添加剂对铝合金稀土转化膜的影响
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摘要
目的寻找有效提高稀土转化膜性能的添加剂体系。方法采用电化学手段研究添加剂(硼酸、柠檬酸钠、磷酸钠、硅酸钠、氟化氢铵、氟化钠、草酸铵)对稀土转化膜的影响,对于具有积极作用的添加剂,使用响应面法进行复配,并优化配方。通过扫描电子显微镜(SEM)、能谱仪(EDS)和电化学测试对优化条件下制备的稀土转化膜性能进行表征。结果向基础转化液中加入氟化钠(NaF)、柠檬酸钠(Na_3C_6H_5O_7)和磷酸钠(Na_3PO_4)可以提高稀土转化膜的电化学性能。经过复配并优化配方,得到最优添加剂体系为0.68g/L氟化钠+0.80g/L磷酸钠。该配方可以抑制铝合金在转化液中的溶解,有利于铈元素的沉积,使铈的沉积量由5.01%提高到了9.60%。优化配方下制备出的膜层更加均匀致密,腐蚀电位提高了0.13 V,点滴时间可达122 s。XRD和EDS结果表明,膜层的主要成分为非晶态的铈锰氧化物。结论 0.68 g/L氟化钠+0.80g/L磷酸钠为最优添加剂配方。在优化体系中制得的稀土膜层的电化学性能得到了提升,表面更加均匀致密。
The work aims to improve the corrosion resistance of rare earth conversion coatings on aluminum alloys. Study the effects of different additives(H_3BO_3, Na_3C_6H_5O_7, Na_3PO_4, Na_2SiO_3, NH_4HF_2, NaF,(NH_4)_2C_2O_4) on the rare earth conversion coating, and compound the additives with positive effects and optimize the formula by response surface methodology.Characterization of rare earth conversion coatings prepared under different conditions was evaluated by scanning electron microscopy(SEM), energy dispersive spectroscopy(EDS), and electrochemical testing. The results showed that the addition of Na F, Na_3C_6H_5O_7 and Na_3PO_4 to the base conversion solution can improve the electrochemical performance of the rare earth conversion coating. After compounding and optimizing the formula, the optimal additive system was 0.68 g/L NaF+0.80 g/L Na_3C_6H_5O_7. The formulation can inhibit the dissolution of the aluminum alloy in the conversion liquid, is favorable for the deposition of Ce, and increases the deposition amount of Ce from 5.01% to 9.60%. The film prepared under the optimized formula is more uniform and dense with good electrochemical performance, corrosion potential increased by 0.13 V, drip time up to122 s. XRD and EDS results showed that the main component of the film is amorphous cerium or manganese oxide.
The work aims to improve the corrosion resistance of rare earth conversion coatings on aluminum alloys. Study the effects of different additives(H_3BO_3, Na_3C_6H_5O_7, Na_3PO_4, Na_2SiO_3, NH_4HF_2, NaF,(NH_4)_2C_2O_4) on the rare earth conversion coating, and compound the additives with positive effects and optimize the formula by response surface methodology.Characterization of rare earth conversion coatings prepared under different conditions was evaluated by scanning electron microscopy(SEM), energy dispersive spectroscopy(EDS), and electrochemical testing. The results showed that the addition of Na F, Na_3C_6H_5O_7 and Na_3PO_4 to the base conversion solution can improve the electrochemical performance of the rare earth conversion coating. After compounding and optimizing the formula, the optimal additive system was 0.68 g/L NaF+0.80 g/L Na_3C_6H_5O_7. The formulation can inhibit the dissolution of the aluminum alloy in the conversion liquid, is favorable for the deposition of Ce, and increases the deposition amount of Ce from 5.01% to 9.60%. The film prepared under the optimized formula is more uniform and dense with good electrochemical performance, corrosion potential increased by 0.13 V, drip time up to122 s. XRD and EDS results showed that the main component of the film is amorphous cerium or manganese oxide.
引文
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[2]赵勇,薛文斌,刘宏芳.稀土铈对铝合金LY12CZ微生物腐蚀行为的影响[J].物理化学学报,2011,27(11):2618-2624.ZHAO Yong,XUE Wen-bin,LIU Hong-fang.Effect of rare earth Ce3+on the microbial induced corrosion behavior of aluminum alloy LY12CZ[J].Acta physicochimica sinica,2011,27(11):2618-2624.
