Development of cerium‐based conversion coatings on 2024‐T3 Al alloy after rare‐earth desmutting

The deposition of Ce‐based conversion coatings onto 2024‐T3 Al alloy sheet was studied using Rutherford backscattering spectroscopy, scanning electron microscopy, Auger electron spectroscopy, x‐ray photoelectron spectroscopy and atomic force microscopy. The Al sheet was pretreated with an alkaline clean followed by treatment in a Ce(IV) and H₂SO₄‐based desmutter. The Ce(IV)‐based conversion coating solution contained 0.1 M CeCl₃·7H₂O and 3% H₂O₂ and was acidified to pH 1.9 with HCl. Upon immersion, there was an induction period that included activation followed by aluminium oxide growth over the matrix and cerium oxide deposition onto cathodic intermetallic particles and along rolling marks on the surface. After the induction period cerium oxide deposited generally across the whole surface and thickened. The strongest anodic sites initially were adjacent to the intermetallic cathodes and resulted in aluminium dissolution but also oxide thickening. Copyright © 2004 John Wiley & Sons, Ltd.     

Conversion‐coating treatment applied to in situ TiB2p reinforced Al?Si‐alloy composite for corrosion protection

In this work, continuous conversion coatings on the surface of in situ TiB₂ particulate reinforced A356 composite were formed successfully by cerium surface treatment for the first time. Scanning electron microscope (SEM) analysis showed that the conversion coatings were inhomogeneous and could be divided into two types of regions, namely, fine crack region and noncrack region. Many cerium‐rich nano‐nodules were uniformly distributed in the whole coatings. Energy dispersive spectroscopy (EDS) analysis testified that the crack coatings mainly covered the interdendritic sites occupied by TiB₂ particulates and Si phases. X‐ray photoelectron spectroscopy (XPS) analysis indicated that the conversion coatings were composed of CeO₂, Ce₂O₃, Ce(OH)₄, Ce(OH)₃, and a little amount of Al₂O₃. The electrochemical polarization tests showed that the cerium‐conversion treatment markedly improved the corrosion resistance of in situ TiB_2p/A356 composite in chloride environment, and the protection degree of the coatings was superior to that of conventional chromate‐conversion coating. According to these results, the formation mechanism of cerium‐conversion coatings was discussed. Copyright © 2008 John Wiley & Sons, Ltd.     

Microstructural characteristics of Ce conversion coatings on Cf/Al composite or Ni?P plated Cf/Al composite

The microstructural characteristics of Ce conversion coatings on carbon fiber reinforced Al matrix (Cf/Al) composites and Ce conversion coatings on Ni? P plated Cf/Al composites were studied by SEM, AFM, TEM and XPS. The Ce conversion coating on the Ni? P plated composite does not have obvious microcracks, which can be found easily in Ce conversion coatings. The Ce conversion coating on Ni? P plated composite has a lower surface roughness profile arithmetic mean deviation (R_a) than Ce conversion coating, as seen by AFM. Because of the inhomogeneity of the material surface and the different levels of deposition of Ce conversion coatings at the different sites, nonhomogeneous sites would promote microcrack formation of the Ce conversion coatings. The Cf/Al composite surface has lessuniformity than Ni? P plated composite, leading to more prominent microcracks. Selected area electron diffraction (SAED) patterns of Ce conversion coating could not be indexed nor matched closely to any of the oxides (Ce₂O₃, Ce₇O₁₂, Ce₆O₁₁) or hydroxides (Ce(OH)₃) that are listed in the Powder Diffraction File maintained by Diffraction Data, but for Ce conversion coating on the Ni? P plated composite the data matched closely with that of CeO₂ or Ce₆O₁₁. The XPS results showed that the Ce conversion coating mainly contained both Ce³⁺ and Ce⁴⁺ species, but Ce⁴⁺ species were the dominant oxidation state on Ni? P coating with Ce conversion deposition. Copyright © 2008 John Wiley & Sons, Ltd.     

