含稀土铝合金表面氧化膜结构与性能关系研究
摘要
铝合金在国民经济以及人们的日常生活中具重要地位，稀土加入铝合金对铝合金的性能改善显著，因而受到国内外的广泛重视。
本文以掺稀土La铝合金和掺稀土Er铝合金为样品，样品中的稀土La和稀土Er的实际含量用ICP测定，并用X射线衍射方法确定了稀土铝合金表面氧化膜中Al_2O_3为尖晶石结构。运用同步辐射技术EXAFS测试方法对不同La．含量的La—Al合金和不同Er含量的Er—Al合金进行测试。结果表明：稀土进入了氧化膜生成了稀土-铝复合氧化膜。Er进入八面体或四面体尖晶石空隙中与氧结合，减少了表面的空位数，从而影响了原子之间的相互作用，使氧化膜的稳定性增强。La进入表面氧化膜以后，La-0键上的电子向Al上转移，使La-0键上的电子云密度变小。Al-0之间的电子云密度增大，La的氧化态增加，而使Al-0间的结合力增强。从而La的第一壳层配位数增大，La-0距离增大。
本文采用电化学的方法对稀土铝合金的耐腐蚀性能进行了研究。TAFEL极化曲线测试结果表明La进入表面氧化膜以后，同时抑制了阴极反应和阳极反应。Er-Al合金中Al-0结合能的改变使氧化膜更加致密，从而抑制了氧在氧化膜中的扩散，即抑制了阴极反应。交流阻抗谱测试结果表明：掺入稀土之后，表面发生腐蚀的趋向减弱。氧化膜的多孔层和阻挡层都得到了改善，变得更为致密，从而保护了金属基体。
The aluminum alloy plays an important role in the country economy and people' s daily life. Since adding rare earth element to the aluminum alloy will obviously improve the alloy' s property, more and researchers take notice ifi the rare earth aluminum alloy.
The quantity of rare earth element in La-Al aluminum alloy and Er-Al aluminum alloy was measured by ICP. The structure of A1203 in the surface oxide film was spinel structure determined by XRD. The result of synchronization radiation technology shows that the rare earth element entered into the oxide film.
The anticorrosion property of the rare earth aluminum alloy was also investigated. TheTAFEL polarization result shows that La restrained both the cathode reaction and anode reaction. In Er-Al alloys the changing of the Al-0 binding energy made the oxide film denser so the cathode reaction and anode reaction. AC impedance shows that the porous layer and the barrier layer in the oxide film become denser and the metal substance was protected.
本文以掺稀土La铝合金和掺稀土Er铝合金为样品，样品中的稀土La和稀土Er的实际含量用ICP测定，并用X射线衍射方法确定了稀土铝合金表面氧化膜中Al_2O_3为尖晶石结构。运用同步辐射技术EXAFS测试方法对不同La．含量的La—Al合金和不同Er含量的Er—Al合金进行测试。结果表明：稀土进入了氧化膜生成了稀土-铝复合氧化膜。Er进入八面体或四面体尖晶石空隙中与氧结合，减少了表面的空位数，从而影响了原子之间的相互作用，使氧化膜的稳定性增强。La进入表面氧化膜以后，La-0键上的电子向Al上转移，使La-0键上的电子云密度变小。Al-0之间的电子云密度增大，La的氧化态增加，而使Al-0间的结合力增强。从而La的第一壳层配位数增大，La-0距离增大。
本文采用电化学的方法对稀土铝合金的耐腐蚀性能进行了研究。TAFEL极化曲线测试结果表明La进入表面氧化膜以后，同时抑制了阴极反应和阳极反应。Er-Al合金中Al-0结合能的改变使氧化膜更加致密，从而抑制了氧在氧化膜中的扩散，即抑制了阴极反应。交流阻抗谱测试结果表明：掺入稀土之后，表面发生腐蚀的趋向减弱。氧化膜的多孔层和阻挡层都得到了改善，变得更为致密，从而保护了金属基体。
The aluminum alloy plays an important role in the country economy and people' s daily life. Since adding rare earth element to the aluminum alloy will obviously improve the alloy' s property, more and researchers take notice ifi the rare earth aluminum alloy.
The quantity of rare earth element in La-Al aluminum alloy and Er-Al aluminum alloy was measured by ICP. The structure of A1203 in the surface oxide film was spinel structure determined by XRD. The result of synchronization radiation technology shows that the rare earth element entered into the oxide film.
