湿法炼锌净化渣—钴镍渣选择性溶出研究
|
摘要
针对湿法炼锌净化渣-钴镍渣的处理问题，本文对该渣的选择性溶出过程进行研究，可为工业上钴镍渣的溶出工艺与综合利用提供依据。实验研究得出主要结论如下：
1．钴镍渣颗粒为包裹型结构。内部是未反应的单质锌，外层是置换反应析出的单质钴、镍；堆积一段时间后，部分锌、钴、镍被空气中的氧气所氧化生成氧化膜，包裹在颗粒的最表层。
2．采用选择性溶出处理钴镍渣，控制过程pH≥3．5，终点pH≥4．0，不仅锌的溶出率很高(溶出率为95％左右)，而且还能有效地将锌与钴镍分离(钴、镍的溶出率均低于10％)，因此选择性溶出适用于钴镍渣的处理：
3．在常温条件下，硫酸选择性溶出钴镍渣放出氢气的反应是准一级反应，表观反应速率常数k~*=0．5617 min~(-1)；
4．钻镍渣溶出过程中，应用钻电极在线监测追踪Co~(2+)浓度变化。实验研究表明，钴电极应用为指示电极的条件是保持溶液体系pH≤2．0；钴镍渣溶出反应开始一段时间后，钴电极指示的电极电势逐渐上升，表明Co~(2+)浓度不断增加，这符合渣中氧化钴不断被H~+溶出生成Co~(2+)的事实，因此，在钴镍渣溶出中钴电极可定性指示Co~(2+)浓度的变化情况。
The selective acid leaching of cobalt and nickel residue generated in the process of ZnSO_4 purification is studied in this paper, which will provide a fundamental basis for the industrial leaching and utilization of cobalt and nickel residue. The main conclusions are as follows:
1. The particulate of cobalt and nickel residue is determined to be surrounded structure. Metal zinc was in the core, and cobalt or nickel generated by displacement reaction was covered outside. After stacking the residue for some time, partial Zn, Co and Ni were oxidized by the oxygen in the air. As a result, a layer of oxidation film was formed and surrounded at the surface of the particulate;
2. The selective acid leaching was introduced to dispose the cobalt and nickel residue at the condition of pH≥3.5 during the leaching process and pH≥4.0 at the end of the reaction. The experiments showed that leaching rate of zinc was 95% approximately, the Co and Ni less than 10%, so Co and Ni were enriched in the solid phase, and were separated from the zinc effectively. Therefore, the selective acid leaching is suitable for the cobalt and nickel residue disposal;
3. At the room temperature, the selective acid leaching of cobalt and nickel residue is the first order reaction, and the constant rate k~* was determined to be 0.5617 min~(-1);
4. The investigations indicate that when cobalt electrode is used to indicate the concentration of Co~(2+), the pH of solution system must be lower than 2.0. The application of cobalt electrode to leaching experiments of cobalt and nickel residue at the pH of 2.0 showed that, after leaching reaction for a little while, the electrode potential indicated by cobalt electrode increased gradually, which suggested that the concentration of Co~(2+) was increasing continuously, which was just consistent with the fact that cobalt and nickel residue was continuously dissolved into cobalt ion. Therefore, cobalt electrode could be used to qualitatively indicate the cobalt ion changes during the acid leaching process of cobalt and nickel residue.