Al合金表面Ce转化膜成膜机理研究

Ce转化膜作为一种Cr转化膜的理想替代品而日益受到人们的重视，但其成膜机理还不很清楚.本文应用自行研制的扫描微参比电极技术（SMRE），原位测量经CeCl3溶液处理的2024-T3 Al合金表面微区电位分布，并结合X光电子能谱（XPS）和交流阻抗谱（EIS），对Ce转化膜的成膜机理进行探讨.结果表明，在CeCl3溶液中，Ce转化膜的形成过程是 Ce3＋和Cl－相互竞争的动态过程.当由Cl－的不均匀吸附引起的局部腐蚀使pH升高时， Ce(OH)3就会首先在局部位置发生沉积.阴极反应过程产生的H2O2可将Ce(OH)3部分氧化成CeO2.     

Characterization of chromate conversion film on tinplate substrate by XPS and electrochemistry methods

The chromate conversion coating formed on commercial tinplate via a cathode electrolytic dichromate treatment has been studied by X‐ray photoelectron spectroscopy (XPS) and electrochemistry methods. Through the analysis of the XPS, it was shown that there existed Cr, O, and Sn in the chromate coating and the chromate film consisted mainly of Cr(OH)₃, Cr₂O₃, Sn, and SnO_x. The current density decreased with increasing of the electric charge. The corrosion resistance for tinplate is relative with the content of chromium in the passivation film. Copyright © 2009 John Wiley & Sons, Ltd.     

Effects of Mn2+ on the chrome‐free colored Ti/Zr‐based conversion coating on 6063 aluminum alloy

The conversion coating with golden color and improved corrosion resistance had been prepared by adding Mn²⁺ in the Ti/Zr conversion coating solution. Comparing with that of conversion coating without Mn²⁺, the optimal treatment time of this conversion coating was much shorter and the corrosion resistance was obviously improved. The effect of Mn²⁺ on the formation of golden Ti/Zr conversion coating was thoroughly investigated by means of energy dispersive X‐ray spectroscopy, SEM, XPS, and Raman and electrochemical workstation. The results showed that the conversion coating had a double‐layer structure: the outer layer consisted of the metal‐organic complex and the inner layer was mainly made up of Na₃AlF₆. Mn²⁺ was oxidized into MnOOH in solution and precipitated on the substrate surface which provided the nucleus to Na₃AlF₆ crystal and accelerated Na₃AlF₆ crystal formation and also made the microstructure of conversion coating change to the cubic. The mechanism of the formation of the conversion coating can be deemed as nucleation, growth of Na₃AlF₆ crystal, and formation of metal‐organic complex. Copyright © 2015 John Wiley & Sons, Ltd.     

Al合金铈盐转化膜缓蚀机理研究

Ce盐作为一种环境友好的Al合金缓蚀剂日益受到重视 ,但缓蚀机理还不很清楚 .本文应用自行研制的扫描微参比电极技术 (SMRE) ,原位测量经CeCl3处理和未处理过的 2 0 2 4 T3Al合金表面微区电位分布 ,并用扫描电子显微镜 (SEM )和X 射线能量散射谱 (EDS)表征样品形貌特征 ,结合其它电化学技术 ,对Ce盐缓蚀机理作了深入探讨 .结果表明 ,经Ce盐处理的Al合金表面可形成一层不均匀分布的转化膜 ,抑制了O2 和电子传输 ,表现为一种优良的阴极缓蚀特性     

Effect of surface treatments on the localized corrosion resistance of the AA2198-T8 aluminum lithium alloy welded by FSW process