The anticorrosion property of the rare earth aluminum alloy was also investigated. TheTAFEL polarization result shows that La restrained both the cathode reaction and anode reaction. In Er-Al alloys the changing of the Al-0 binding energy made the oxide film denser so the cathode reaction and anode reaction. AC impedance shows that the porous layer and the barrier layer in the oxide film become denser and the metal substance was protected.
引文
1 潘复生等．我国稀土铝合金的研究和应用．轻合金加工技术．1990，(3)：1～12
2 张密林，鲁化一等．稀土．1988，(5)：34
3 王绍芩，周小平．中国稀土学报．1987，(3)：53
4 赵乃勤，姚家鑫等．稀土对6063铝合金组织性能的影响．天津大学学报．1995，28(3)：375
5 薛文彬等，铝合金微氧化陶瓷膜的相分布及其形成．材料研究学报．1997，11(2)：169
6 王冰，赵敏寿．稀土LD_(31)挤压铝合金阳极氧化着色及其性能研究．材料保护．1990，23(3)：8
7 姜晓霞，林树智等．铝合金锻件中氧化膜来源的探索．轻金属．1990，12：53
8 Mondofo L F. Aluminum Alloys: Structure and Properties [M]. London:Butterworth & Co(publishers) Ltd, 1976. 807.
9 Habazaki H, Shimizu K, Skeldon P. Etal. Effects of Alloying Elements in Anodizing of Aluminum [J]. Transactions of the Institute of Metal Finishing. 1997, 75(1): 18～23.
10 Thompson G E, Wood G C. Anodic Films on Aluminium[J].Treatise on Materials Science and Technology. 1983,23:250～253.
11 F. Keller. M.S. Hunter and D.L Robinson. J. Electrochem. Soc. 1953,100:411
12 T. P. Hoar and G.C. Wood. Electrochima Acta. 1962, 7: 333 33,614,1982:34,44,1983
13 M.Koda, H. Takahashi and M.Nagayama. J.Metal Finish,Sco. Japan. 1982,33: 614, 1983,34:44
14 杜先智，张亚增．铝合金阳极氧化膜的制备和研究．太阳能学报．1995，16(2)：191
15 杨蔺孝，杨芩．铝材耐膜耐烧蚀特种氧化成膜机理的研究与应用[J]．电镀与环保．1992，12(2)：13
16 马胜利等．A1-3．8Cu—0.4Mg合金阳极氧化膜的组织与性能研究．兵器材料
科学与工程．1999，22(4) ：41
17 B.R.W.Hinton. et al.The Inhibition of Aluminum Corrosion by Cerium Corrosion by Cerium Cations. Metals Forum. 1 984 , 7(4) : 211-217
18 D.R. Arott et al. Auger and XPS Studies of Cerium Corrosion Inhibition on 7075 Aluminum Alloy. Applications of Surface Science. 1985,22/23:236-251
19 International Patent(WO/8806639) . Hinton B R W. Corros. Sci. 1989, 29(8) : 967
20 B.R.W.Hinton et al. Cerium Conversion Coatings for the Corrosion Protection of Aluminium . Materials Forum. 1986,9(3) : 162-165
21 Arnott D R. Corros. Sci.. 1989,45(1) : 12
22 Arnott D R Cerium Conversion Coatings for the Corrosion Protection of Aluminum. Met.Forum. 1986,9(3) : 162
23 Hinton B R W. The Inhibition of Al Alloy Corrosion by Rare Earth Metal Cations. Corrosion . Australas. 1985, 10(3) : 12
24 Arnott D R.. Cationic Film-Forming Inhibitions for the Corrosion Protection of Al 7075 Alloy in Chloride Solutions. Mater. Perform. 1987, 26(8) : 42-47