1．钴镍渣颗粒为包裹型结构。内部是未反应的单质锌，外层是置换反应析出的单质钴、镍；堆积一段时间后，部分锌、钴、镍被空气中的氧气所氧化生成氧化膜，包裹在颗粒的最表层。
2．采用选择性溶出处理钴镍渣，控制过程pH≥3．5，终点pH≥4．0，不仅锌的溶出率很高(溶出率为95％左右)，而且还能有效地将锌与钴镍分离(钴、镍的溶出率均低于10％)，因此选择性溶出适用于钴镍渣的处理：
3．在常温条件下，硫酸选择性溶出钴镍渣放出氢气的反应是准一级反应，表观反应速率常数k~*=0．5617 min~(-1)；
4．钻镍渣溶出过程中，应用钻电极在线监测追踪Co~(2+)浓度变化。实验研究表明，钴电极应用为指示电极的条件是保持溶液体系pH≤2．0；钴镍渣溶出反应开始一段时间后，钴电极指示的电极电势逐渐上升，表明Co~(2+)浓度不断增加，这符合渣中氧化钴不断被H~+溶出生成Co~(2+)的事实，因此，在钴镍渣溶出中钴电极可定性指示Co~(2+)浓度的变化情况。
The selective acid leaching of cobalt and nickel residue generated in the process of ZnSO_4 purification is studied in this paper, which will provide a fundamental basis for the industrial leaching and utilization of cobalt and nickel residue. The main conclusions are as follows:
1. The particulate of cobalt and nickel residue is determined to be surrounded structure. Metal zinc was in the core, and cobalt or nickel generated by displacement reaction was covered outside. After stacking the residue for some time, partial Zn, Co and Ni were oxidized by the oxygen in the air. As a result, a layer of oxidation film was formed and surrounded at the surface of the particulate;
2. The selective acid leaching was introduced to dispose the cobalt and nickel residue at the condition of pH≥3.5 during the leaching process and pH≥4.0 at the end of the reaction. The experiments showed that leaching rate of zinc was 95% approximately, the Co and Ni less than 10%, so Co and Ni were enriched in the solid phase, and were separated from the zinc effectively. Therefore, the selective acid leaching is suitable for the cobalt and nickel residue disposal;
3. At the room temperature, the selective acid leaching of cobalt and nickel residue is the first order reaction, and the constant rate k~* was determined to be 0.5617 min~(-1);
4. The investigations indicate that when cobalt electrode is used to indicate the concentration of Co~(2+), the pH of solution system must be lower than 2.0. The application of cobalt electrode to leaching experiments of cobalt and nickel residue at the pH of 2.0 showed that, after leaching reaction for a little while, the electrode potential indicated by cobalt electrode increased gradually, which suggested that the concentration of Co~(2+) was increasing continuously, which was just consistent with the fact that cobalt and nickel residue was continuously dissolved into cobalt ion. Therefore, cobalt electrode could be used to qualitatively indicate the cobalt ion changes during the acid leaching process of cobalt and nickel residue.
引文
[1]彭容秋．铅锌冶金学[M]．北京：科学出版社，2003
[2]赵天从．重金属冶金学(下册)[M]．北京：冶金工业出版社，1981
[3] Dennis, William Herbert. Metallurgy of the non-ferrous metals [M]. London: Pitman, 1961
[4]谢高阳．无机化学丛书[M]．北京：科学出版社，1996
[5] Honeycombe, R. W. K. Steels: microstructure and properties [M]. London: Edward Arnold, 1981
[6] Honeycombe, R. W. K. Metallurgy and materials science-a series of student texts [M]. London: Edward Arnold, 1981
[7]刘大星．锌湿法冶金技术的国内外现状及发展趋势[C]．有色金属，2001专辑
[8]Φ．M．罗斯库托夫．铅锌冶金学(曾广冼，刘宗志译，刘宗志校)[M]．北京：冶金工业出版社，1960，4
[9]陈友强．浅议粗铅火法精炼工艺[J].有色冶金设计与研究，2005，26(2)：8-11
[10]刘沈宁．粗铅火法精炼工业实践[J]．中国有色冶金，2004(04)：22-26
[11]蒋继穆．我国锌冶炼现状及近年来的技术进展[J]．中国有色冶金，2006(05)：19-23
[12]刘三军，欧乐明．中国锌冶炼工业现状[J]．矿产保护与利用，2003(06)：36-40
[13]梅光贵，王德润，周敬元，等．湿法炼锌学[M]．长沙：中南大学出版社，2001
