电镀铜镍合金用阳极材料的研究
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摘要
本文在充分调研和研究阳极材料性能的基础上,针对拟定的铜、镍阳极材料,结合实验室赫尔槽实验和小型电镀生产线中试实验,选择无氧铜、含磷铜、镍圆饼、含硫镍和铜镍合金阳极,主要对两种铜镍合金镀液进行了试验研究。研究了阳极溶解情况、铜粉现象、镀液的电流效率、均镀能力、稳定性等性能。
试验结果表明,三乙醇胺可和Cu~+生成稳定的络合物,络合常数很大,导致镀液中产生大量的Cu~+离子,进而生成铜粉。Cu~+的存在导致铜优先沉积。三乙醇胺为主络合剂的镀液中镍阳极易产生钝化,不利于阳极溶解。三乙醇胺不宜用作无氰电镀铜镍合金的主络合剂和辅络合剂。
NJKM-01对铜镍的络合性能虽无三乙醇胺高,但以NJKM-01为主络合剂的镀液不易产生铜粉,可实现铜镍共沉积。该镀液中使用无氧铜、磷铜角、镍圆饼、含硫镍等均可正常溶解,很少发生钝化现象。实验证明,从抑制产生铜粉的角度考虑,使用含磷铜阳极,特别是使用高磷铜(含磷量1.53%)铜阳极可有效抑制铜粉的产生。在长时间电镀后,添加双氧水使镀液中积累的少量Cu~+氧化成Cu~(2+),可明显改善阴极镀层质量。
本文对不同配方改变工艺条件进行了试验,探讨了温度、电流密度、搅拌速度(滚桶转速)等对试验结果的影响。经优选,经优选,使用阳极篮表面积分别为40.5dm~2磷铜角(套阳极袋)和40.5dm~2镍圆饼阳极,铜、镍阳极电流分别使用30A和30A的情况下,能生产出符合工艺要求的电镀铜镍合金坯饼,电镀工艺稳定。为我国的造币业提供了一种新的选择,具有深远的实际意义和应用前景。
On the basis of investigating and studying the characters of the positive pole,the text studies the reacting effects of the liquid where electroplating Copper-Nickel alloy through Heecao test and small electroplating line test using many materials as positive pole,such as non-oxidized copper,copper including phosphorus,nickel pancake,nickel including sulphur and Copper-Nickel alloy.In this research,it studies the dissolving state of the positive pole,copper power,electric current efficiency,the capacity of even electroplating,and stability.
The result indicates that it produces a lot of Cu~+ and copper power next in the electroplating liquid because the complexing constant of complex agents created from triethanolamine and Cu~+ is large.Cu~+ makes copper deposit preferentially.Tin as positive pole is blunt easily and it is bad for positive pole to dissolve in the electroplating liquid where triethanolamine is main complex agent,triethanolamine is unsuitable for main complex agent and subsidiary complex agent to electroplate Copper-Nickel alloy.
NJKM-01's function to complex copper and nickel is not better than triethanolamine's,but it produces few copper power and can make copper and nickel deposit simultaneously in the electroplating liquid where using NJKM-01 as main complex agent,non-oxidized copper,copper including phosphorus,nickel pancake,nickel including sulphur can dissolve and are not blunt easily. The research proves that using phosphorus-copper,especially copper including phosphorus of high rate (1.53%),can restrain the production of copper power efficaciously.After long electroplates,it can improve the quality of electroplating layer of negative pole that add H_2O_2 to make the few Cu~+ oxidtze Cu~(2+).
The text studies that different directions change craft conditions in the research and approaches that temperature,the density of electric current,the steep of stirring affect the result of research.through selecting preferentially,on the situation of using copper including phosphorus and nickel pancake as positive pole,and electric current being both 30A and 30A,it can produce coin pancakes electroplated Copper-Nickel alloy which satisfy the demand of craft.This provides another choice for minting career in our country,and it has actual significance and applied future.
