热浸镀Galfan表面镧盐转化膜的生长和耐腐蚀性能的研究
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摘要
在热浸镀Galfan镀层表面制备了镧盐转化膜,采用扫描电镜及能谱分析(SEM/EDS)、X射线光电子能谱分析(XPS)、原子力扫描探针显微分析(AFM)研究镧盐转化膜的表面形貌、化学成分和结构。通过中性盐雾试验、电化学极化分析和电化学阻抗研究膜层的耐腐蚀性能,确定最佳成膜时间。结果表明:镧盐转化膜成膜不均匀,优先在晶界或相界等活性区域;随着处理时间的延长,膜层的厚度增加;膜层上存在裂纹,且裂纹随着处理时间的延长而变宽,处理时间超过30 min时,膜层脱落,耐腐蚀性能降低;镧盐转化膜由La的氧化物/氢氧化物以及少量的Al和Zn的氧化物/氢氧化物组成。与未经处理的热浸镀Galfan镀层相比,镧盐转化膜显著减低基体的腐蚀速率,明显提高其耐腐蚀性能。
Lanthanum nitrate conversion coating was prepared on a hot-dip Galfan steel by dipping in a passivation solution of La(NO3)3. The surface morphology, chemical composition and structure of the coating were characterized by scanning electron microscopy(SEM) with X- ray energy dispersive spectrometer(EDS), X-ray photoelectron spectroscopy(XPS) and atomic force microscope(AFM). The corrosion resistance of the conversion film coated steel was assessed by neutral salt spray tests(NSS), electrochemical polarization curve and electrochemical impedance spectroscopy(EIS). The results showed that the conversion coating was not uniform, which had grown preferentially on grain- and phase-boundaries as well as other active sites. The thickness of the coating increased, while cracks in the coating expanded gradually with the increasing dipping- time. The coating spall off after dipping for more than 30 min, and therewith the protective performance of the coating degraded. In comparison with the blank Galfan steel, the corrosion rate of the conversion film coated Galfan steel lowered down significantly.
Lanthanum nitrate conversion coating was prepared on a hot-dip Galfan steel by dipping in a passivation solution of La(NO3)3. The surface morphology, chemical composition and structure of the coating were characterized by scanning electron microscopy(SEM) with X- ray energy dispersive spectrometer(EDS), X-ray photoelectron spectroscopy(XPS) and atomic force microscope(AFM). The corrosion resistance of the conversion film coated steel was assessed by neutral salt spray tests(NSS), electrochemical polarization curve and electrochemical impedance spectroscopy(EIS). The results showed that the conversion coating was not uniform, which had grown preferentially on grain- and phase-boundaries as well as other active sites. The thickness of the coating increased, while cracks in the coating expanded gradually with the increasing dipping- time. The coating spall off after dipping for more than 30 min, and therewith the protective performance of the coating degraded. In comparison with the blank Galfan steel, the corrosion rate of the conversion film coated Galfan steel lowered down significantly.