[14]吴攀，刘丛强，杨元根，等．土法炼锌废渣堆中的重金属及其释放规律[J]．中国环境科学，2002，22(2)：109-113
[15]陈世琯．铜、锌、铅火法冶金现状及21世纪初展望[J]．上海有色金属，1997，18(3)：135-141
[16]叶军乔，何静，曾令成．ISP烧结工艺的特点及发展趋势[J]．有色冶金设计与研究，2004，25(1)：3-9
[17]郭天立，高良宾．当代竖罐炼锌技术述评[J]．中国有色冶金，2007(01)：5-7
[18]王立宇，周宪民，王宝文，等．提高竖罐蒸馏工序锌冶炼回收率的途径[J]．有色矿冶，2007，23(4)：37-39
[19] Casaroli S J G, Cohen B, Tong A R, et al. Cementation for metal removal in zinc electrowinning circuits [J]. Minerals Engineering, 2005, 18 (13-14): 1282-1288
[20] LIU Hai-xia, Papangelakis V G. Thermodynamic equilibrium of the O_2-ZnSO_4-H_2SO_4-H_2O system from 25 to 250℃ [J]. Fluid Phase Equilibria, 2005, 234 (1-2):??122-130
[21]杨显万，邱定藩．湿法冶金[M]．北京：冶金工业出版社，1998
[22]魏昶，王吉坤．湿法炼锌理论与应用[M]．昆明：云南科技出版社，2003
[23]刘春侠，谢刚，王吉坤，等．锌湿法净化钴镍渣的综合回收[J]．有色金属(冶炼部分)，2006(03)：2-4
[24]马进，陈利春，秦永宏．锌粉置换除钴的研究及应用[J]．有色冶炼，2002(01)：30-32
[25] WANG Yan, ZHOU Chun-shan. Hydrometallurgical process for recovery of cobalt from zinc plant residue [J]. Hydrometallurgy, 2002, 63 (3): 225-234
[26] Rao K A, Natarajan R, Padmanabhan N P H. Studies on recovery of copper, nickel, cobalt and molybdenum values from a bulk sulphide concentrate of an Indian uranium ore [J]. Hydrometallurgy, 2001, 62 (2): 115-124
[27]陈海清，刘亚雄．从硫酸锌溶液净化渣回收锌和钴[J]．湖南有色金属，2006，22(2)：12-15
[28]赵廷凯．氨法处理湿法炼锌净化钴渣制取锌粉和回收钴：[博士学位论文]．长沙：中南大学，2001
[29] Stanojevi D, Nikoli B, Todorovi M. Evaluation of cobalt from cobaltic waste products from the production of electrolytic zinc and cadmium [J]. Hydrometallurgy, 2000,54(2-3): 151-160
[30]洪涛．氧化沉淀法分离炼锌除钴渣中锌钴的研究：[硕士学位论文]．西安：西安建筑科技大学，2003
[31]蓝德均．高锰酸钾氧化沉钴的研究及应用：[硕士学位论文]．昆明：昆明理工大学，2003
[32] Brian K. Tait. Cobalt-nickel separation: the extraction of cobalt(Ⅱ) and nickel(Ⅱ) by Cyanex 301, Cyanex 302 and Cyanex 272 [J]. Hydrometallurgy, 1993, 32(3): 365 -372
[33]王靖芳，杨文斌，冯彦琳．P507萃取锌、镉的机理[J]．山西大学学报(自然科学版)，1994，17(01)：38-41
[34] Berend Wassink, David Dreisinger, Jane Howard. Solvent extraction separation of zinc and cadmium from nickel and cobalt using Aliquat 336, a strong base anion exchanger, in the chloride and thiocyanate forms [J]. Hydrometallurgy, 2000, 57(3): 235-252
[35]牛聪伟，王开毅，舒万艮．用非平衡溶剂萃取法分离钴镍的研究[J].有色金属(冶炼部分)，2000(04)：6-8
[36]吴月顺，宋其圣，俞海云，等．P 5709萃取钴(Ⅱ)镍(Ⅱ)的动力学研究[J]．山东大学学报(自然科学版)．2001，36(02)：210-215
[37] LU Li-zhu, ZHANG Da-li, XIE Hui-qin, et al. Extraction and Separation of Cadmium and Zinc with a Mixture of Di-(2-Ethylhexyl)-Dithiophosphoric Acid and Trioctyl Amine [J]. Chinese Journal of Chemical Engineering, 1999, 7 (02): 132-138
[38] Alamdari E K, Moradkhani D, Darvishi D, et al. Synergistic effect of MEHPA on co-extraction of zinc and cadmium with DEHPA [J]. Minerals Engineering, 2004, 17 (1): 89-92
[39]杨大锦；谢刚；王吉坤，等．硫酸锌溶液的萃取工艺研究[J]．有色金属(冶炼部分)，2006(02)：9-13
[40]宁模功，张允恭．从湿法炼锌工艺产出的钴镍渣中回收锌[J]．湿法冶金，2002，21(1)：39-45
[41]宁模功，张允恭．处理湿法炼锌净化钴镍渣的试验研究[J]．有色金属(冶炼部分)，2001(1)：10-19
[42]彭容秋．重金属冶金学[M]．长沙：中南大学出版社，2004
[43]赵廷凯，唐漠堂．湿法炼锌净化钴渣新处理工艺[J]．中南工业大学学报，2001，32(4)：371-375
[44]傅献彩，沈文霞，姚天扬．物理化学(第4版)[M]．北京：高等教育出版，1990
[45]王琪．化学动力学导论[M]．长春：吉林人民出版社，1982．
[46]赵学庄．化学反应动力学原理[M]．北京：高等教育出版社，1984
[47]孙宁，柴德洪，杨春艳．气体容量法定碳中几个问题的研究[J]．哈尔滨师范大学自然科学学报，1995，11(2)：75-77．
[48] Samih A H, Mohamed A M. Influence of promoted and unpromoteddecomposition products of ammonium metavanadate on the pyrolysis of NaClO_2 [J].Journal of Analytical and Applied Pyrolysis, 2004, 72(1): 75-82.