25 Arnott D R. Cationic Film Forming Inhibitions for the Protection of Al 7075 Alloy Against Corrosion in Aqueous Chloride Solutions. Corros. Sci.. 1989, 45(1) : 12
26 Arnott D R. Auger and XPS Study of Cerium Corrosion Inhibition on 7075 Aluminum Alloy. Appl.Sufr.Sci.. 1985, 22-23(1) : 236
27 Mansfeld F. Elemination of Al Alloys by Surface Modification. Proc-Electrochem Soc.. 1996,308:95-15
28 Mansfeld F. Corrosion. 1989, 45(8) : 615
29黄长山等．关于三价铬电镀铬层增厚问题的研究．电镀与涂饰．1992，14(6) ：3
30黎文献等．混合稀土对6063合金耐蚀性能的影响．中南工业大学学报． 1 989
31 Azaroff L V. X-ray Spectroscopy. New York. McGraw-Hill. 1974
32 D.E.Sawyers et al, Phys.Rev. Lett. 1971, (27): 1204
33 E.A.Stern.. Phys.Rev. B.. 1974, 10(8):3027
34 F.W. Lytle. D.E.Sawyers and E.A.Stern. Phys.Rev. B. 1975, 11(12): 4825
35 E.A.Stern. et al, Phys. Rev. B. 1975, 11(12): 4836
36 H.Peterson. Z. Essper. T edr. Fiz.. 1941, 11: 60
37 A.I.Kostarev. Z. Essper. Tedr. Fiz. 1941, 11:60
38 L.V. Azaroff and D.M. Pease. X-ray Spectroscopy. McGraw Hill. New York. 1974, 6
39 王其武，刘文汗．X射线吸收精细结构及其应用．北京．科学出版社．1994
40 姜晓明，修立松．同步辐射及其应用．北京科学技术出版社．1996
41 马礼敦，杨福家．同步辐射应用概论．复旦大学出版社．2001
42 Stern, E.A..Phys. Rev.. 1974, (10):3027
43 J.J. Rehr. Phys. Rev. Lett.. 1992, (69):3397
44 J.J. Rehr. et al, Phys. Rev. B. 1994, (49):12347
45 E.A. Stern et al, Physica. B. 1995, (208&209):121
46 A.Filliponi. et al Solid. State.Commun.. 1991, (78): 265
48 Wyckoff, R.W.G.. Crystal Structures (interscience Publishers, Inc. New York).Vol. 1.
49 Lee, P.A. and Pendry, J.B.. Phys. Rev. 1975, (11). 2795
50 汪夏燕．可充碱锰电池改性二氧化锰改性机理的研究．[硕士学位论文]湘潭大学．1999，3
51 Tarkar,Krischner. Monatsh.Chem.. 1960, (91): 659
52 J.Beretka. M. J. Ridge. JCSA. 1967, (12): 2106
53 Nagel, D.J. and Baun, W.L.. X-ray Spectroscopy ed. By Azaroff. L.V..McGraw-Hill. New York. 1974, 445,
54 Agawall, B.K. and Verma, L.P.J.Phys. C.1970, (3):535
55 Dehmer J L, Dill D.J. Chem Phys. 1976,(65):5327, Phys Rev Lett, 1975, 35:213
2 张密林，鲁化一等．稀土．1988，(5)：34
3 王绍芩，周小平．中国稀土学报．1987，(3)：53
4 赵乃勤，姚家鑫等．稀土对6063铝合金组织性能的影响．天津大学学报．1995，28(3)：375
5 薛文彬等，铝合金微氧化陶瓷膜的相分布及其形成．材料研究学报．1997，11(2)：169
6 王冰，赵敏寿．稀土LD_(31)挤压铝合金阳极氧化着色及其性能研究．材料保护．1990，23(3)：8
7 姜晓霞，林树智等．铝合金锻件中氧化膜来源的探索．轻金属．1990，12：53
8 Mondofo L F. Aluminum Alloys: Structure and Properties [M]. London:Butterworth & Co(publishers) Ltd, 1976. 807.
9 Habazaki H, Shimizu K, Skeldon P. Etal. Effects of Alloying Elements in Anodizing of Aluminum [J]. Transactions of the Institute of Metal Finishing. 1997, 75(1): 18～23.
