锌和镀锌钢的稀土表面改性

通过在Ce(NO_3)_3水溶液中对锌和电镀锌钢进行化学转化(钝化)处理,在试样表面形成了铈转化膜。利用电子探针显微分析(EPMA)、X射线光电子能谱(XPS)和X射线衍射(XRD)等研究了转化膜的形貌、成分和结构,探讨了锌表面铈转化膜的形成机理。在氯化钠溶液中测定了试样的腐蚀率、极化曲线和电化学交流阻抗谱(EIS)等腐蚀性能参量,并与未钝化和普通铬酸盐钝化试样的情况作了对比。结果表明,本实验得到的锌表面稀土转化膜主要是由CeO_2、Ce_2O_3和ZnO组成的复合氧化物膜,铈转化膜的存在阻碍了锌在电化学腐蚀过程中的阴极反应和阳极反应,导致电荷传递电阻增大,腐蚀率降低。在一定条件下,铈转化膜对锌和镀锌钢的肪蚀效果优于铬酸盐转化膜。     

锌镀层表面稀土转化膜成膜机理分析(Ⅰ)

将镀锌层浸泡于以Ce(NO3)3.6H2O为主盐、以30%H2O2为氧化剂的稀土转化膜处理液中,通过计算界面上pH可达到的最大值、Ce-H2O系电位-pH图及Zn-H2O系电位-pH图,推断稀土转化膜可能是由ZnO、CeO2、Ce2O3、Ce(OH)3及Ce(OH)4构成;同时利用X射线光电子能谱仪对该铈盐转化膜表面进行成分分析,结果表明,铈盐转化膜主要是由ZnO、CeO2、Ce2O3、Ce(OH)3、Ce(OH)4构成的复合膜层,这与热力学分析计算相吻合。     

Effect of cerium and lanthanum additives on plasma electrolytic oxidation of AZ31 magnesium alloy

Plasma electrolytic oxidation（PEO） coatings on AZ31 magnesium（Mg） alloy were developed using the aqueous solution with alkaline silicate and sodium hydroxide as a base electrolyte system.The effects of cerium（Ce） nitrate and lanthanum（La） nitrate additives on the voltage response,microstructure,compositions and corrosion resistance of PEO coatings were investigated by scanning electron microscopy（SEM）,energy-dispersive spectrum（EDS）,X-ray diffraction（XRD） and potentiodynamic polarization tests,etc.The results showed that Ce and La additives increased the stable voltage and compactness of the PEO coatings,while,those did not change the compositions of the PEO coatings.The corrosion resistance of the PEO coating obtained in solutions with La nitrate of 0.1 g/L was the best,followed by that with Ce nitrate of 0.1 g/L and that without additives.     

Improving Corrosion Resistance of Cf/Mg Composites using Rare Earth Conversion Coatings

The surface of carbon fiber reinforced Mg matrix (Cf/Mg) composites was modified by treatment of rare earth conversion coating, and nontoxic, non-pollution Ce conversion coatings were prepared. The effect of the coatings on corrosion behaviors of composites was investigated by electrochemical polarization technology and electrochemical impedance spectroscopy (EIS) in 3.5% NaCl solution. The higher Ecorr and lower icorr were obtained by Ce conversion coatings. EIS results showed that the higher values of R2 were obtained by treatment containing CeCl3, the high corrosion resistance occured in treatment containing CeCl3, the low corrosion resistance in uncoating sample, the coating of treatment containing Ce(NO3)3 was medium. The microstructure of Ce conversion coatings was observed by scanning electron microscopy (SEM), and the elements of corresponding for coatings was characterized by energy dispersive spectrometer (EDS). The micro-cracks and Ce-riched spherical particles were characteristics of these coatings.     

Preparation and Corrosion Resistance of Rare Earth Conversion Coatings on AZ91 Magnesium Alloy

Magnesiumalloysarewidelyusedinweaponin dustry,spacenavigationandhavegoodpotentialof applicationanddevelopmentindailycommunication facilitiesduetotheirpropertiesoflightweightandhighstrength[1].Appliedasstructuralmaterials,mag nesiumalloysmayeasilycrackduet…     

Fabrication of a novel Mg-RE(Nd,Ce) intermetallic compound coating by molten salt diffusion and its effect on corrosion resistance of magnesium alloys