[49] Joshua C W, Andrew Z, Daniel M, Matt T, et al. Sodium borohydride hydrolysiskinetics comparison for nickel, cobalt, and ruthenium boride catalysts [J]. Journal ofPower Sources, 2008, 19 (1): 335-339.
[50] Kohei U, Kazuhisa T, Yasushi S, Masahiko M, et al. Production of hydrogen bysteam reforming of ethanol over cobalt and nickel catalysts supported onperovskite-type oxides [J]. Catalysis Communications, 2008, 9(5): 600-604.
[51]毛云中，凌霞，陈屹．钴的检测方法进展[J]．理化检验一化学分册2006，42(10)：861-864
[52]龚竹青．理论电化学导论[M]．长沙：中南工业大学出版社，1988
[53]邝生鲁．应用电化学[M]．武汉：华中理工大学社，1994
[54]B．B．达马斯会，O．A．佩特里．电化学动力学导论(谷林镁，秦尔华译)[M]．北京：科学出版社，1989
[55] ZENG Wen-ming, CHEN Nian-yi. Potential - pH diagrams of Al-H_2O system [J].Transactions of Nonferrous Metals Society of China, 1997, 7 (2): 34-37.
[56] DEAN J A. Lange's Handbook of chemistry (15th Edition) [M]. McGraw Hill,1999
[57]叶大伦，胡建华．实用无机物热力学数据手册(第2版)．北京：冶金工业出版社，2002
[58]陈小文，白新德，薛祥义，等．电位-pH平衡图及其在核材料腐蚀研究中的应用[J]．清华大学学报(自然科学版)，2002，42(5)：692-695
[59]钟文彬，杨玉玺，张昭．湿化学法制备四氧化三钴的研究-热力学分析[J]．四川有色金属，3001(01)：23-26
[60]曾桂生．硫酸锌溶液中锌粉置换除钻的机理研究：[博士学位论文]．昆明：昆明理工大学，2006
[61] Cooper K R, Kelly R G. Crack tip chemistry and electrochemistry of environmental cracks in AA 7050 [J]. Corrosion Science, 2007, 49 (6): 2636-2662
[62] Fratesi R, Roventi G. Corrosion resistance of Zn-Ni alloy coatings in industrial production [J]. Surface and Coatings Technology, 1996, 82 (1-2): 158-164
[2]赵天从．重金属冶金学(下册)[M]．北京：冶金工业出版社，1981
[3] Dennis, William Herbert. Metallurgy of the non-ferrous metals [M]. London: Pitman, 1961
[4]谢高阳．无机化学丛书[M]．北京：科学出版社，1996
[5] Honeycombe, R. W. K. Steels: microstructure and properties [M]. London: Edward Arnold, 1981
[6] Honeycombe, R. W. K. Metallurgy and materials science-a series of student texts [M]. London: Edward Arnold, 1981
[7]刘大星．锌湿法冶金技术的国内外现状及发展趋势[C]．有色金属，2001专辑
[8]Φ．M．罗斯库托夫．铅锌冶金学(曾广冼，刘宗志译，刘宗志校)[M]．北京：冶金工业出版社，1960，4
[9]陈友强．浅议粗铅火法精炼工艺[J].有色冶金设计与研究，2005，26(2)：8-11
[10]刘沈宁．粗铅火法精炼工业实践[J]．中国有色冶金，2004(04)：22-26
[11]蒋继穆．我国锌冶炼现状及近年来的技术进展[J]．中国有色冶金，2006(05)：19-23
[12]刘三军，欧乐明．中国锌冶炼工业现状[J]．矿产保护与利用，2003(06)：36-40
[13]梅光贵，王德润，周敬元，等．湿法炼锌学[M]．长沙：中南大学出版社，2001
[14]吴攀，刘丛强，杨元根，等．土法炼锌废渣堆中的重金属及其释放规律[J]．中国环境科学，2002，22(2)：109-113
[15]陈世琯．铜、锌、铅火法冶金现状及21世纪初展望[J]．上海有色金属，1997，18(3)：135-141
[16]叶军乔，何静，曾令成．ISP烧结工艺的特点及发展趋势[J]．有色冶金设计与研究，2004，25(1)：3-9
