The effect of cerium pre-treatment on the corrosion resistance of steel sheets

The steel samples have been coated with cerium layer by cathodic electrolytic deposition from the Ce(NO₃)₃·6H₂O solution in aqueous ethyleneglycol in the presence of hydrogen peroxide. The influence of the coating parameters (cathodic current density, pH, cerium concentration, hydrogen peroxide concentration, temperature, and treatment duration) on the surface properties; the optimum conditions of the formation of corrosion preventing coating have been elucidated. Hydrogen peroxide concentration and pH are the major factors influencing the deposition process. The corrosion resistance has been further enhanced after treatment with Na₃PO₄·12H₂O solution. The cerium-coated samples have been subsequently coated by cathodic electrostatic deposition from the colloidal solution of the paint. The coated materials have been subjected to mechanical testing (hardness, impact, cross cut, bending, and cupping tests), and their structure has been visualized by electron microscopy. The cerium coating has been found to improve the steel corrosion resistance by 15%.     

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.     

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.     

Growth behaviour of cerium-based conversion coating on Zn-5%Al alloy

Cerium-based conversion coatings were deposited on a Zn-5%Al alloy by immersing the alloy in cerium nitrate aqueous solutions with various immersion times. The growth behaviour of the cerium-based conversion coating on the Zn-5%Al alloy was investigated by the electrochemical impedance spectroscopy (EIS), SEM, energy dispersive spectroscopy (EDS), and XPS techniques. The results reveal that the coating mainly consists of ZnO, Zn(OH)₂, Ce(OH)₄, Ce(OH)₃, CeO₂, and Ce₂O₃. The growth of the cerium-based conversion coating is accompanied by metal dissolution. The dissolution mainly occurs on the η-Zn surface of the phase boundary and continues to extend to the Zn-rich phase as the coating grows. EIS results show that with increasing immersion time, the corrosion resistance of the Ce conversion coating gradually increases in the early growth stage and then decreases when the cracks appear.     

Passivation of zinc coatings in cerium-containing solutions

Process was developed for no-chromate passivation of zinc coatings in a solution containing 20-40 g L^-1 of cerium nitrate, 5-25 mL L^-1 H₂O₂, and 2-8 g L^-1 of an additive (8-10 g L^-1 of malic acid and 4-8 g L^-1 of sodium nitrate) at a temperature of 40-60°C and pH 2.5-3.5. It was shown that cerium-containing passivating coatings on zinc-plated steel articles compare well in corrosion resistance and protecting capacity with iridescent chromate coatings. It was found that cerium-containing coatings are capable of self-healing and sustain a thermal shock without degradation of their characteristics.     

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.     

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…     

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.     

Experimental and theoretical studies on the corrosion properties of some conducting polymer coatings

In this study, the effects of poly(N-ethylaniline) (PNEA) monolayer coating and PPY/PNEA and PNEA/PPY bilayer coatings, which were formed on the low carbon steel (LCS) surface by electropolymerization in 0.1 M monomer + 0.3 M oxalic acid medium, on the corrosion of the LCS in 1 M H₂SO₄ medium have been investigated. LCS electrodes, which were coated with each of these conductive polymer layers, were held in 1 M H₂SO₄ medium for various time periods, in order to obtain current potential curves, and with the help of these curves, the corrosion parameters have been determined. Experimental findings show that the LCS coated with polymer layers prevent the corrosion of bare LCS in 1 M H₂SO₄ medium and bilayer PPY/PNEA and PNEA/PPY coatings are better than monolayer PNEA coating. In order to elucidate the interaction between the coatings and the metal, theoretical calculations have been done using AM1 semiempirical method. The calculated data have been found to support experimental findings.     

Zn-Al-[V10O28]6-双层氢氧化物掺杂对LY12铝合金表面溶胶-凝胶涂层性能的影响

采用共沉淀法制备Zn-Al-[V₁₀O₂₈]^6-双层氢氧化物(以下简称LDH-V), 研究不同添加浓度(0.0、0.25×10^-3、0.75×10^-3、1.5×10^-3、3.0×10^-3 mol·L^-1)的LDH-V对LY12 铝合金溶胶-凝胶涂层形貌、耐蚀性的影响. 采用扫描电子显微镜(SEM)和傅里叶变换红外(FTIR)光谱研究LDH-V对涂层形貌和结构的影响. 运用中性盐雾实验对涂层进行耐蚀性评估. 利用电化学方法对涂层在0.05 mol·L^-1的NaCl 溶液中的腐蚀行为进行研究. 探讨加入LDH-V后溶胶-凝胶涂层的耐蚀机理. 结果表明, 一定量LDH-V的加入不仅可以提高溶胶-凝胶涂层的耐蚀性能, 还可对涂层被破坏区域进行自修复, 起到延缓铝合金基体腐蚀的作用. 然而, 当LDH-V的添加溶度超过一定值时, 会破坏涂层的完整性并降低涂层的腐蚀防护性能. 实验结果表明LDH-V最佳的添加浓度为1.5×10^-3mol·L^-1.     

