低磷化学镀镍工艺的研究
|
摘要
低磷化学镀镍因其优异的可焊性而被广泛的应用在电子领域。因此,研究低磷化学镀镍工艺有重大的实际意义和推广价值。
本文分别对乳酸丙酸体系、柠檬酸乙酸体系、丁二酸苹果酸体系三个化学镀镍络合体系进行了研究。分别采用增重法、X射线荧光光谱仪(XRF)、贴滤纸法、挂锡法研究了不同体系对镀速、磷含量、孔隙率、可焊性的影响,并通过体视显微镜和原子力显微镜(AFM)对不同体系的镀层进行表面形貌的观察。通过上述比较确定了乳酸丙酸体系作为低磷化学镀镍的基础体系。
将乳酸丙酸体系作为低磷化学镀镍的基础体系,研究了镀液中各成分以及工艺条件对化学镀镍镀速和磷含量的影响,发现提高Ni2+/H2PO2―、增加络合剂和醋酸钠浓度、提高pH值都有利于得到低磷镀层,并确定了各工艺参数的用量范围。通过正交试验,得到了磷含量较低的化学镀镍工艺。这种工艺得到的镀层磷含量为2.46mass%。
在上述低磷化学镀镍工艺的基础上,分别研究了三乙醇胺、丙二酸、丁二酸、苹果酸以及乙二胺对镀层外观、镀液稳定性、孔隙率、可焊性、镀速磷含量、微观形貌的影响,从而确定了丁二酸适合作为低磷化学镀镍的络合剂。并通过周期试验检验了镀液的性能和寿命。通过测定添加不同络合剂条件下的阳极极化曲线和阴极极化曲线,发现三乙醇胺加入可以使次亚磷酸钠的氧化速度先增大后减小,丁二酸则使得氧化速度增大;三乙醇胺和丁二酸的加入均使得镍还原电位正移,还原电流增大,但三乙醇胺会使还原电流逐渐增大,而丁二酸会使还原电流先减小后增大。
Electroless nickel of low-phosphorous coatings have been widely applied in electronic fields because of its great solderability. Therefore, the study of electroless nickel plating technics of low-phosphorous is of great practical significance and value.
In this paper, lactic acid and propionic acid system , citric acid and acetic acid, succinic acid and malic acid system which are the complexing agent systems were researched. The deposition rate is measured through weighing by electro-balance; the P content is analyzed by X-ray fluorescence spectrum(XRF); the porosity is determined by GB5935-86; surface morphology is observed by stereomicroscope and atom force microscope(AFM); the solderability is tested by immersion tin. Through compared the different complexing agent systems, lactic acid and propionic acid system is determined as the electroless nickel of low- phosphorous based system.
After determined the based system, the effect of composition in the electrole nickel plating solution and process condition on deposition rate and P content is discussed. Through the research obtained that increase Ni2+/H2PO2― , the concentration of complexing agent and sodium acetate and pH is propitious to low-phosphorous coatings. At the same time the scale of process condition is confirmed. Through orthogonal test, gets the best formula of electroless nickel of low-phosphorous. The P content of the coating obtained from the satisfactory electroless nickel plating is 2.46 mass%.
Based on the satisfactory electroless nickel plating technic of low-phosphorous, then study the effect of Triethanolamine, Propandioic, Succinic acid, Malic acid and Ethylene diamine on coating appearance, bath stability, porosity, deposition rate, P content and the surface microtopography. Through these research obtain that Succinic acid is suitable for the complexing agent of electroless nickel of low-phosphorous. The turnover test is made to detect the bath life and the performance of the bath. Then, LVC is applied to study the effect of complexing agent on the cathode polarization curves and anodic polarization curves, The results show that the Triethanolamine can cause sodium hypophosphite oxidation rate increase and then decrease,succinic acid can make sodium hypophosphite oxidation rate increase; triethanolamine and succinic acid can cause the nickel reduction potential is positively shifted and reducing current increased. But triethanolamine can make nickel reduction rate increase, succinic acid cause nickel reduction rate decrease and then increase.