[3]孙晓麟,赵霞,金祖权,等.草酸阳极氧化法制备铝合金氧化膜及其防腐蚀性能[J].材料保护,2018,51(2):5-8.SUN Xiao-lin,ZHAO Xia,JIN Zu-quan,et al.Anticorrosion properties of aluminum oxide films prepared by anodic oxidation in oxalic acid electrolyte[J].Materials protection,2018,51(2):5-8.
[4]YASAKAU K,TEDIM J,ZHELUDKEVICH M,et al.Cerium molybdate nanowires for active corrosion protection of aluminium alloys[J].Corrosion science,2012,58:41-51.
[5]LIANG Cheng-hao,WANG Shu-sen,HUANG Nai-bao,et al.Effects of lanthanum and cerium mixed rare earth metal on abrasion and corrosion resistance of AM60magnesium alloy[J].Rare metal materials&engineering,2015,44(3):521-526.
[6]王慧婷,史娜,刘章,等.6xxx系铝合金表面腐蚀及其防腐的研究现状[J].表面技术,2018(1):160-167.WANG Hui-ting,SHI Na,LIU Zhang,et al.Surface corrosion and corrosion prevention of 6xxx-series aluminium alloy[J].Surface technology,2018(1):160-167.
[7]ARNOTT D R,RYAN N E,HINTON B R W,et al.Auger and XPS studies of cerium corrosion inhibition on 7075aluminum alloy[J].Applications of surface science,1985,22-23:236-251.
[8]李久青,高陆生,卢翠英,等.铝合金表面四价铈盐转化膜及其耐蚀性[J].腐蚀科学与防护技术,1996,8(4):271-275.LI Jiu-qing,GAO Lu-sheng,LU Cui-ying,et al.Corrosion resistance of a conversion film formed on aluminium by tetravalent cerium salt[J].Corrosion science and protection technology,1996,8(4):271-275.
[9]李久青,田虹,卢翠英.铝合金稀土转化膜碱性成膜工艺T3/T7的研究[J].腐蚀科学与防护技术,1998,10(2):39-43.LI Jiu-qing,TIAN Hong,LU Cui-ying.The alkaline film-forming technology of rare-earth conversion film on aluminum and its alloy[J].Corrosion science and protection technology,1998,10(2):39-43.
[10]MANSFELD F,WANG Y,SHIH H.The Ce-Mo process for the development of a stainless aluminum[J].Electrochimica acta,1992,37(12):2277-2282.
[11]李波涛,何昌协,徐志飞.6061铝合金表面稀土铈盐法处理工艺研究[J].有色金属加工,2018,47(3):39-42.LI Bo-tao,HE Chang-xie,XU Zhi-fei.Study on treatment process of rare earth ceriometry on surface of 6061 aluminum alloy[J].Nonferrous metals processing,2018,47(3):39-42.
[12]陈道琪,范洪远,陈志文,等.稀土在铝合金表面处理中的应用及研究进展[J].表面技术,2007,36(3):58-60.CHEN Dao-qi,FAN Hong-yuan,CHEN Zhi-wen,et al.The application and developments of rare-earth elements in surface treatments of aluminum alloy[J].Surface technology,2007,36(3):58-60.
[13]关玉芹,武卫社,杜军,等.6063铝合金表面Ce-Mn/Mo复合转化膜的制备及性能[J].表面技术,2014(6):79-83.GUAN Yu-qin,WU Wei-she,DU Jun,et al.Study on preparation and properties of Ce-Mn/Mo composite conversion coating on 6063 aluminum alloy[J].Surface technology,2014(6):79-83.
[14]许继辉.铝合金表面稀土转化膜的制备及耐蚀性研究[D].青岛:中国海洋大学,2009.XU Ji-hui.Study on preparation and corrosion resistance of rare earth conversion coating for aluminum alloy[D].Qingdao:Ocean University of China,2009.
[15]ALESSANDRO de N,PAUSSA L,GOBESSI A,et al.Cerium conversion coating and sol-gel multilayer system for corrosion protection of AA6060[J].Surface&coatings technology,2016,287:33-43.
[16]冯晋尧,曲丰作,徐同宽,等.P2缓蚀剂处理铝合金的耐腐蚀性能研究[J].表面技术,2016,45(5):214-218.FENG Jin-yao,QU Feng-zuo,XU Tong-kuan,et al.Corrosion resistance of P2 inhibitor treatment of aluminum alloy[J].Surface technology,2016,45(5):214-218.
[17]张军军.铝合金表面Ce-Mn转化膜常温制备及表征[D].广州:华南理工大学,2010.ZHANG Jun-jun.Preparation at room temperature and characterization of Ce-Mn conversion coating on Al alloy[D].Guangzhou:South China University of Technology,2010.