EIS investigation of a Ce-based posttreatment step on the corrosion behaviour of Alclad AA2024 anodized in TSA

In the aircraft industry, anodizing and posttreatment steps use Cr (VI) compounds, which, despite offering good corrosion resistance and self-healing properties, are highly toxic and carcinogenic. Ce compounds are recognized as efficient corrosion inhibitors for Al alloys, and several works report self-healing ability for these chemicals. In this investigation, the corrosion resistance of Alclad AA2024-T3 alloy anodized in tartaric-sulphuric acid (TSA) bath and posttreated in a solution comprising cerium nitrate without and with hydrogen peroxide was evaluated. The purpose is to investigate the potentiality of using hydrothermal treatment in Ce nitrate solution as candidate to replace Cr (VI) posttreatment. The aim is to provide a posttreatment step which, while improving the corrosion resistance, does not plug the mouths of the pores maintaining the adhesion properties of the porous anodic layer. Microstructural characterization was carried out by SEM-EDS whereas corrosion resistance was evaluated by EIS. The surface analysis showed that the posttreatments, all performed at 50°C, kept the open structure of the pores. EIS analysis showed that the posttreatments performed in the H₂O₂ solution for short immersion times were the most effective in improving the corrosion resistance of the samples, whereas electrical equivalent circuit (EEC) fitting of the data indicated sealing of the porous layer during the immersion of the different samples in the test solution. SEM-EDS analysis of the samples posttreated in the H₂O₂ containing solution, prior and after the corrosion test, showed the presence of Ce oxy-hydroxide randomly deposited on the sample surface, indicating that Ce could be incorporated/stored in the anodic layer.     

Effect of formulation of silica‐based solution on corrosion resistance of silicate coating on hot‐dip galvanized steel

Several silica‐based solutions with 50 g/l of SiO₂ were prepared from sodium silicate solutions and silica sol; the silicate conversion coatings were obtained by immersing hot‐dip galvanized steel sheets in these solutions. These solutions were characterized using high‐resolution transmission electron microscopy and ²⁹Si nuclear magnetic resonance; the morphology of the coatings was observed by SEM and atomic force microscopy while the corrosion resistance was evaluated by electrochemical measurements as well as neutral salt spray tests. The results show that the coatings obtained from the single silica sol solution had poor adhesion and the coating obtained from the sodium silicate solution with low SiO₂/Na₂O molar ratio was uneven. By adding the silica sol to the silicate solution with low molar ratio, uniform coatings with better protection property were obtained. According to the results of ²⁹Si nuclear magnetic resonance spectra, the effects of the distribution of silicate anions with various polymerization degrees in the silica‐based solutions on the microstructure and corrosion resistance of the silicate coatings are discussed. Copyright © 2016 John Wiley & Sons, Ltd.     

Photoinduced formation of hydrogen peroxide in aqueous solutions of adenine derivatives at 77 K

The amount of hydrogen peroxide in aqueous solutions of adenine (A), adenosine (Ado), cytidine (Cyt), and thymine (T) containing 0.1 M NaCl and irradiated with near-UV light at 77 K is determined. It is established by comparing the results to data obtained earlier that the amount of H₂O₂ detected in the defrosted samples following identical irradiation falls in the order Ado > adenosine-5′-diphosphate (ADP) > A >> Cyt. The formation of H₂O₂ was not detected for T. The formation of H₂O₂ in solutions of adenine derivatives was observed when the samples were irradiated with light having wavelengths in the ranges λ = 240–400 nm and 290–450 nm. The latter covers only the long wave absorption range of these compounds. It is shown that the change in the intensity of irradiation that strongly affected the intensity оf EPR signals of irradiated samples prior to defrosting affected the amount of detected H₂O₂ only slightly, and the effect was not unidirectional. The results from determining H₂O₂ in the samples of adenine derivatives are compared to estimates of the content of free peroxyl radicals, obtained by analyzing EPR spectra. Plausible mechanisms of the processes are discussed.     

Use of rare earth metal salt solutions for corrosion protection of aluminum alloys and mild steel

The rare earth metal salt (REMS) compounds which are non-toxic and inexpensive have been used successfully for the corrosion protection of commercial aluminum alloys as well as of mild steel. The resistance to localized corrosion of aluminum alloys such as Al 2024, Al 6061 and Al 7075 has been greatly improved by immersion in hot cerium salt solutions. Cerium oxides/hydroxides were formed at sites where intermetallic compounds containing copper were located and eliminated the formation of local cathodes. REMS solutions were also used for sealing of anodized layer on Al alloys replacing toxic chromates. In addition to increased corrosion resistance excellent paint adhesion was observed. Cerium nitrate and yttrium sulfate solutions produced the most satisfactory results. Cerium salts were also applied successfully as inhibitors and as pretreatment for the corrosion protection of carbon steel in hot NH₃/water solutions used in absorption heat pumps. Factorial design experiments have been used to determine the optimum concentrations of CeCl₃ and H₂O₂ as well as the treatment time used in the cerating process for mild steel. The corrosion protection provided by the cerated layer was further improved by cathodic polarization in cerium chloride. A dual corrosion protection strategy employing cerating and addition of a REMS to the working solution is expected to provide long-lasting corrosion protection of mild steel. Dedicated to the ninetieth anniversary of Ya.M. Kolotyrkin’s birth. This article was submitted by the author in English.     