本文分别对乳酸丙酸体系、柠檬酸乙酸体系、丁二酸苹果酸体系三个化学镀镍络合体系进行了研究。分别采用增重法、X射线荧光光谱仪(XRF)、贴滤纸法、挂锡法研究了不同体系对镀速、磷含量、孔隙率、可焊性的影响,并通过体视显微镜和原子力显微镜(AFM)对不同体系的镀层进行表面形貌的观察。通过上述比较确定了乳酸丙酸体系作为低磷化学镀镍的基础体系。
将乳酸丙酸体系作为低磷化学镀镍的基础体系,研究了镀液中各成分以及工艺条件对化学镀镍镀速和磷含量的影响,发现提高Ni2+/H2PO2―、增加络合剂和醋酸钠浓度、提高pH值都有利于得到低磷镀层,并确定了各工艺参数的用量范围。通过正交试验,得到了磷含量较低的化学镀镍工艺。这种工艺得到的镀层磷含量为2.46mass%。
在上述低磷化学镀镍工艺的基础上,分别研究了三乙醇胺、丙二酸、丁二酸、苹果酸以及乙二胺对镀层外观、镀液稳定性、孔隙率、可焊性、镀速磷含量、微观形貌的影响,从而确定了丁二酸适合作为低磷化学镀镍的络合剂。并通过周期试验检验了镀液的性能和寿命。通过测定添加不同络合剂条件下的阳极极化曲线和阴极极化曲线,发现三乙醇胺加入可以使次亚磷酸钠的氧化速度先增大后减小,丁二酸则使得氧化速度增大;三乙醇胺和丁二酸的加入均使得镍还原电位正移,还原电流增大,但三乙醇胺会使还原电流逐渐增大,而丁二酸会使还原电流先减小后增大。
Electroless nickel of low-phosphorous coatings have been widely applied in electronic fields because of its great solderability. Therefore, the study of electroless nickel plating technics of low-phosphorous is of great practical significance and value.
In this paper, lactic acid and propionic acid system , citric acid and acetic acid, succinic acid and malic acid system which are the complexing agent systems were researched. The deposition rate is measured through weighing by electro-balance; the P content is analyzed by X-ray fluorescence spectrum(XRF); the porosity is determined by GB5935-86; surface morphology is observed by stereomicroscope and atom force microscope(AFM); the solderability is tested by immersion tin. Through compared the different complexing agent systems, lactic acid and propionic acid system is determined as the electroless nickel of low- phosphorous based system.
After determined the based system, the effect of composition in the electrole nickel plating solution and process condition on deposition rate and P content is discussed. Through the research obtained that increase Ni2+/H2PO2― , the concentration of complexing agent and sodium acetate and pH is propitious to low-phosphorous coatings. At the same time the scale of process condition is confirmed. Through orthogonal test, gets the best formula of electroless nickel of low-phosphorous. The P content of the coating obtained from the satisfactory electroless nickel plating is 2.46 mass%.
Based on the satisfactory electroless nickel plating technic of low-phosphorous, then study the effect of Triethanolamine, Propandioic, Succinic acid, Malic acid and Ethylene diamine on coating appearance, bath stability, porosity, deposition rate, P content and the surface microtopography. Through these research obtain that Succinic acid is suitable for the complexing agent of electroless nickel of low-phosphorous. The turnover test is made to detect the bath life and the performance of the bath. Then, LVC is applied to study the effect of complexing agent on the cathode polarization curves and anodic polarization curves, The results show that the Triethanolamine can cause sodium hypophosphite oxidation rate increase and then decrease,succinic acid can make sodium hypophosphite oxidation rate increase; triethanolamine and succinic acid can cause the nickel reduction potential is positively shifted and reducing current increased. But triethanolamine can make nickel reduction rate increase, succinic acid cause nickel reduction rate decrease and then increase.
