluminum alloy AA 3003 H14. Nano-indentation tests of these OIH films have been performed to study the effect of colloidal nanoparticles on coating micro/nano structure and their mechanical properties. The study reveals that colloidal nanoparticles improve the corrosion resistance of OIH coatings by formation of a protective barrier to diffusion of corrosive species to the metal surface. The optimum content of colloidal nanoparticles that can provide best corrosion protection has been determined. Electrochemical study provides useful insight into the significance of interaction between the sol–gel hybrid and silica particles in the corrosion protection mechanism.     

Hybrid nanocomposite coating by sol–gel method: a review

The development of environmentally friendly process for pretreatments of metallic substrates is a field of growing research due to the ban against chromates used as protective pretreatments. Among the possible candidates for environmentally friendly pretreatments of aluminum alloys are the silica-based sol–gel coatings. Such coatings are able to form an Si–O–Al conversion layer providing a stable alumina/sol–gel film interface, which inhibits the onset of corrosion. Sol–gel technology offers a wide range of chemical mechanisms and exhibits high potential substitutes for the environmentally unfriendly chromate metal-surface pretreatment. Sol–gel derived organo-silicate hybrid coatings, preloaded with organic corrosion inhibitors, have been developed to provide active corrosion protection when integrity of the coating is compromised. The incorporation of organic corrosion inhibitors into hybrid coatings has been achieved as a result of physical entrapment of the inhibitor within the coating material at the stage of film formation and cross-linking. Sol–gel derived coatings, especially the hybrid films, provide a dense barrier against electrolyte uptake, and offer a wide range of applications as corrosion protective, hydrophilic coatings, hydrophobic anti-reflective coatings, migration barriers against liquid and volatile compounds, antibacterial modification of textiles and water-repellent antistatic textiles. In this paper, the novel applications of the sol–gel derived coatings are presented and discussed.     

Improving the formation and protective properties of silane films by the combined use of electrodeposition and nanoparticles incorporation

The electrodeposition and nano-silica incorporation were used together to prepare the novel composite dodecyltrimethoxysilane/SiO₂ thin films from silane sol-gel system on aluminum substrate. The results showed that both the two techniques can improve the films formation and their protectiveness. The influences of the deposition potential and the silica content in silane solution were investigated. A “critical deposition potential” and a “critical silica content” were both observed, under which the obtained silane films had the highest protective properties. The enhancement in film thickness has been detected by these two techniques from the elemental depth profiles of silane films as measured by secondary-ion mass spectroscopy (SIMS). Current-time curves were on-line recorded on aluminum electrodes in silane solutions. As compared with that in blank solution, the current response was found to be larger in silica-contained precursor, probably suggesting that the silica particles participate in the film deposition.     

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.     

Modification of bis-silane solutions with rare-earth cations for improved corrosion protection of galvanized steel substrates

Chemical formulations based on silane solutions are currently used for the pre-treatment of metallic substrates. These pre-treatments provide corrosion protection of the metallic substrates due to the good barrier properties of the silane films that form on the surface. The corrosion protection of silane-based pre-treatments can be improved by adding dopants to the silane solutions. The dopants must present corrosion inhibition properties and must keep or improve the barrier properties of the silane film without modification of surface functionality and bulk properties.     

Electrochemical behavior of hydrophobic silane–zeolite coatings for corrosion protection of aluminum substrate

The anticorrosive properties of a silane–zeolite composite coating applied on a 6061 aluminum substrate was investigated. The composite film, deposited by dip-coating technique, was prepared with different contents of SAPO34 powder (60–90 wt%) with the purpose of evaluating the protective action offered by the zeolite-filled silane matrix. Corrosion protection performance, during immersion in 3.5% NaCl solution, was evaluated by means of a potentiodynamic polarization test and electrochemical impedance spectroscopy (EIS). The coating evidenced good barrier properties and high hydrophobicity. The addition of zeolite in the silane matrix induced, as expected, a reduction of cathodic and anodic current. The zeolite improved the barrier properties of the hybrid sol–gel films, enhancing the resistance to localized corrosion attacks. Better results were observed for the sample with 80 wt% of zeolite filler that evidenced still acceptable protective action after 3 days of immersion in the sodium chloride solution.     

Preparation and characteristics of thin film with wear-resistant behavior on HDPE surface polymerized by C2H2–H2–SiH4 plasma

Plasma-polymerized deposition of an acetylene–hydrogen–silane mixture (C₂H₂–H₂–SiH₄) to obtain thin film with good wear behavior on a high-density polyethylene (HDPE) surface was present in this work. It was found that the bond between thin film and HDPE substrate was excellent and H₂ gas in system led the deposited thin film to better adhesive properties, but slower thin film deposition rate. Surface wear-resistant properties of modified HDPE were improved with the input of SiH₄. Infrared and X-ray photoelectron spectroscopy spectra suggested that there be large quantities of >CO, O H, C Si, and Si O groups in thin film and that the ratio of C to Si was increased due to the addition of SiH₄ and H₂, which inferred that the thin film structure and components lie between organic and inorganic materials. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 70: 1561–1566, 1998