试验结果表明,三乙醇胺可和Cu~+生成稳定的络合物,络合常数很大,导致镀液中产生大量的Cu~+离子,进而生成铜粉。Cu~+的存在导致铜优先沉积。三乙醇胺为主络合剂的镀液中镍阳极易产生钝化,不利于阳极溶解。三乙醇胺不宜用作无氰电镀铜镍合金的主络合剂和辅络合剂。
NJKM-01对铜镍的络合性能虽无三乙醇胺高,但以NJKM-01为主络合剂的镀液不易产生铜粉,可实现铜镍共沉积。该镀液中使用无氧铜、磷铜角、镍圆饼、含硫镍等均可正常溶解,很少发生钝化现象。实验证明,从抑制产生铜粉的角度考虑,使用含磷铜阳极,特别是使用高磷铜(含磷量1.53%)铜阳极可有效抑制铜粉的产生。在长时间电镀后,添加双氧水使镀液中积累的少量Cu~+氧化成Cu~(2+),可明显改善阴极镀层质量。
本文对不同配方改变工艺条件进行了试验,探讨了温度、电流密度、搅拌速度(滚桶转速)等对试验结果的影响。经优选,经优选,使用阳极篮表面积分别为40.5dm~2磷铜角(套阳极袋)和40.5dm~2镍圆饼阳极,铜、镍阳极电流分别使用30A和30A的情况下,能生产出符合工艺要求的电镀铜镍合金坯饼,电镀工艺稳定。为我国的造币业提供了一种新的选择,具有深远的实际意义和应用前景。
On the basis of investigating and studying the characters of the positive pole,the text studies the reacting effects of the liquid where electroplating Copper-Nickel alloy through Heecao test and small electroplating line test using many materials as positive pole,such as non-oxidized copper,copper including phosphorus,nickel pancake,nickel including sulphur and Copper-Nickel alloy.In this research,it studies the dissolving state of the positive pole,copper power,electric current efficiency,the capacity of even electroplating,and stability.
The result indicates that it produces a lot of Cu~+ and copper power next in the electroplating liquid because the complexing constant of complex agents created from triethanolamine and Cu~+ is large.Cu~+ makes copper deposit preferentially.Tin as positive pole is blunt easily and it is bad for positive pole to dissolve in the electroplating liquid where triethanolamine is main complex agent,triethanolamine is unsuitable for main complex agent and subsidiary complex agent to electroplate Copper-Nickel alloy.
NJKM-01's function to complex copper and nickel is not better than triethanolamine's,but it produces few copper power and can make copper and nickel deposit simultaneously in the electroplating liquid where using NJKM-01 as main complex agent,non-oxidized copper,copper including phosphorus,nickel pancake,nickel including sulphur can dissolve and are not blunt easily. The research proves that using phosphorus-copper,especially copper including phosphorus of high rate (1.53%),can restrain the production of copper power efficaciously.After long electroplates,it can improve the quality of electroplating layer of negative pole that add H_2O_2 to make the few Cu~+ oxidtze Cu~(2+).
The text studies that different directions change craft conditions in the research and approaches that temperature,the density of electric current,the steep of stirring affect the result of research.through selecting preferentially,on the situation of using copper including phosphorus and nickel pancake as positive pole,and electric current being both 30A and 30A,it can produce coin pancakes electroplated Copper-Nickel alloy which satisfy the demand of craft.This provides another choice for minting career in our country,and it has actual significance and applied future.
引文
[1]WESTA-IM ABS Coin Blank Plant Operating Manual,2001
[2]程良等,论硫酸盐光亮镀铜的阳极行为,Electroplating&Pollution Control,1999,Vol.19 No.3,10-13.
[3]周腾芳等,谈谈硫酸盐光亮镀铜的磷铜阳极.材料保护,2001,第34卷第10期,31-33.
[4]张立伦,影响酸性电镀铜用磷铜阳极质量因素的探导,电镀与涂饰,2006,Vol.25,No.9.35-38.
[5]张允成,胡如南,向荣,电镀手册,1997,159-163.
[6]冯升平,阳极磷铜的检验与判定,孔化与电镀,2003,No.9,31-34.
[7]陈国良等,酸性介质中铜阳极溶解出和阴极沉积过程的EQCM,漳州师范学院学报,2005,No.4,50-52.
[8]Nerers R P,Hungerford RL,Palmer EW,Iron Age,1954,174,114.
[9]Safranek W H,Faust C L,Plating,1955,42,154
[10]马洪芳等,电镀阳极浅析,材料保护,2001,No.8,43.
[11]Surface Technology,1981,14(4),309-321.
[12]蒋雄,电镀与涂饰,1984,4,2.
[13]赖依聂尔,库特荚夫采夫,电镀原理,张治平,王秀容等译,北京机械工业出版社,1964,350.
[14]沈锡宽等,印制电路技术,北京科学出版社,1987,204.
[15]邵性波泽,《西德》实用电镀技术(第三版)国防工业出版社,1985,1237
[16](美)弗利德里克A洛温海姆,现代电镀(第三版)机械工业出版社,1982,235-236.
[17]香港金属表面处理学会,表面处理通讯(第19期),1997,19,22
[18]袁中圣,电路板资讯,台北,1993,65,89-94.