引文
1姜晓霞,沈伟.化学理论与实践.北京,国防工业出版社,2000:4~7
2 W.J. Cheong, Ben L. Luan, David W. Shoesmith. The Effects of Stabilizers on the Bath Stability of Electroless Ni Deposition and the Deposit. 2004, 229: 282~300
3李宁,屠振密.化学镀实用技术.化学工业出版社, 2004:52~56
4 Guofeng Cui, Ning Li, Deyu Li et al. The Physical and Electrochemical Properities of Electroless Deposited Nickel-phosphorous Black Coatings. Surface & Coatings Technology. 2006,200(24):6808~6814
5薛雷刚,印仁和,贺岩峰等.无铅无镉光亮化学镀Ni-P合金.电镀与精饰. 2007, 29(2):27~31
6 Martyak, et al. Electroless Nickel Plating Solution. USP5306334, 1994
7王殿龙,苏韧,戴长松.无铅无镉光亮化学镀镍.电镀与涂饰. 2007, 26(1):41~43
8李健三,李异,廖景娱.低温化学镀镍工艺级镀层性能的研究.材料与表面处理. 2002, 16(3)-37-40
9 R.Lambert, J.Duquette. A Study of Electroless Nickel Coatings Containing Low Phosphorous. This Solid Films. 1989, 177(1-2): 207~223
10 Msllory, Jr. Electroless Nickel Baths for Enhancing Hardness. USP 5494710. 1996
11方景礼,叶向荣,方晶.低磷化学镀镍层的组成和结构.应用化学. 1992, 9(5):34~38
12 Xu-Cheng Wang, Wen-bin Cai, Wei-Jiang et al. Effects of Ligands on Electroless Ni-P Alloy Plating Form Alkaline Citrate-ammonia Solution. Surface & Coating Technology. 2003, 168(2-3): 300~306
13张永忠.丙烯基硫脲对低磷林化学镀镍沉积过程的影响.腐蚀科学与防护技术. 1999, 11(2):122~125
14张永忠,吴宜勇,姚玫.低磷化学镀镍工艺,电镀与环保. 1995, 15(5):18~20
15张喜生,李华飞.泡沫基体上低磷化学镀镍工艺.电镀与涂饰. 2007, 26(2):22~24
16迟明磊,李宁.低磷乳酸-丙酸体系化学镀镍工艺的研究.表面技术. 2006,25(4):50~52
17 Y.C.Sohn, Jin Yu, S.K.Kang et al. Effect of Phosphorous Content on The Reaction of Electroless Ni-P with Sn and Crystallization of Ni-P. Journal of Electronic Materials. 2004, 33(55):790~795
18 J.T. Winowlin Jappes, B.Ramamoorthy, P.Kesavan Nair. A Study on The Influence of Process on Efficiency and Crystallinity of Electroless Ni-P Deposits. Journal of Materials Processing Technology. 2005, 169(2): 308~313
19 Hongxia Guo, Zhenping Qin, Jie Wei et al. Synthesis of Novel Magenetic Spheres by Electroless Nickel Coating of Polymer Spheres. Surface and Coatings Technology. 2005, 200(7):2531~2536
20 S.C. Mehta, D.A. Smith, U,Erb. Study of Grain Growth in Electrodeposited Nanocrystalline Nickel-1.2wt.% Phosphorous Alloy. Materials Science and Engineering. 1995, 204(1-2):227~232
21 Msllory, Jr. Electroless Nickel Baths for Enhancing Hardness. USP 5494710. 1996
22方景礼,叶向荣,陈中法.影响化学镀镍Ni-P层可焊性的因素.电镀与精饰. 1990, 12(6):3~6
23 Y.S. Huang, X.T. Zeng, X.F. Hu et al. Corrosion Resistance Properties of Electroless Nickel Composite Coating. Electrochemical Acta. 2004, 49(25): 4313~4319