A novel Mg-rare earth(Nd,Ce) coating containing intermetallic compound was fabricated on the surface of the AZ91D magnesium alloy by bathing the sample in a NaCl-KCl-LiCl-NdCl_3-CeCl_3 molten salt. The cross-sectional morphology, microstructure and phase composition of the coating were investigated by scanning electron microscopy(SEM), transmission electron microscopy(TEM) and energy dispersive spectroscopy(EDS). The corrosion resistance was characterized by the potentiodynamic polarization curves. The SEM observation indicated that a continuous and compact diffusion coating was obtained on the surface of SMATed AZ91D magnesium alloy and the XRD and TEM investigations revealed that the new phases were Al_2Ce and Al_2Nd intermetallic. The potentiodynamic polarization curves showed that the Mg-RE coating improved the corrosion resistance of the AZ91D magnesium alloy, and the corrosion current density of the coated sample was about 1510 mA /cm~2 lower than the uncoated sample.     

Investigation of rare earth sealing of porous micro-arc oxidation coating formed on AZ91D magnesium alloy

Magnesium and its alloys have been used in many industries, but they are reactive and require protection against aggressive envi-ronments. In this study, oxide coatings were applied on AZ91D magnesium alloy using micro-arc oxidation (MAO) process. Then, in order to seal the pores of the MAO coatings, the samples were immersed in cerium bath for different times. The surface morphologies and composi-tions of the coatings were analyzed by scanning electron microscopy (SEM) and X-ray energy dispersive spectroscopy (EDS), respectively. The corrosion behavior of the coatings was investigated with electrochemical impedance spectroscopy (EIS) and potentiodynamic polariza-tion tests in 3.5 wt.% NaCl solution. The amount of the porosity of the coating was measured by electrochemical method. It was found that the sealing treatments by immersion in cerium bath successfully sealed the pores of the MAO coatings. The results of the corrosion tests showed that the MAO coating which was sealed in Ce bath for 10 min enhanced the corrosion resistance of the substrate significantly. Fur-thermore, this coating had the lowest amount of the porosity among the coatings.)     

铝管表面硅烷稀土复合膜的制备及性能研究

在60℃时采用浸渍法制备硅烷稀土复合膜,通过先在试样表面自组装一层γ-氨丙基三乙氧基(γ-APS)硅烷薄膜,再在膜上沉积稀土铈转化膜制得硅烷稀土复合膜。采用电化学、失重和盐雾实验对铝管表面硅烷稀土复合膜的耐蚀性进行考察。线性电位扫描、Tafel曲线和交流阻抗(EIS)的结果均表明其耐蚀性与空白样相比,极化电阻和自腐蚀电流均提高了两个数量级,阻抗阻值提高了2倍;盐雾实验结果也表明其抗蚀能力提高了3倍;SEM显示其复合膜层均匀致密,EDS检测分析表明复合膜主要由N,O,Si,Al和Ce等元素组成;初步探讨了复合膜的耐蚀机制。     

Preparation and Performance of Rare Earths Chemical Conversion Film on Magnesium Alloy

Golden yellow cerium conversion film was obtained on magnesium alloys surface by immersion method and the preparation parameters were established. The influence of different process parameters on the surface morphology and performance of the conversion film were analyzed by means of SEM and electrochemical method. Formation dynamics about cerium conversion film on magnesium alloy in solution containing cerium salt and the anti-corrosion behavior of the conversion film in 3.5% NaCl solution were studied by electrochemical method respectively. The results shows that the conversion film is more compact at room temperature when concentration of cerium sulfate is 10 g·L-1 in the solution; the open circuit potential of the magnesium sample moves up to positive direction about 100 mV, the surface of conversion film becomes even and lustrous, and the adhesion intensity of conversion film increases when adding aluminum nitrate into the solution containing cerium salt. The pH value of the solution and immersion time of the sample in the solution also affect the surface morphology and anti-corrosion property of the conversion film. After covered by rare earths conversion film, the anti-corrosion property of magnesium alloy is obviously improved. Rare earth conversion film has self-repairing capability in corrosion medium.     