引文
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3 F.Rosalbino,E.Angelini,D.Macciò,A.Saccone,S.Delfino,Application of EIS to assess the effect of rare earths small addition on the corrosion behaviour of Zn-5%Al(Galfan)alloy in neutral aerated sodium chloride solution,Electrochimica Acta,54(4),1204(2009)
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5 S.Feliu,V.Barranco,XPS study of the surface chemistry of conventional hot-dip galvanised pure Zn,galvanneal and Zn-Al alloy coatings on steel,Acta Materialia,51(18),5413(2003)
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8 XU Qiaoyu,WANG Haixia,JIANG Rui,Formation and corrosion resistance of titanium containing conversion film on hot-dip Galvanized steel,Chinese Journal of Materials Research,28(7),521(2014)(许乔瑜,王海霞,姜瑞,热浸镀锌层钛盐转化膜的制备和耐蚀性能,材料研究学报,28(7),521(2014))
9 YANG Lihui,LI Junqing,YU Xiang,ZHANG Milin,Molybdate conversion coatings on AZ31 magnesium alloy,The Chinese Journal of Nonferrous Metals,18(7),1211(2008)(杨黎晖,李峻青,于湘,张密林,AZ31镁合金钼酸盐转化膜,中国有色金属学报,18(7),1211(2008))
10 L.Jiang,M.Wolpers,P.Volovitch,K.Ogle,An atomic emission spectroelectrochemical study of passive film formation and dissolution on galvanized steel treated with silicate conversion coatings,Surface&Coatings Technology,206(13),3151(2012)
11 KONG Gang,ZHANG Shuanghong,SUN Ziwen,CHE Chunshan,LU Jintang,Effect of size of silica powder on preparation of silicate conversion coatings on Galvanized steel,Chinese Journal of Materials Research,28(6),462(2014)(孔纲,张双红,孙子文,车淳山,卢锦堂,二氧化硅粉体粒度对硅酸盐转化膜制备的影响,材料研究学报,28(6),462(2014))
12 G.Rossana,M.L.Abel,M.A.Baker,B.Dunn,J.F.Watts,The adsorption of an epoxy acrylate resin on aluminum alloy conversion coatings,International Journal of Adhesion and Adhesives,31(7),687(2011)
13 ZHENG Runfeng,LIANG Haocheng,SHAO Lin,Study of composition and corrosion protection afforded by phytic acid conversion coatings applied to AZ91 magnesium alloy,Journal of Dalian University of Technology,46(1),16(2006)(郑润芬,梁浩成,邵林,AZ91D镁合金植酸转化膜组成与耐腐蚀性能研究,大连理工大学学报,46(1),16(2006))
14 LU Jintang,ZHANG Shuanghong,KONG Gong,CHE Chunshan,Composition and Corrosion resistance of molybdate/silane composite films on Galvanized steel,Journal of South China University of Technology(Natural Science Edition.,37(12),12(2009)(卢锦堂,张双红,孔纲,车淳山,镀锌钢上钼酸盐/硅烷复合膜的组成与耐蚀性,华南理工大学学报:自然科学版,37(12),12(2009))
15 M.F.Montemor,W.Trabelsi,M.Zheludevich,M.G.S.Ferreira,Modification of bis-silane solutions with rare-earth cations for improved corrosion protection of galvanized steel substrates,Progress in Organic Coatings,57(1),67(2006)
16 S.H.Zhang,G.Kong,J.T.Lu,C.S.Che,L.Y.Liu,Growth behavior of lanthanum conversion coating on hot-dip galvanized steel,Surface&Coatings Technology,259,654(2014)
17 KONG Gang,WU Shuang,LIN Dexin,WANG Xia,LI Hanchang,LU Jintang,Growth mechanism of cerium salt conversion coating modified with citric acid on galvanized steel,The Chinese Journal of Nonferrous Metals,22(5),1390(2012)(孔纲,吴双,林德鑫,王霞,黎汉昌,卢锦堂,热镀锌层柠檬酸改进型铈盐转化膜的生长机理,中国有色金属学报,22(5),1390(2012))