In this work, the effect of eight types of surface treatments on the corrosion resistance of friction stir welded samples of an AA2198-T8 Al-Cu-Li alloy were tested and compared in an attempt to find suitable alternatives to toxic and carcinogenic hexavalent chromium treatments. All the samples were anodized and subjected to different post-anodizing treatments. The post-anodizing treatments were (1) hydrothermal treatment in Ce (NO₃)₃ 6H₂O solution; (2) hydrothermal treatment in Ce (NO₃)₃ 6H₂O solution with H₂O₂; (3) hydrothermal treatment in boiling water; (4) hexavalent chromium conversion coating; and (5) immersion in BTSE (bis-1,2-(triethoxysilyl) ethane. The corrosion resistance of the treated samples was evaluated by immersion tests in sodium chloride solution (0.1 mol L⁻¹ NaCl) and electrochemical impedance spectroscopy (EIS) of the friction stir weldment. The results showed that among the alternative treatments, the Ce-containing solutions presented the best corrosion resistance, especially when used without peroxide.     

基于电化学噪声研究缓蚀剂对AA6063铝合金点蚀的影响

采用电化学噪声(ECN)、电化学阻抗谱(EIS)和极化曲线研究了AA6063 铝合金在3% (w) NaCl 溶液中的亚稳态点蚀萌发和稳态点蚀生长特征, 着重探讨了CeCl₃、Na₂CrO₄、8-羟基喹啉(8-HQ)等三种不同类型缓蚀剂对亚稳态和稳态点蚀的抑制机理. 结果表明: 当铝合金表面阴极相(Al-Si-Fe)周边的Al 基体发生局部溶解后,会导致邻近区域pH值升高(>8.4), 引起Ce(OH)₃在蚀点中心区的阴极相表面优先沉积, 从而抑制局部腐蚀的阴极去极化过程. 随着缓蚀剂浓度的提高, 亚稳态噪声峰的平均积分电量(q)随之递减, 但噪声峰的平均寿命几乎没有变化, 表明Ce³⁺并不能直接加速亚稳态蚀点的修复, 但可降低蚀点内金属Al 的溶解速率. CrO₄^2-不但可加速蚀点修复, 还可降低亚稳态蚀点的形核速率. 8-HQ主要与Al³⁺、Mg²⁺等形成不溶性螯合物并沉积在铝合金表面,提高了铝基体的全面抗腐蚀能力, 但并不能显著提高其耐点蚀能力.     

Al 6061/SiCp稀土转化膜的组成、结构及性能

铝金属基复合材料以其多方面的优异性能在航空、航天、汽车、电子和光学等工业领域中显示出了十分广泛的应用前景［１ ,２］．某些种类的（如ＳｉＣ颗粒增强）铝金属基复合材料已经开始走向工业规模的应用［３］．然而,在铝金属基复合材料中由于增强体的存在使其内部组织结构极不均匀,在使用环境中极易形成腐蚀微电池而遭受点蚀、剥蚀、磨蚀等等腐蚀形式的破坏［４ ,５］ ．适用于常规铝合金防腐处理方法的阳极氧化法和铬酸盐化学氧化法（Ａｌｏｄｉｎｅ法）存在着下述弊端而不能对铝金属基复合材料起到有效的防腐作用：１）铝金属基复合…     

Preparation of anticorrosion hybrid silica sol–gel coating using Ce(NO3)3 as catalyst

In this report, hybrid silica sol–gel coating was prepared using Ce(NO₃)₃ (Sol-Ce) as catalyst. Structure, surface morphology and anticorrosion ability of Sol-Ce solution/coating were studied by infrared spectroscopy (IR), scanning electron microscopy, energy dispersive spectrometer (EDS), potentiodynamic scan (PDS) and electrochemical impedance spectroscopy (EIS). IR results showed that Ce(NO₃)₃ had a stronger influence on reactivity of alkoxysilane. EDS results revealed that the fraction of Fe in Sol-Ce coating was significantly lower than regular acid-catalyzed hybrid silica sol–gel coating (Sol-Ac) and Sol-Ac with Ce(NO₃)₃-doped coating (Sol-Ac/Ce). The results of PDS and EIS demonstrated that Sol-Ce coating had better anticorrosion ability than Sol-Ac and Sol-Ac/Ce on carbon steel. The enhanced anticorrosion performance of the Sol-Ce coating might result from the following two reasons: (a) Ce(NO₃)₃ as a catalyst could alleviate the negative effects of low pH with using acid catalyst (dissolution of carbon steel) and (b) Ce(NO₃)₃ could impede corrosion of carbon steel as corrosion inhibitor.     