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.     

Synthesis of cerium orthophosphates with monazite and rhabdophane structure from phosphoric acid solutions in the presence of hydrogen peroxide

It has been proposed to conduct the synthesis of cerium(III) orthophosphates by reacting cerium(IV) compounds with hydrogen peroxide in the presence of concentrated orthophosphoric acid at ambient temperature. It has been shown that the reaction of H₂O₂ with CeO₂ suspensions in H₃PO₄ medium produces CePO₄ · xH₂O (rhabdophane structure), while that with CeO₂ solutions in concentrated H₃PO₄ results in CePO₄ (monazite structure).     

Corrosion behavior of tantalum alloying on γ‐TiAl by double‐glow plasma surface metallurgy technique

The Ta coating with corrosion resistance is grown on the γ‐TiAl substrate by double‐glow plasma surface metallurgy technique, followed by the electrochemical test in 10 wt%, 20 wt% HCl and 10 wt%, 40 wt% H₂SO₄ solution. The data of nanohardness and elastic modulus are collected by the nanoindention test. The adhesion strength of Ta coating is investigated by means of the scratch test. The study of corrosion resistance is performed using potentiodynamic polarization and electrochemical impedance spectroscopy and measured by SEM and X‐ray diffraction. Results highlight that the Ta coating is tightly bonded to the γ‐TiAl substrate, consisting of the deposition layer and diffusion layer. Experimental data indicate that the Ta coating presents excellent corrosion resistance, which is confirmed by the high values of polarization resistance (R_p) and the low values of corrosion current density (i_corr). The surface nanohardness of the Ta coating is improved from 3.41 to 7.29 GPa, nearly twice of that of the substrate. The Ta₂O₅ formed on the coating is able to hold back the penetration of adverse ions inwardly, owing to its dense structure and adhesion effect. Copyright © 2017 John Wiley & Sons, Ltd.     

The influence of Ce3+ ions on the corrosion rate of stainless steel in acidic solutions of different pH-values

The corrosion resistance of AISI 420 stainless steel in 0.1 mol L^?1 H₂SO₄ + 0.1 mol L^?1 Na₂SO₄ solutions at different pH-values and the inhibiting effect of Ce³⁺ ions was studied using electrochemical polarization methods. The results reveal decreasing of the corrosion rate with an increasing the pH of the solution, which demonstrates the progressive protective character of the inhibitor used. At pH lower than 3.33, the corrosion inhibition was most probably a result of the competitive adsorption of Ce³⁺ with H⁺ ions on the cathodic sites of the electrode surface, and it was found to be dependent on the relative concentration of H⁺/Ce³⁺. The peroxide generated from the oxygen reduction reaction at pH 3.33 was found to be capable oxidize trivalent cerium (Ce) to the tetravalent state. As obtained hydroxide precipitates act as diffusion barrier hindering the corrosion processes, whereafter a spontaneous passivity occurs on the steel surface at this pH.     

Electrosynthesis of hydrogen peroxide in solutions of salts that form molecular addition products (peroxo solvates) with it

The possibility of electrosynthesis of hydrogen peroxide in the electroreduction of oxygen in a gas-diffusion electrode in solutions of salts that form the molecular addition products (peroxo solvates) with H₂O₂ was studied. In KF and potassium and sodium phosphate solutions, H₂O₂ was obtained at concentrations of 2.3–3.6 M at current densities of 0.1–0.15 A/cm² and current efficiencies of 75–92%. The resulting solutions were concentrated to 11–27 M to give solid peroxo solvates with high hydrogen peroxide contents (22–50%). These results demonstrate that the application of gas-diffusion electrodes for electrosynthesis of inorganic products can be significantly expanded.     

Effect of Cu in electroless Ni–Cu–P coating on passivation process

Electroless Ni–P and Ni–Cu–P coatings were passivated by chromate conversion treatment respectively. The anticorrosive performances of passivated coatings were investigated by potentiodynamic polarization and electrochemical impedance spectroscopy measurements. The passivated Ni–Cu–P coating exhibited a high corrosion resistance with the i_corr of 0.236 μA/cm,² while the value of passivated Ni–P coating was only 1.030 μA/cm,² indicating the passive film could improve the corrosion resistance of Ni–Cu–P coating to a significant extent. High‐resolution X‐ray photoelectron spectroscopy was used to determine the chemical states of elements detected in the passive film. Compared with passivated Ni–P coating, the passive film on Ni–Cu–P coating exhibited a higher ratio of Cr₂O₃ to Cr(OH)₃ with the value of 72:28, which was the main factor for passivated Ni–Cu–P coating showing excellent corrosion resistance. The effect of Cu in electroless Ni–Cu–P coating on passivation process was discussed by the contrast experiment. Copyright © 2016 John Wiley & Sons, Ltd.