[17]郭天立，高良宾．当代竖罐炼锌技术述评[J]．中国有色冶金，2007(01)：5-7
[18]王立宇，周宪民，王宝文，等．提高竖罐蒸馏工序锌冶炼回收率的途径[J]．有色矿冶，2007，23(4)：37-39
[19] Casaroli S J G, Cohen B, Tong A R, et al. Cementation for metal removal in zinc electrowinning circuits [J]. Minerals Engineering, 2005, 18 (13-14): 1282-1288
[20] LIU Hai-xia, Papangelakis V G. Thermodynamic equilibrium of the O_2-ZnSO_4-H_2SO_4-H_2O system from 25 to 250℃ [J]. Fluid Phase Equilibria, 2005, 234 (1-2):??122-130
[21]杨显万，邱定藩．湿法冶金[M]．北京：冶金工业出版社，1998
[22]魏昶，王吉坤．湿法炼锌理论与应用[M]．昆明：云南科技出版社，2003
[23]刘春侠，谢刚，王吉坤，等．锌湿法净化钴镍渣的综合回收[J]．有色金属(冶炼部分)，2006(03)：2-4
[24]马进，陈利春，秦永宏．锌粉置换除钴的研究及应用[J]．有色冶炼，2002(01)：30-32
[25] WANG Yan, ZHOU Chun-shan. Hydrometallurgical process for recovery of cobalt from zinc plant residue [J]. Hydrometallurgy, 2002, 63 (3): 225-234
[26] Rao K A, Natarajan R, Padmanabhan N P H. Studies on recovery of copper, nickel, cobalt and molybdenum values from a bulk sulphide concentrate of an Indian uranium ore [J]. Hydrometallurgy, 2001, 62 (2): 115-124
[27]陈海清，刘亚雄．从硫酸锌溶液净化渣回收锌和钴[J]．湖南有色金属，2006，22(2)：12-15
[28]赵廷凯．氨法处理湿法炼锌净化钴渣制取锌粉和回收钴：[博士学位论文]．长沙：中南大学，2001
[29] Stanojevi D, Nikoli B, Todorovi M. Evaluation of cobalt from cobaltic waste products from the production of electrolytic zinc and cadmium [J]. Hydrometallurgy, 2000,54(2-3): 151-160
[30]洪涛．氧化沉淀法分离炼锌除钴渣中锌钴的研究：[硕士学位论文]．西安：西安建筑科技大学，2003
[31]蓝德均．高锰酸钾氧化沉钴的研究及应用：[硕士学位论文]．昆明：昆明理工大学，2003
[32] Brian K. Tait. Cobalt-nickel separation: the extraction of cobalt(Ⅱ) and nickel(Ⅱ) by Cyanex 301, Cyanex 302 and Cyanex 272 [J]. Hydrometallurgy, 1993, 32(3): 365 -372
[33]王靖芳，杨文斌，冯彦琳．P507萃取锌、镉的机理[J]．山西大学学报(自然科学版)，1994，17(01)：38-41
[34] Berend Wassink, David Dreisinger, Jane Howard. Solvent extraction separation of zinc and cadmium from nickel and cobalt using Aliquat 336, a strong base anion exchanger, in the chloride and thiocyanate forms [J]. Hydrometallurgy, 2000, 57(3): 235-252
[35]牛聪伟，王开毅，舒万艮．用非平衡溶剂萃取法分离钴镍的研究[J].有色金属(冶炼部分)，2000(04)：6-8
[36]吴月顺，宋其圣，俞海云，等．P 5709萃取钴(Ⅱ)镍(Ⅱ)的动力学研究[J]．山东大学学报(自然科学版)．2001，36(02)：210-215
[37] LU Li-zhu, ZHANG Da-li, XIE Hui-qin, et al. Extraction and Separation of Cadmium and Zinc with a Mixture of Di-(2-Ethylhexyl)-Dithiophosphoric Acid and Trioctyl Amine [J]. Chinese Journal of Chemical Engineering, 1999, 7 (02): 132-138