Electrochemical corrosion behavior of nanocrystalline zinc coatings in 3.5% NaCl solutions

The corrosion behavior of electrodeposited nanocrystalline (NC) zinc coatings with an average grain size of 43 nm was investigated in 3.5% NaCl solutions in comparison with conventional polycrystalline (PC) zinc coatings by using electrochemical measurement and surface analysis techniques. Both polarization curve and electrochemical impedance spectroscopy (EIS) results indicate that NC and PC coatings are in active state at the corrosion potentials, and NC coatings have much higher corrosion resistance than PC ones. The corrosion products on both coating surfaces are mainly composed of ZnO and Zn₅(OH)₈Cl₂·H₂O, but the corrosion products can form a relatively more protective layer on NC coating surfaces than on PC coatings. The EIS characteristics and corrosion processes of PC and NC zinc coatings during 330 h of immersion were discussed in detail.     

Conversion coatings of Mg-alloy AZ91D using trihexyl(tetradecyl) phosphonium bis(trifluoromethanesulfonyl)amide ionic liquid

This work reveals the performance of a trihexyl(tetradecyl)phosphonium bis(trifluoromethanesulfonyl)amide ([P6,6,6,14][NTf2]) ionic liquid (IL) conversion coating upon AZ91D. Such conversion coatings represent a novel avenue for chromate replacement. An optimization of coating performance was pursued by careful alloy pretreatment to generate a surface on which the coating performs best, as the AZ91 substrate is distinctly different from pure or dilute Mg alloys. The results reveal that a functional conversion coating can be achieved, retarding anodic dissolution kinetics, causing a significant decrease in corrosion rate. The coating efficacy is closely tied to the pretreatment performed, which dictates both the microstructural and electrochemical heterogeneity of the surface. The resulting coatings were found to contain MgxFx and phosphonium cation related components, the proportions of which were dependent on the pretreatment.     

The formation mechanism and biocorrosion property of CaSiO3/CaHPO4 · 2H2O composite conversion coating on the extruded Mg‐Zn‐Ca alloy for bone implant application·

In this work, a calcium silicate and calcium phosphate (CaSiO₃/CaHPO₄ · 2H₂O) composite coating was applied by a chemical reaction to an extruded Mg‐Zn‐Ca magnesium alloy. SEM observation showed that a flat and sand‐like conversion coating was formed. X‐ray diffractometer (XRD) analysis indicated that the conversion coating was composed of CaHPO₄ · 2H₂O and a little amount of CaSiO₃. The formation mechanism of CaSiO₃/CaHPO₄ · 2H₂O composite conversion coatings was discussed. The electrochemical polarization tests showed that the conversion coating markedly improved the biocorrosion resistance of Mg‐Zn‐Ca alloy in Hank's solution. Copyright © 2010 John Wiley & Sons, Ltd.     

Electrochemical corrosion behaviors and corrosion protection properties of Ni–Co alloy coating prepared on sintered NdFeB permanent magnet

In this study, a protective Ni–Co alloy coating was prepared on sintered NdFeB magnet applying electrodeposition technique. A pure nickel coating was also studied for a comparison. The microstructure, surface morphologies, and chemical composition of coatings were investigated using X-ray diffraction, scanning electron microscope, and energy dispersive spectroscopy, respectively. The corrosion protection properties of coatings for NdFeB magnet in neutral 3.5 wt.% NaCl solutions were evaluated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques. The microstructure and surface morphologies analysis showed that the addition of cobalt element into matrix metal Ni altered the preferential orientation of pure nickel coating from (2 0 0) crystal face for pure nickel coating to (1 1 1) crystal face for Ni–Co alloy coating, and made the surface morphologies more compact and uniform due to the grain-refining. The results of potentiodynamic polarization test showed that compared with pure nickel coating, Ni–Co alloy coating exhibited much nobler corrosion potential (E _corr) and lower corrosion current density (j _corr), indicating better anticorrosive properties. The long-term immersion test by dint of EIS indicated that the Ni–Co alloy coating still presented high impedance value of 1.9 × 10⁵ Ω cm² with the immersion time of 576 h indicating the excellent anticorrosive properties, and corrosion protection properties of nickel coating for NdFeB magnet practically disappeared with the immersion time of 144 h, which also indicated that the Ni–Co alloy coating provided better corrosion protection properties for the NdFeB magnet compared with nickel coating.     