24 Guofeng Cui, Ning Li, Deyu Li et al. Study of Optimized Complexing Agent for Low-phosphorus Electroless Nickel Plating Bath. The Electrochamical Society. 2005, 152(10): 1~6
25于德超,谈定生,王松泰.化学镀镍技术在电子工业的应用.电镀与涂饰. 2007, 26(4):42~45
26 V.F. Makarov, Y. V. Prusov, I.O. Lebedeva. Electroless Deposition of Nickel Coatings with High Phosphorus Content. Russian Journal of Applied Chemistry. 2005, 78(1):82~84
27 M. Schlesinger, M. Paunovic. Modern Electroplating. Electrochemical Acta. 2001,46(9):1385~1386
28邹建平,贺子凯,黄鑫等.钢基体中温酸性化学镀镍的研究.电镀与涂饰. 2005, 24(6):12~16
29张道礼,龚树萍,周东祥.不同络合剂对化学镀镍过程的影响.材料开发与应用. 2000, 15(1):5~8
30 Mallory, Tr. Method for Deposition Electroless Nickel Phorous Alloys. USP6020021, 2000
31 Y.S. huang, F.Z. Cui. Effect of Complexing Agent on The Morphology and Microstructure of Electroless Deposited Ni-P Alloy. Surface and Coating. 2007,201(9-11):5416~5418
32陈一胜,张乐观,王勇.稀土对化学镀镍溶液稳定性的影响.材料保护. 2002, 35(4):1~3
33 Feldstein, et al. Non-ionic Stabilizers in Composite Electroless Plating. UPS5863616, 1999
34聂书红,蔡珣.碘化钾在酸性镍磷镀液中的应用.机械工程材料. 2002, 26(5):6~9
35 Martyak, et al. Electroless Nickel Plating Baths. UPS5258061, 1993
36 Hollander, et al. Lead-free Chemical Nickel Alloy. UPS6911269, 2005
37 Gulla, et al. Stabilized Electroless Plating Solutions. UPS4189324, 1980
38黄友升,李林.稳定剂M12在化学镀镍中的作用.电镀与环保. 2001,21(117):21~23
39 Dahms. Acidic Nickel Baths Containg 1-(2-sulfoethy1)-Pyridiniumbetaine. USP5264112,1993
40孙克宁,张亦林.化学镀Ni-P工艺研究.电镀与环保. 1998, 18(3):18~22
41徐瑞东,郭忠诚.新型化学镀镍光亮剂的研究.材料保护. 2002, 35(6):30~32
42崔国锋,李宁,黎德育等.化学镀镍液的缓冲容量与沉积速度的关系.电镀与环保. 2003, 23(6):19~22
43张喜生,李华飞.泡沫基体上低磷化学镀镍工艺.电镀与涂饰. 2007,26(2):22~24
44罗建东.中温低磷化学镀镍工艺研究.电镀与环保. 2002,22(2):11~12
45 W.L.Liu, S.H. Hsieh, T.K.Tsai et al. Temperature and pH Dependence of The Electroless Ni-P Deposition on Silicon. Thin Solid Films. 2006, 510(1):102~106
46王桂香,李宁.用混合电位理论研究塑料化学镀镍过程.材料保护. 2005, 38(5): 1~5
47 Kwang-lung lin, Jia-weiHwang. Effevt of Thiourea and Lead Zcetate on The Deposition of Electroless Nickel. Materials Chemistry and Physics. 2002,76(2):204~211
48刘海萍,李宁,毕四富.用正交试验法优选化学镀镍四元符合添加剂.材料保护. 2006, 39(10):30~33
49邹建平,贺子凯,黄鑫等.中温酸性化学镀镍络合剂的研究.电镀与涂饰. 2004, 23(5):19~22
50孙景庄,薛惠茹.提高化学镀镍层含磷量的研究.电镀与环保. 1995, 3(83):15~18
51 M. Ebn Touhami, E. Chassaing, M.Cherkaoui. Modelisation of Ni-P Electroless Deposition in Ammoniacal Solutions. Electrochimica Acta. 2003, 48:3651~3658
52 A.M. Fundo, L.M. Abrantes. The Electrocatalytic Behaviour of Electroless Ni-P Alloys. Journal of Electroanalytical Chemistry. 2007, 600:63~79
53韩克平,方景礼.乙酸钠加速化学镀镍的研究.表面技术. 1997, 26(2):8~10