10 Thompson G E, Wood G C. Anodic Films on Aluminium[J].Treatise on Materials Science and Technology. 1983,23:250～253.
11 F. Keller. M.S. Hunter and D.L Robinson. J. Electrochem. Soc. 1953,100:411
12 T. P. Hoar and G.C. Wood. Electrochima Acta. 1962, 7: 333 33,614,1982:34,44,1983
13 M.Koda, H. Takahashi and M.Nagayama. J.Metal Finish,Sco. Japan. 1982,33: 614, 1983,34:44
14 杜先智，张亚增．铝合金阳极氧化膜的制备和研究．太阳能学报．1995，16(2)：191
15 杨蔺孝，杨芩．铝材耐膜耐烧蚀特种氧化成膜机理的研究与应用[J]．电镀与环保．1992，12(2)：13
16 马胜利等．A1-3．8Cu—0.4Mg合金阳极氧化膜的组织与性能研究．兵器材料
科学与工程．1999，22(4) ：41
17 B.R.W.Hinton. et al.The Inhibition of Aluminum Corrosion by Cerium Corrosion by Cerium Cations. Metals Forum. 1 984 , 7(4) : 211-217
18 D.R. Arott et al. Auger and XPS Studies of Cerium Corrosion Inhibition on 7075 Aluminum Alloy. Applications of Surface Science. 1985,22/23:236-251
19 International Patent(WO/8806639) . Hinton B R W. Corros. Sci. 1989, 29(8) : 967
20 B.R.W.Hinton et al. Cerium Conversion Coatings for the Corrosion Protection of Aluminium . Materials Forum. 1986,9(3) : 162-165
21 Arnott D R. Corros. Sci.. 1989,45(1) : 12
22 Arnott D R Cerium Conversion Coatings for the Corrosion Protection of Aluminum. Met.Forum. 1986,9(3) : 162
23 Hinton B R W. The Inhibition of Al Alloy Corrosion by Rare Earth Metal Cations. Corrosion . Australas. 1985, 10(3) : 12
24 Arnott D R.. Cationic Film-Forming Inhibitions for the Corrosion Protection of Al 7075 Alloy in Chloride Solutions. Mater. Perform. 1987, 26(8) : 42-47
25 Arnott D R. Cationic Film Forming Inhibitions for the Protection of Al 7075 Alloy Against Corrosion in Aqueous Chloride Solutions. Corros. Sci.. 1989, 45(1) : 12
26 Arnott D R. Auger and XPS Study of Cerium Corrosion Inhibition on 7075 Aluminum Alloy. Appl.Sufr.Sci.. 1985, 22-23(1) : 236
27 Mansfeld F. Elemination of Al Alloys by Surface Modification. Proc-Electrochem Soc.. 1996,308:95-15
28 Mansfeld F. Corrosion. 1989, 45(8) : 615
29黄长山等．关于三价铬电镀铬层增厚问题的研究．电镀与涂饰．1992，14(6) ：3
30黎文献等．混合稀土对6063合金耐蚀性能的影响．中南工业大学学报． 1 989
31 Azaroff L V. X-ray Spectroscopy. New York. McGraw-Hill. 1974
32 D.E.Sawyers et al, Phys.Rev. Lett. 1971, (27): 1204
33 E.A.Stern.. Phys.Rev. B.. 1974, 10(8):3027
34 F.W. Lytle. D.E.Sawyers and E.A.Stern. Phys.Rev. B. 1975, 11(12): 4825
35 E.A.Stern. et al, Phys. Rev. B. 1975, 11(12): 4836
36 H.Peterson. Z. Essper. T edr. Fiz.. 1941, 11: 60
37 A.I.Kostarev. Z. Essper. Tedr. Fiz. 1941, 11:60
38 L.V. Azaroff and D.M. Pease. X-ray Spectroscopy. McGraw Hill. New York. 1974, 6
39 王其武，刘文汗．X射线吸收精细结构及其应用．北京．科学出版社．1994
40 姜晓明，修立松．同步辐射及其应用．北京科学技术出版社．1996
41 马礼敦，杨福家．同步辐射应用概论．复旦大学出版社．2001
42 Stern, E.A..Phys. Rev.. 1974, (10):3027
43 J.J. Rehr. Phys. Rev. Lett.. 1992, (69):3397
44 J.J. Rehr. et al, Phys. Rev. B. 1994, (49):12347
45 E.A. Stern et al, Physica. B. 1995, (208&209):121
46 A.Filliponi. et al Solid. State.Commun.. 1991, (78): 265
48 Wyckoff, R.W.G.. Crystal Structures (interscience Publishers, Inc. New York).Vol. 1.
49 Lee, P.A. and Pendry, J.B.. Phys. Rev. 1975, (11). 2795
50 汪夏燕．可充碱锰电池改性二氧化锰改性机理的研究．[硕士学位论文]湘潭大学．1999，3
51 Tarkar,Krischner. Monatsh.Chem.. 1960, (91): 659
52 J.Beretka. M. J. Ridge. JCSA. 1967, (12): 2106
53 Nagel, D.J. and Baun, W.L.. X-ray Spectroscopy ed. By Azaroff. L.V..McGraw-Hill. New York. 1974, 445,
54 Agawall, B.K. and Verma, L.P.J.Phys. C.1970, (3):535
55 Dehmer J L, Dill D.J. Chem Phys. 1976,(65):5327, Phys Rev Lett, 1975, 35:213