Surface evaluation and electrochemical behavior of cerium conversion coating modified with silane on magnesium alloy

A new cerium conversion coating modified with the hydrolysis silane is designed for AZ31 magnesium alloy, which aims at assessing the surface characterizations and electrochemical behaviors between the cerium conversion coating with and without the silane modified. The effect of the silane addictive is studied by scanning electron microscopy (SEM) and X‐ray photoelectron spectroscopy (XPS). The adhesion of the coatings is undertaken according to the American Society for Testing and Materials (ASTM) standard D3359‐08 cross tape test. The electrochemical behavior is evacuated by polarization experiment and electrochemical impedance spectroscopy (EIS) in NaCl electrolyte. The results show that the addition of bis‐[triethoxysilylpropyl] tetrasulfide (BTESPT) to loosen and porous cerium conversion coating leads to the formation of a more compact and homogenous film, higher resistance to water uptake and better adhesion to substrate. Electrochemical measurements show that, compared with the non‐modified cerium conversion coating, the coating modified with the silane exhibits better anticorrosion properties. Copyright © 2014 John Wiley & Sons, Ltd.     

Inhibition effect of cerium in hybrid sol–gel films on aluminium alloy AA2024

Aluminium alloys such as AA2024 are susceptible to severe corrosion attack in aggressive solutions (e.g. chlorides). Conversion coatings, like chromate, or rare earth conversion coatings are usually applied in order to improve corrosion behaviour of aluminium alloys. Methacrylate‐based hybrid films deposited with sol–gel technique might be an alternative to conversion coatings. Barrier properties, paint adhesion and possibly self‐healing ability are important aspects for replacement of chromate‐based pre‐treatments. This work evaluates the behaviour of cerium as corrosion inhibitor in methacrylate silane‐based hybrid films containing SiO₂ nano‐particles on AA2024. Hybrid films were deposited on aluminium alloy AA2024 by means of dip‐coating technique. Two different types of coating were applied: a non‐inhibited film consisting of two layers (non‐inhibited system) and a similar film doped with cerium nitrate in an intermediate layer (inhibited system). The film thickness was 5 µm for the non‐inhibited system and 8 µm for the inhibited system. Film morphology and composition were investigated by means of GDOES (glow discharge optical emission spectroscopy). Moreover, GDOES qualitative composition profiles were recorded in order to investigate Ce content in the hybrid films as a function of immersion time in 0.05 M NaCl solution. The electrochemical behaviour of the hybrid films was studied in the same electrolyte by means of EIS technique (electrochemical impedance spectroscopy). Electrochemical measurements provide evidence that the inhibited system containing cerium displays recovery of electrochemical properties. This behaviour is not observed for the non‐inhibited coating. GDOES measurements provide evidence that the behaviour of inhibited system can be related to migration of Ce species to the substrate/coating interface. Copyright © 2010 John Wiley & Sons, Ltd.     