[19]林英毅,印制电路、表面贴装,,1999,1,88-92;
[20]黄子勋,吴纯素等,电镀理论,北京中国农业机械出版社,1982,1,42.
[21]周国定,徐群杰,碱性介质中铜镍合金及铜电极的光电化学研究,中国腐蚀与防护学报,1998第18卷151-154
[22]程良等,再谈硫酸盐光亮镀铜的磷铜阳极,电镀与涂饰,1999,Vol.18,No.2,20-26.
[23]Sricharaenchaikit,Plating and Surf.Fin,1999,86(10),66.
[24]刘学雷等,硫酸盐镀铜溶液中铜阳极性能研究.Plating and Finishing,2001,Vol.23No.4,36-37.
[25]宁波神化,产品分类信息.
[26]方景礼,多元络合物电镀,1983
[27]Singb VB.Sarabi AA Plating,Plating and Surf.Fi,n1996,83(10),54
[28]屠振密,电镀合金原理与工艺,1993,85-90
[29]Saubestre EB,1958,45,927
[30]A J Bard,Encyclopedia of Electrodeposited of the Elements,1976,第12卷
[31]黄清安 袁海涛等,电镀铜—镍合金时的阴极行为研究,材料保护,1993,第26卷,4-6.
[32]张顺清.锌镍合金电镀工艺的研究[J].电镀与环保,1989,(6);11-13
[33]王鸿建.电镀工艺学[M]哈尔滨:哈尔滨工业大学出版社,1989
[2]程良等,论硫酸盐光亮镀铜的阳极行为,Electroplating&Pollution Control,1999,Vol.19 No.3,10-13.
[3]周腾芳等,谈谈硫酸盐光亮镀铜的磷铜阳极.材料保护,2001,第34卷第10期,31-33.
[4]张立伦,影响酸性电镀铜用磷铜阳极质量因素的探导,电镀与涂饰,2006,Vol.25,No.9.35-38.
[5]张允成,胡如南,向荣,电镀手册,1997,159-163.
[6]冯升平,阳极磷铜的检验与判定,孔化与电镀,2003,No.9,31-34.
[7]陈国良等,酸性介质中铜阳极溶解出和阴极沉积过程的EQCM,漳州师范学院学报,2005,No.4,50-52.
[8]Nerers R P,Hungerford RL,Palmer EW,Iron Age,1954,174,114.
[9]Safranek W H,Faust C L,Plating,1955,42,154
[10]马洪芳等,电镀阳极浅析,材料保护,2001,No.8,43.
[11]Surface Technology,1981,14(4),309-321.
[12]蒋雄,电镀与涂饰,1984,4,2.
[13]赖依聂尔,库特荚夫采夫,电镀原理,张治平,王秀容等译,北京机械工业出版社,1964,350.
[14]沈锡宽等,印制电路技术,北京科学出版社,1987,204.
[15]邵性波泽,《西德》实用电镀技术(第三版)国防工业出版社,1985,1237
[16](美)弗利德里克A洛温海姆,现代电镀(第三版)机械工业出版社,1982,235-236.
[17]香港金属表面处理学会,表面处理通讯(第19期),1997,19,22
[18]袁中圣,电路板资讯,台北,1993,65,89-94.
[19]林英毅,印制电路、表面贴装,,1999,1,88-92;
[20]黄子勋,吴纯素等,电镀理论,北京中国农业机械出版社,1982,1,42.
[21]周国定,徐群杰,碱性介质中铜镍合金及铜电极的光电化学研究,中国腐蚀与防护学报,1998第18卷151-154
[22]程良等,再谈硫酸盐光亮镀铜的磷铜阳极,电镀与涂饰,1999,Vol.18,No.2,20-26.
[23]Sricharaenchaikit,Plating and Surf.Fin,1999,86(10),66.
[24]刘学雷等,硫酸盐镀铜溶液中铜阳极性能研究.Plating and Finishing,2001,Vol.23No.4,36-37.
[25]宁波神化,产品分类信息.
[26]方景礼,多元络合物电镀,1983
[27]Singb VB.Sarabi AA Plating,Plating and Surf.Fi,n1996,83(10),54
[28]屠振密,电镀合金原理与工艺,1993,85-90
[29]Saubestre EB,1958,45,927
[30]A J Bard,Encyclopedia of Electrodeposited of the Elements,1976,第12卷
[31]黄清安 袁海涛等,电镀铜—镍合金时的阴极行为研究,材料保护,1993,第26卷,4-6.
[32]张顺清.锌镍合金电镀工艺的研究[J].电镀与环保,1989,(6);11-13
[33]王鸿建.电镀工艺学[M]哈尔滨:哈尔滨工业大学出版社,1989