18 M.Olivier,A.Lanzutti,C.Motte,L.Fedrizzi,Influence of oxidizing ability of the medium on the growth of lanthanide layers on galvanized steel,Corrosion Science,52(4),1428(2010)
19 A.Conde,M.A.Arenas,A.D.Frutos,J.Damborenea,Effective corrosion protection of 8090 alloy by cerium conversion coatings,Electrochimica Acta,53(26),7760(2008)
20 GU Baoshan,GONG Li,YANG Peiyan,Study on performance and corrosion resistance mechanism of rare metal conversion coating on Al alloy surface,Rare Metal And Engineering,43(2),429(2014)(顾宝珊,宫丽,杨培燕,铝合金表面稀土转化膜性能与耐蚀机理研究,稀有金属材料与工程,43(2),429(2014))
21 V.I.Nefedov,M.N.Firsov,I.S.Shaplygin,Electronic structures of MRh O2,MRh2O4,Rh MO4and Rh2MO6on the basis of X-ray spectroscopy and ESCA data,Journal of Electron Spectroscopy&Related Phenomena,26(1),65(1982)
22 L.Yang,J.Li,X.Yu,M.L.Zhang,X.M.Huang,Lanthanum-based conversion coating on Mg–8Li alloy,Applied Surface Science,255(5),2338(2008)
23 C.Yang,H.Fan,S.Qiu,Y.X.Xi,Y.F.Fu,Microstructure and dielectric properties of La2O3films prepared by ion beam assistant electron-beam evaporation,Journal of Non-Crystalline Solids,355(1),33(2009)
24 F.Rueda,J.Mendialdua,A.Rodriguez,R.Casanovo,Y.Barbaux,Gengembre,L,Jalowiecki.Characterization of Venezuelan Laterites By X-Ray Photoelectron Spectroscopy,Journal of Electron Spectroscopy&Related Phenomena,82,135(1996)
25 M.Machkova,E.A.Matter,S.Kozhukharov,V.Kozhukharov,Effect of the anionic part of various Ce(III)salts on the corrosion inhibition efficiency of AA2024 aluminium alloy,Corrosion Science,69(6),396(2013)
26 S.C.Tjong,H.W.Huo,Corrosion protection of in situ Al-based composite by cerium conversion treatment,Journal of Materials Engineering&Performance,18(1),88(2009)
27 YANG Zhenhai,XU Ning,QIU Zhuxian,Measurement of aluminium corrosion potential-p H and the polarization curve,Journal of Northeastern University(Natural Science),21(4),401(2000)(杨振海,徐宁,邱竹贤,铝的电位-p H图及铝腐蚀曲线的测定,东北大学学报:自然科学版,21(4),401(2000))
28 ZHANG Jianghong,ZHANG Yingjie,YAN Yuxing,Investigation on the mechanism of forming rare earth conversion coating on zinc plating,Chinese Rare Earths,31(1),69(2010)(章江洪,张英杰,闫宇星,锌镀层表面稀土转化膜成膜机理分析,稀土,31(1),69(2010))
29 WANG Bing,LIU Qingyou,WANG Xiangdong,JIA Shujun,LU Ji,DONG Han,Inhibitive mechanism of Ce-ion and La-ion for carbon steel in Na Cl solution,Journal of Chinese Society for Corrosion and Protection,27(3),151(2007)(汪兵,刘清友,王向东,贾书君,卢吉,董瀚,稀土Ce和La对碳钢在Na Cl溶液中的缓蚀机理,中国腐蚀与防护学报,27(3),151(2007))
2 A.P.Yadav,H.Katayama,K.Noda,H.Masuda,A.Nishikata,T.Tsuru,Effect of Al on the galvanic ability of Zn-Al coating under thin layer of electrolyte,Electrochimica Acta,52(7),2411(2007)
3 F.Rosalbino,E.Angelini,D.Macciò,A.Saccone,S.Delfino,Application of EIS to assess the effect of rare earths small addition on the corrosion behaviour of Zn-5%Al(Galfan)alloy in neutral aerated sodium chloride solution,Electrochimica Acta,54(4),1204(2009)