2 W.J. Cheong, Ben L. Luan, David W. Shoesmith. The Effects of Stabilizers on the Bath Stability of Electroless Ni Deposition and the Deposit. 2004, 229: 282~300
3李宁,屠振密.化学镀实用技术.化学工业出版社, 2004:52~56
4 Guofeng Cui, Ning Li, Deyu Li et al. The Physical and Electrochemical Properities of Electroless Deposited Nickel-phosphorous Black Coatings. Surface & Coatings Technology. 2006,200(24):6808~6814
5薛雷刚,印仁和,贺岩峰等.无铅无镉光亮化学镀Ni-P合金.电镀与精饰. 2007, 29(2):27~31
6 Martyak, et al. Electroless Nickel Plating Solution. USP5306334, 1994
7王殿龙,苏韧,戴长松.无铅无镉光亮化学镀镍.电镀与涂饰. 2007, 26(1):41~43
8李健三,李异,廖景娱.低温化学镀镍工艺级镀层性能的研究.材料与表面处理. 2002, 16(3)-37-40
9 R.Lambert, J.Duquette. A Study of Electroless Nickel Coatings Containing Low Phosphorous. This Solid Films. 1989, 177(1-2): 207~223
10 Msllory, Jr. Electroless Nickel Baths for Enhancing Hardness. USP 5494710. 1996
11方景礼,叶向荣,方晶.低磷化学镀镍层的组成和结构.应用化学. 1992, 9(5):34~38
12 Xu-Cheng Wang, Wen-bin Cai, Wei-Jiang et al. Effects of Ligands on Electroless Ni-P Alloy Plating Form Alkaline Citrate-ammonia Solution. Surface & Coating Technology. 2003, 168(2-3): 300~306
13张永忠.丙烯基硫脲对低磷林化学镀镍沉积过程的影响.腐蚀科学与防护技术. 1999, 11(2):122~125
14张永忠,吴宜勇,姚玫.低磷化学镀镍工艺,电镀与环保. 1995, 15(5):18~20
15张喜生,李华飞.泡沫基体上低磷化学镀镍工艺.电镀与涂饰. 2007, 26(2):22~24
16迟明磊,李宁.低磷乳酸-丙酸体系化学镀镍工艺的研究.表面技术. 2006,25(4):50~52
17 Y.C.Sohn, Jin Yu, S.K.Kang et al. Effect of Phosphorous Content on The Reaction of Electroless Ni-P with Sn and Crystallization of Ni-P. Journal of Electronic Materials. 2004, 33(55):790~795
18 J.T. Winowlin Jappes, B.Ramamoorthy, P.Kesavan Nair. A Study on The Influence of Process on Efficiency and Crystallinity of Electroless Ni-P Deposits. Journal of Materials Processing Technology. 2005, 169(2): 308~313
19 Hongxia Guo, Zhenping Qin, Jie Wei et al. Synthesis of Novel Magenetic Spheres by Electroless Nickel Coating of Polymer Spheres. Surface and Coatings Technology. 2005, 200(7):2531~2536
20 S.C. Mehta, D.A. Smith, U,Erb. Study of Grain Growth in Electrodeposited Nanocrystalline Nickel-1.2wt.% Phosphorous Alloy. Materials Science and Engineering. 1995, 204(1-2):227~232
21 Msllory, Jr. Electroless Nickel Baths for Enhancing Hardness. USP 5494710. 1996
22方景礼,叶向荣,陈中法.影响化学镀镍Ni-P层可焊性的因素.电镀与精饰. 1990, 12(6):3~6
23 Y.S. Huang, X.T. Zeng, X.F. Hu et al. Corrosion Resistance Properties of Electroless Nickel Composite Coating. Electrochemical Acta. 2004, 49(25): 4313~4319