[38] Alamdari E K, Moradkhani D, Darvishi D, et al. Synergistic effect of MEHPA on co-extraction of zinc and cadmium with DEHPA [J]. Minerals Engineering, 2004, 17 (1): 89-92
[39]杨大锦；谢刚；王吉坤，等．硫酸锌溶液的萃取工艺研究[J]．有色金属(冶炼部分)，2006(02)：9-13
[40]宁模功，张允恭．从湿法炼锌工艺产出的钴镍渣中回收锌[J]．湿法冶金，2002，21(1)：39-45
[41]宁模功，张允恭．处理湿法炼锌净化钴镍渣的试验研究[J]．有色金属(冶炼部分)，2001(1)：10-19
[42]彭容秋．重金属冶金学[M]．长沙：中南大学出版社，2004
[43]赵廷凯，唐漠堂．湿法炼锌净化钴渣新处理工艺[J]．中南工业大学学报，2001，32(4)：371-375
[44]傅献彩，沈文霞，姚天扬．物理化学(第4版)[M]．北京：高等教育出版，1990
[45]王琪．化学动力学导论[M]．长春：吉林人民出版社，1982．
[46]赵学庄．化学反应动力学原理[M]．北京：高等教育出版社，1984
[47]孙宁，柴德洪，杨春艳．气体容量法定碳中几个问题的研究[J]．哈尔滨师范大学自然科学学报，1995，11(2)：75-77．
[48] Samih A H, Mohamed A M. Influence of promoted and unpromoteddecomposition products of ammonium metavanadate on the pyrolysis of NaClO_2 [J].Journal of Analytical and Applied Pyrolysis, 2004, 72(1): 75-82.
[49] Joshua C W, Andrew Z, Daniel M, Matt T, et al. Sodium borohydride hydrolysiskinetics comparison for nickel, cobalt, and ruthenium boride catalysts [J]. Journal ofPower Sources, 2008, 19 (1): 335-339.
[50] Kohei U, Kazuhisa T, Yasushi S, Masahiko M, et al. Production of hydrogen bysteam reforming of ethanol over cobalt and nickel catalysts supported onperovskite-type oxides [J]. Catalysis Communications, 2008, 9(5): 600-604.
[51]毛云中，凌霞，陈屹．钴的检测方法进展[J]．理化检验一化学分册2006，42(10)：861-864
[52]龚竹青．理论电化学导论[M]．长沙：中南工业大学出版社，1988
[53]邝生鲁．应用电化学[M]．武汉：华中理工大学社，1994
[54]B．B．达马斯会，O．A．佩特里．电化学动力学导论(谷林镁，秦尔华译)[M]．北京：科学出版社，1989
[55] ZENG Wen-ming, CHEN Nian-yi. Potential - pH diagrams of Al-H_2O system [J].Transactions of Nonferrous Metals Society of China, 1997, 7 (2): 34-37.
[56] DEAN J A. Lange's Handbook of chemistry (15th Edition) [M]. McGraw Hill,1999
[57]叶大伦，胡建华．实用无机物热力学数据手册(第2版)．北京：冶金工业出版社，2002
[58]陈小文，白新德，薛祥义，等．电位-pH平衡图及其在核材料腐蚀研究中的应用[J]．清华大学学报(自然科学版)，2002，42(5)：692-695
[59]钟文彬，杨玉玺，张昭．湿化学法制备四氧化三钴的研究-热力学分析[J]．四川有色金属，3001(01)：23-26
[60]曾桂生．硫酸锌溶液中锌粉置换除钻的机理研究：[博士学位论文]．昆明：昆明理工大学，2006
[61] Cooper K R, Kelly R G. Crack tip chemistry and electrochemistry of environmental cracks in AA 7050 [J]. Corrosion Science, 2007, 49 (6): 2636-2662
[62] Fratesi R, Roventi G. Corrosion resistance of Zn-Ni alloy coatings in industrial production [J]. Surface and Coatings Technology, 1996, 82 (1-2): 158-164