4 LU Jintang,JIANG Aihua,CHE Chunshan,KONG Gang,Progress in research of hot-dipped Zn-Al alloying coating,Materials Protection,41(7),47(2008)(卢锦堂,江爱华,车淳山,孔纲,热浸Zn-Al合金镀层的研究进展,材料保护,41(7),47(2008))
5 S.Feliu,V.Barranco,XPS study of the surface chemistry of conventional hot-dip galvanised pure Zn,galvanneal and Zn-Al alloy coatings on steel,Acta Materialia,51(18),5413(2003)
6 J.C.Zocoola,H.E.Townsend,A.R.Borzillo,J.B.Horton,Atmospheric corrosion behavior of aluminum-zinc alloy-coated steel,Astm Special Technical Publication,646,165(1978)
7 ZHANG Changqiao,ZHU Chengfu,YU Ping,MOU Shanliang,SUN Ying,The microstructure of Zn-5%Al hot dip coating and study on its corrosion resistant mechanism,Journal of Materials Engineering,4,24(2002)(张长桥,主沉浮,于萍,牟善良,孙瑛,Zn-5%Al合金热浸镀层微结构及其防腐机理研究,材料工程,4,24(2002))
8 XU Qiaoyu,WANG Haixia,JIANG Rui,Formation and corrosion resistance of titanium containing conversion film on hot-dip Galvanized steel,Chinese Journal of Materials Research,28(7),521(2014)(许乔瑜,王海霞,姜瑞,热浸镀锌层钛盐转化膜的制备和耐蚀性能,材料研究学报,28(7),521(2014))
9 YANG Lihui,LI Junqing,YU Xiang,ZHANG Milin,Molybdate conversion coatings on AZ31 magnesium alloy,The Chinese Journal of Nonferrous Metals,18(7),1211(2008)(杨黎晖,李峻青,于湘,张密林,AZ31镁合金钼酸盐转化膜,中国有色金属学报,18(7),1211(2008))
10 L.Jiang,M.Wolpers,P.Volovitch,K.Ogle,An atomic emission spectroelectrochemical study of passive film formation and dissolution on galvanized steel treated with silicate conversion coatings,Surface&Coatings Technology,206(13),3151(2012)
11 KONG Gang,ZHANG Shuanghong,SUN Ziwen,CHE Chunshan,LU Jintang,Effect of size of silica powder on preparation of silicate conversion coatings on Galvanized steel,Chinese Journal of Materials Research,28(6),462(2014)(孔纲,张双红,孙子文,车淳山,卢锦堂,二氧化硅粉体粒度对硅酸盐转化膜制备的影响,材料研究学报,28(6),462(2014))
12 G.Rossana,M.L.Abel,M.A.Baker,B.Dunn,J.F.Watts,The adsorption of an epoxy acrylate resin on aluminum alloy conversion coatings,International Journal of Adhesion and Adhesives,31(7),687(2011)
13 ZHENG Runfeng,LIANG Haocheng,SHAO Lin,Study of composition and corrosion protection afforded by phytic acid conversion coatings applied to AZ91 magnesium alloy,Journal of Dalian University of Technology,46(1),16(2006)(郑润芬,梁浩成,邵林,AZ91D镁合金植酸转化膜组成与耐腐蚀性能研究,大连理工大学学报,46(1),16(2006))
14 LU Jintang,ZHANG Shuanghong,KONG Gong,CHE Chunshan,Composition and Corrosion resistance of molybdate/silane composite films on Galvanized steel,Journal of South China University of Technology(Natural Science Edition.,37(12),12(2009)(卢锦堂,张双红,孔纲,车淳山,镀锌钢上钼酸盐/硅烷复合膜的组成与耐蚀性,华南理工大学学报:自然科学版,37(12),12(2009))
15 M.F.Montemor,W.Trabelsi,M.Zheludevich,M.G.S.Ferreira,Modification of bis-silane solutions with rare-earth cations for improved corrosion protection of galvanized steel substrates,Progress in Organic Coatings,57(1),67(2006)