Preparation and adhesive properties of colored Ti/Zr-based conversion coating on aluminum foil for lithium battery packaging

In this study, an aluminum (Al) foil used for lithium ion battery packaging film was treated with titanium (Ti)/zirconium (Zr) solution containing hexafluorotitanic acid and hexafluorozirconic acid using tannic acid as a colorant and metavanadate as an accelerator, respectively, and a golden conversion coating was successfully deposited on the surface of Al foil. The morphology and composition of the coating were characterized by scanning electron microscopy, energy dispersive spectroscopy, and X-ray photoelectron spectroscopy, and the hydrophilicity was assessed by contact angle measurement. The effect of Ti/Zr treatment on the adhesion properties of Al foil was evaluated by T-peeling test and compared with that of traditional chromate-phosphate treatment. The results show that tannic acid contributes to the formation of the golden coating, and metavanadate accelerates the formation of the conversion coating. The results also indicate that the Ti/Zr-based conversion coating is mainly composed of Al₂O₃, Al (OH)₃, AlF₃, TiO₂/ZrO₂, NH₄VO₃, and V₂O₅. The Ti/Zr treatment cannot only improve the heat-sealing strength, but also the T-peeling strength by approximately 12 times compared with that of untreated Al foil. Thus, Ti/Zr treatment has the potential to replace the traditional chromate conversion treatment.     

Surface Pretreatments of AA5083 Aluminum Alloy with Enhanced Corrosion Protection for Cerium-Based Conversion Coatings Application: Combined Experimental and Computational Analysis

The effects of surface pretreatments on the cerium-based conversion coating applied on an AA5083 aluminum alloy were investigated using a combination of scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), polarization testing, and electrochemical impedance spectroscopy. Two steps of pretreatments containing acidic or alkaline solutions were applied to the surface to study the effects of surface pretreatments. Among the pretreated samples, the sample prepared by the pretreatment of the alkaline solution then acid washing presented higher corrosion protection (~3 orders of magnitude higher than the sample without pretreatment). This pretreatment provided a more active surface for the deposition of the cerium layer and provided a more suitable substrate for film formation, and made a more uniform film. The surface morphology of samples confirmed that the best surface coverage was presented by alkaline solution then acid washing pretreatment. The presence of cerium in the (EDS) analysis demonstrated that pretreatment with the alkaline solution then acid washing resulted in a higher deposition of the cerium layer on the aluminum surface. After selecting the best surface pretreatment, various deposition times of cerium baths were investigated. The best deposition time was achieved at 10 min, and after this critical time, a cracked film formed on the surface that could not be protective. The corrosion resistance of cerium-based conversion coatings obtained by electrochemical tests were used for training three computational techniques (artificial neural network (ANN), adaptive neuro-fuzzy inference system (ANFIS), and support vector machine regression (SVMR)) based on Pretreatment-1 (acidic or alkaline cleaning: pH (1)), Pretreatment-2 (acidic or alkaline cleaning: pH (2)), and deposition time in the cerium bath as an input. Various statistical criteria showed that the ANFIS model (R² = 0.99, MSE = 48.83, and MAE = 3.49) could forecast the corrosion behavior of a cerium-based conversion coating more accurately than other models. Finally, due to the robust performance of ANFIS in modeling, the effect of each parameter was studied.     

环氧树脂涂覆LY12铝合金在NaCl溶液中的阻抗模型

分别研究了裸LY12铝合金及涂覆环氧树脂涂层后合金在3.5％NaCl溶液中的电化学阻抗谱（EIS）.结果表明,LY12铝合金在点蚀电位以下阻抗谱上出现两个容抗弧,高频段对应Cl－参与的成膜阻抗,低频段对应铝阳极溶解的电化学反应阻抗.合金发生点蚀后出现低频感抗弧.合金/电极在NaCl溶液中先发生涂层吸水,当水及O2抵达基体后建立起电化学反应界面,合金遭受腐蚀；受涂层阻挡的影响,腐蚀产物的扩散逐渐成为控制步骤；当扩散速度较慢的Cl－抵达涂层/金属界面后,与界面处聚集的腐蚀产物间发生化学反应,完成成膜过程,阻抗谱上出现盐膜的阻抗,而扩散阻抗消失.提出了不同浸泡失效阶段涂层电极体系的阻抗模型.