Post treatment of silane and cerium salt as chromate replacers on galvanized steel

A complex film on hot-dip galvanized steel sheet (HDG) was prepared by immersing the sheet in 0.1wt.% Ce(NO3)3 solution and 5vol.% silane solution in turn. The corrosion protection of the complex film was evaluated by potentiodynamic linear polarization(LPR), electrochemical impendence spectra (EIS) and natural salt spray (NSS) tests and compared with that of single cerium film and silane film. The results showed that, the presence of these films on the zinc coating hindered corrosion reaction by reducing the rate of both anodic and cathodic reaction in the corrosion process, and the corrosion protection of the complex film was much better than that of single cerium film or silane film and closed to that of chromate film, because the polarization resistance Rp and electrochemical impendence were increased markedly. Microstructure and chemical composition of these pretreated films were also investigated by scanning electron microscopy (SEM) and AES.     

Corrosion behavior of rare earth cerium based conversion coating on aluminum alloy

The present paper focused on the use of the salt of rare earth cerium as corrosion inhibitor of aluminum by using cathodic electrolytic passivation method.The corrosion resistance and the microphology of the cerium passivation film were studied by the methods of electrochemical method,scanning electron microscopy(SEM),and energy dispersive spectroscopic analysis.From the results,it was shown that good corrosion resistance of cerium-based passive coating was obtained when the compositions were as follows:CeCl3·7H2O,0.05 mol/L;H2O2,30 ml/L;current density,1.1 mA/cm2;temperature,40 oC;time,9 min.SEM and EDS revealed that the cerium conversion coatings formed on the surface of aluminum alloy were related to cerium hydroxide/hydrated oxide depositions.     

Influence of lanthanum as additive and post-treatment on the corrosion protection properties and surface morphology of mild steel chemically treated by a cerium conversion coating

The influence of cerium conversion coating (CeCC) modified by lanthanum in two forms of additive and post-treatment solution on the corrosion resistance, surface morphology and surface chemistry of the mild steel was studied. Corrosion resistance was evaluated by electrochemical impedance spectroscopy, while the scanning electron microscopy, X-ray photoelectron spectroscopy and contact angle test were employed to investigate the surface characteristics. Results reveal that the CeCC post-treated by lanthanum containing solution gives rise to the deposition of a crack free and uniform conversion coating with enhanced corrosion resistance on the steel surface. Also, the surface free energy is increased after post-treatment.     

镁合金微弧氧化研究

在两种体系中研究了镁合金的微弧氧化.对比实验表明,磷酸盐体系中钕对氧化膜外观、厚度和耐蚀性有较大改善,提高钕盐浓度效果更佳;硅酸盐体系中,用稀土盐溶液浸泡试样后,制得的试样表面颜色较白,膜层分布更均匀,起弧容易.两种体系中用稀土转化膜取代镁合金表面的自然氧化膜进行微弧氧化处理,获得的陶瓷层分布更加均匀,表面更光滑致密,耐蚀性显著加强.     

Study on Anticorrosive Cerium Conversion Coating of Cf/6061Al Composite Surface

The optimum chemical passivation process of the rare earth metal (REM) conversion coating on the Cf/6061Al composite surface was introduced in this paper and its polarization curves properties were investigated. Ridge-like coatings were found by scanning electro microscope (SEM) observations, and the Al matrix and carbon fibre reinforcement were both coated with Ce conversion coatings, with some minor cracks. The energy dispersive spectroscopy (EDS) plane scan analysis indicates that the major elements in the coating are Ce, O, Si, Al and the Ce content reaches 47.48%(mass fraction). The Ce conversion coatings increase the corrosion resisting properties of Cf/6061Al composite, with a higher free corrosion potential (Ecorr) and a lower free corrosion current density (icorr) for the coated composite than those of the bare composite. And the Boehmite-treatment would enhance the corrosion resistance of the REM conversion coating. The cathodic polarization and anodic polarization were retarded by REM conversion coating, resulting in an improved corrosion resistance.     

锌表面稀土化学钝化及耐蚀性研究

采用三价铈盐对锌进行化学钝化处理 ,研究了有关工艺参数对锌表面稀土转化膜耐蚀性的影响 ,测量了钝化过程中试样的交流阻抗谱 (EIS)和表面显微硬度的变化 ,探讨了稀土转化膜的形成机理 ,并对成膜动力学进行了分析。随着钝化液的铈盐浓度、pH值、温度和处理时间的增加 ,稀土转化膜的耐蚀性也相应提高 ,一定条件下可达到或优于铬酸盐钝化的防蚀性能。稀土钝化成膜反应动力学符合Arrhenius方程 ,反应活化能约为 6 4 8kJ/mol。     

Composition and corrosion resistance of cerium conversion films on 2195Al-Li alloy