16 S.H.Zhang,G.Kong,J.T.Lu,C.S.Che,L.Y.Liu,Growth behavior of lanthanum conversion coating on hot-dip galvanized steel,Surface&Coatings Technology,259,654(2014)
17 KONG Gang,WU Shuang,LIN Dexin,WANG Xia,LI Hanchang,LU Jintang,Growth mechanism of cerium salt conversion coating modified with citric acid on galvanized steel,The Chinese Journal of Nonferrous Metals,22(5),1390(2012)(孔纲,吴双,林德鑫,王霞,黎汉昌,卢锦堂,热镀锌层柠檬酸改进型铈盐转化膜的生长机理,中国有色金属学报,22(5),1390(2012))
18 M.Olivier,A.Lanzutti,C.Motte,L.Fedrizzi,Influence of oxidizing ability of the medium on the growth of lanthanide layers on galvanized steel,Corrosion Science,52(4),1428(2010)
19 A.Conde,M.A.Arenas,A.D.Frutos,J.Damborenea,Effective corrosion protection of 8090 alloy by cerium conversion coatings,Electrochimica Acta,53(26),7760(2008)
20 GU Baoshan,GONG Li,YANG Peiyan,Study on performance and corrosion resistance mechanism of rare metal conversion coating on Al alloy surface,Rare Metal And Engineering,43(2),429(2014)(顾宝珊,宫丽,杨培燕,铝合金表面稀土转化膜性能与耐蚀机理研究,稀有金属材料与工程,43(2),429(2014))
21 V.I.Nefedov,M.N.Firsov,I.S.Shaplygin,Electronic structures of MRh O2,MRh2O4,Rh MO4and Rh2MO6on the basis of X-ray spectroscopy and ESCA data,Journal of Electron Spectroscopy&Related Phenomena,26(1),65(1982)
22 L.Yang,J.Li,X.Yu,M.L.Zhang,X.M.Huang,Lanthanum-based conversion coating on Mg–8Li alloy,Applied Surface Science,255(5),2338(2008)
23 C.Yang,H.Fan,S.Qiu,Y.X.Xi,Y.F.Fu,Microstructure and dielectric properties of La2O3films prepared by ion beam assistant electron-beam evaporation,Journal of Non-Crystalline Solids,355(1),33(2009)
24 F.Rueda,J.Mendialdua,A.Rodriguez,R.Casanovo,Y.Barbaux,Gengembre,L,Jalowiecki.Characterization of Venezuelan Laterites By X-Ray Photoelectron Spectroscopy,Journal of Electron Spectroscopy&Related Phenomena,82,135(1996)
25 M.Machkova,E.A.Matter,S.Kozhukharov,V.Kozhukharov,Effect of the anionic part of various Ce(III)salts on the corrosion inhibition efficiency of AA2024 aluminium alloy,Corrosion Science,69(6),396(2013)
26 S.C.Tjong,H.W.Huo,Corrosion protection of in situ Al-based composite by cerium conversion treatment,Journal of Materials Engineering&Performance,18(1),88(2009)
27 YANG Zhenhai,XU Ning,QIU Zhuxian,Measurement of aluminium corrosion potential-p H and the polarization curve,Journal of Northeastern University(Natural Science),21(4),401(2000)(杨振海,徐宁,邱竹贤,铝的电位-p H图及铝腐蚀曲线的测定,东北大学学报:自然科学版,21(4),401(2000))
28 ZHANG Jianghong,ZHANG Yingjie,YAN Yuxing,Investigation on the mechanism of forming rare earth conversion coating on zinc plating,Chinese Rare Earths,31(1),69(2010)(章江洪,张英杰,闫宇星,锌镀层表面稀土转化膜成膜机理分析,稀土,31(1),69(2010))
29 WANG Bing,LIU Qingyou,WANG Xiangdong,JIA Shujun,LU Ji,DONG Han,Inhibitive mechanism of Ce-ion and La-ion for carbon steel in Na Cl solution,Journal of Chinese Society for Corrosion and Protection,27(3),151(2007)(汪兵,刘清友,王向东,贾书君,卢吉,董瀚,稀土Ce和La对碳钢在Na Cl溶液中的缓蚀机理,中国腐蚀与防护学报,27(3),151(2007))