24 Guofeng Cui, Ning Li, Deyu Li et al. Study of Optimized Complexing Agent for Low-phosphorus Electroless Nickel Plating Bath. The Electrochamical Society. 2005, 152(10): 1~6
25于德超,谈定生,王松泰.化学镀镍技术在电子工业的应用.电镀与涂饰. 2007, 26(4):42~45
26 V.F. Makarov, Y. V. Prusov, I.O. Lebedeva. Electroless Deposition of Nickel Coatings with High Phosphorus Content. Russian Journal of Applied Chemistry. 2005, 78(1):82~84
27 M. Schlesinger, M. Paunovic. Modern Electroplating. Electrochemical Acta. 2001,46(9):1385~1386
28邹建平,贺子凯,黄鑫等.钢基体中温酸性化学镀镍的研究.电镀与涂饰. 2005, 24(6):12~16
29张道礼,龚树萍,周东祥.不同络合剂对化学镀镍过程的影响.材料开发与应用. 2000, 15(1):5~8
30 Mallory, Tr. Method for Deposition Electroless Nickel Phorous Alloys. USP6020021, 2000
31 Y.S. huang, F.Z. Cui. Effect of Complexing Agent on The Morphology and Microstructure of Electroless Deposited Ni-P Alloy. Surface and Coating. 2007,201(9-11):5416~5418
32陈一胜,张乐观,王勇.稀土对化学镀镍溶液稳定性的影响.材料保护. 2002, 35(4):1~3
33 Feldstein, et al. Non-ionic Stabilizers in Composite Electroless Plating. UPS5863616, 1999
34聂书红,蔡珣.碘化钾在酸性镍磷镀液中的应用.机械工程材料. 2002, 26(5):6~9
35 Martyak, et al. Electroless Nickel Plating Baths. UPS5258061, 1993
36 Hollander, et al. Lead-free Chemical Nickel Alloy. UPS6911269, 2005
37 Gulla, et al. Stabilized Electroless Plating Solutions. UPS4189324, 1980
38黄友升,李林.稳定剂M12在化学镀镍中的作用.电镀与环保. 2001,21(117):21~23
39 Dahms. Acidic Nickel Baths Containg 1-(2-sulfoethy1)-Pyridiniumbetaine. USP5264112,1993
40孙克宁,张亦林.化学镀Ni-P工艺研究.电镀与环保. 1998, 18(3):18~22
41徐瑞东,郭忠诚.新型化学镀镍光亮剂的研究.材料保护. 2002, 35(6):30~32
42崔国锋,李宁,黎德育等.化学镀镍液的缓冲容量与沉积速度的关系.电镀与环保. 2003, 23(6):19~22
43张喜生,李华飞.泡沫基体上低磷化学镀镍工艺.电镀与涂饰. 2007,26(2):22~24
44罗建东.中温低磷化学镀镍工艺研究.电镀与环保. 2002,22(2):11~12
45 W.L.Liu, S.H. Hsieh, T.K.Tsai et al. Temperature and pH Dependence of The Electroless Ni-P Deposition on Silicon. Thin Solid Films. 2006, 510(1):102~106
46王桂香,李宁.用混合电位理论研究塑料化学镀镍过程.材料保护. 2005, 38(5): 1~5
47 Kwang-lung lin, Jia-weiHwang. Effevt of Thiourea and Lead Zcetate on The Deposition of Electroless Nickel. Materials Chemistry and Physics. 2002,76(2):204~211
48刘海萍,李宁,毕四富.用正交试验法优选化学镀镍四元符合添加剂.材料保护. 2006, 39(10):30~33
49邹建平,贺子凯,黄鑫等.中温酸性化学镀镍络合剂的研究.电镀与涂饰. 2004, 23(5):19~22
50孙景庄,薛惠茹.提高化学镀镍层含磷量的研究.电镀与环保. 1995, 3(83):15~18
51 M. Ebn Touhami, E. Chassaing, M.Cherkaoui. Modelisation of Ni-P Electroless Deposition in Ammoniacal Solutions. Electrochimica Acta. 2003, 48:3651~3658
52 A.M. Fundo, L.M. Abrantes. The Electrocatalytic Behaviour of Electroless Ni-P Alloys. Journal of Electroanalytical Chemistry. 2007, 600:63~79
53韩克平,方景礼.乙酸钠加速化学镀镍的研究.表面技术. 1997, 26(2):8~10