The Ce conversion films on 2195Al-Li alloy without and with post-treatment were studied and the corrosion resistance was evalu-ated as well. The surface morphology was observed by scanning electron microscopy (SEM), and the chemical composition was characterized by X-ray photoelectron spectroscopy (XPS). The corrosion behaviors of 2195Al-Li alloy and conversion coating were assessed by means of potentiodynamic polarization curves. The experimental results indicated that after post-treatment the surface quality was improved signifi-cantly. According to XPS, the conversion coating after post-treatment was mainly composed of CeO2, Ce2O3, Ce-OH and a little MoO3 and MoO2. The results of potentiodynamic polarization curves revealed that the conversion coating with post-treatment possessed better corrosion resistance than bare alloy and Ce conversion coating without post-treatment.     

Corrosion behavior of rare earth cerium based conversion coating on aluminum alloy

The present paper focused on the use of the salt of rare earth cerium as corrosion inhibitor of aluminum by using cathodic electrolytic passivation method. The corrosion resistance and the microphology of the cerium passivation film were studied by the methods of electrochemical method, scanning electron microscopy (SEM), and energy dispersive spectroscopic analysis. From the results, it was shown that good corrosion resistance of cerium-based passive coating was obtained when the compositions were as follows: CeCl₃·7H₂O, 0.05 mol/L; H₂O₂, 30 ml/L; current density, 1.1 mA/cm²; temperature, 40 °C; time, 9 min. SEM and EDS revealed that the cerium conversion coatings formed on the surface of aluminum alloy were related to cerium hydroxide/hydrated oxide depositions.     

Using EIS to evaluate anti-corrosion properties of the SiC_p/5A06 aluminium MMC treated by cerium conversion coatings

This paper evaluated the protection effect of the cerium conversion coatings on the SiCp/5A06 Al composite and the 5A06 Al alloy.Electrochemical impedance spectroscopy(EIS) was employed to examine the variation of the electrochemical variables of the samples treated and immersed in 3.5% NaCl solution at 35 °C for 1 h,which showed the enhancement of charge transfer resistance(Rt) and coating film resistance(Rc),i.e.,the corrosion resistance of the conversion coated samples was improved.The best protection effect was found for the samples treated for 60 min with 1000 μg/g CeCl3·7H2O/3.5% NaCl solution at 45 °C,followed with dried at 100 °C for 30 min.SEM/EDS examinations confirmed that the enhancement in corrosion resistance properties of these materials was due to the precipitation of cerium oxides/ hydroxides over the cathodic intermetallics and SiC particulates.The XPS results revealed that the conversion coatings were composed of CeO2,Ce2O3,Ce(OH)3,Ce(OH)4,and Al2O3.     

Effects of copper and manganese cations on cerium-based conversion coating on galvanized steel: Corrosion resistance and microstructure characterizations

The cerium conversion coating (CeCC) containing copper and manganese cations was applied to the galvanized steel. The microstructure and the composition of specimen were analyzed by field emission scanning electron microscopy (FE-SEM) and energy dispersive spectroscopy (EDS). Electrochemical impedance spectroscopy (EIS) and polarization tests were conducted in 3.5 wt% NaCl solution to investigate the coating corrosion resistance. The results show that there are improvements in corrosion resistance and microstructure of CeCC containing copper and manganese cations but copper ions increase corrosion resistance of CeCC from 5800 to 27000 Ω?cm².     

Investigation of Formation and Inhibition Mechanism of Cerium Conversion Films on Al 2024 Alloy

To study the mechanism of formation and inhibition of Ce conversion films on A1 2024-T3 alloy, scanning microreference electrode technique (SMRE) is used to probe the potential map on A1 2024-T3 in CeC13 solution, the localized corrosion of A1 alloy decreases with immersion time and disappears finally, which results from the competition of Cl^- aggression and Ce^3 inhibition on alloy surface. The results of X-ray photoelectron spectroscopy (XPS) indicate that the Ce conversion films consist of Al2O3, CeO2 and Ce2O3 (Ce(OH)3), and CeO2/Ce2O3 ratio decreases with the immersion time. When a critical pH for Ce(OH)3 formation was reached, Ce(OH)3 will precipitate on the micro cathodic area on alloy surface. Consequently, H2O2, the product of the catholic reaction will oxidize a part of Ce(OH)3 to CeO2, which appears a better corrosion resistance for Al alloys.