在铝硅合金上化学沉积Ni-P、Ni-Cu-P的工艺及性能研究
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摘要
本文研究了在铝硅合金表面化学沉积Ni-P和Ni-Cu-P合金镀层的工艺和性能。通过XRD、SEM、DSC、IM6电化学工作站等手段对两种合金镀层的组织结构、成分和性能进行了研究，并对铝硅合金表面化学沉积镍的机理作了初步的探讨，讨论了铜元素对镀层性能的作用和影响。主要的实验内容和结果包括：
(1)本文采用一次浸镍的预处理方法，在铝硅合金表面上化学沉积致密、均匀的Ni-P、Ni-Cu-P合金镀层，采用调节化学沉积Ni-P、Ni-Cu-P合金镀液成分和环境条件对合金镀液的工艺进行了研究，优选出最佳的工艺参数，并研究了各因素对化学沉积Ni-P、Ni-Cu-P合金镀层结构的影响和合金镀层的性能。
(2)利用XRD、SEM、DSC等手段对Ni-P、Ni-Cu-P合金镀层的结构、表面形貌、成分进行了分析。XRD结果表明Ni-P、Ni-Cu-P合金镀层均为非晶态结构，从表面形貌可以看出Ni-Cu-P合金镀层中的铜元素有细化晶粒的作用。DSC分析结果表明，化学沉积Ni-P合金镀层的晶化温度低于化学沉积Ni-Cu-P合金镀层的晶化温度。
(3)采用IM6电化学工作站对化学沉积Ni-P、Ni-Cu-P合金镀层进行耐腐蚀研究，结果表明化学沉积Ni-P合金镀层在酸碱盐中的耐腐蚀电位比化学沉积Ni-Cu-P合金镀层的耐腐蚀电位低，而且化学沉积的Ni-Cu-P合金镀层在酸碱盐中的阳极极化曲线比化学沉积Ni-P合金镀层的阳极极化曲线往正的方向偏移。
(4)利用MVK-H3硬度测试仪测得化学沉积Ni-P、Ni-Cu-P合金镀层随着热处理温度的增高，合金镀层的硬度先增加然后又将低，Ni-Cu-P合金镀层的最大硬度值和Ni-P合金镀层的最大硬度相差不多。
(5)通过采用红点法对化学沉积Ni-P、Ni-Cu-P合金镀层的孔隙率进行测试得出，Ni-P合金镀层的孔隙率比Ni-Cu-P合金镀层的孔隙率低。
In this paper, the electrodeposition technology of the Ni-P and Ni-Cu-P alloy coatings on the aluminum and silicon alloy substrate were studied. By means of XRD. SEM, DSC, IM6 electrochemistry workstation etc.. The morphology, structure, content and performances of the Ni-P and Ni-Cu-P alloy coating were analyzed. The deposition mechanism of electroless nickel on aluminum and silicon alloy was discussed tentatively and argued on copper by the action and influence of the coating performance. The main content of the experiments and the results included:
(1) By one dip nickel pretreatment, a compact and evengranular Ni-P and Ni-Cu-P alloy coating were deposited on the aluminum and silicon alloy substrate. By changing the content and condition of electroless bath, the technology and coating performance were studied. The optimal electroplating conditions and the influence of technology parameters were acquired.
(2) The analysis results of XRD indicated that the Ni-P and Ni-Cu-P alloy coatings were amorphous structure. The surface shape indicated that the copper could diminish the crystal. The DSC results made know that the crystal temperature of the Ni-P alloy coating was lower than the Ni-Cu-P alloy coating's.
(3) The results showed that the erode voltage of the Ni-P alloy coatings was lower than the Ni-Cu-P alloy coatings' by IM6 electrochemistry station in acid and alkali and salt solutions. At the same time, anodic polarization curves of Ni-Cu-P alloy coatings shifted to the positive direction relative to the Ni-P alloy coatings' in acid and alkali and salt solutions.
(4) By the MVK-H3 hardness instrument, the hardness of the two coatings increased, and then decreased with the heat treatment temperatures. And the maximal hardness of Ni-Cu-P the alloy coating was the same to the Ni-P alloy coating's.
(5) The testing results indicated that the hole rate of the Ni-P alloy coating was lower than the Ni-P alloy coating by hongdian means.
(1)本文采用一次浸镍的预处理方法，在铝硅合金表面上化学沉积致密、均匀的Ni-P、Ni-Cu-P合金镀层，采用调节化学沉积Ni-P、Ni-Cu-P合金镀液成分和环境条件对合金镀液的工艺进行了研究，优选出最佳的工艺参数，并研究了各因素对化学沉积Ni-P、Ni-Cu-P合金镀层结构的影响和合金镀层的性能。
(2)利用XRD、SEM、DSC等手段对Ni-P、Ni-Cu-P合金镀层的结构、表面形貌、成分进行了分析。XRD结果表明Ni-P、Ni-Cu-P合金镀层均为非晶态结构，从表面形貌可以看出Ni-Cu-P合金镀层中的铜元素有细化晶粒的作用。DSC分析结果表明，化学沉积Ni-P合金镀层的晶化温度低于化学沉积Ni-Cu-P合金镀层的晶化温度。
(3)采用IM6电化学工作站对化学沉积Ni-P、Ni-Cu-P合金镀层进行耐腐蚀研究，结果表明化学沉积Ni-P合金镀层在酸碱盐中的耐腐蚀电位比化学沉积Ni-Cu-P合金镀层的耐腐蚀电位低，而且化学沉积的Ni-Cu-P合金镀层在酸碱盐中的阳极极化曲线比化学沉积Ni-P合金镀层的阳极极化曲线往正的方向偏移。
(4)利用MVK-H3硬度测试仪测得化学沉积Ni-P、Ni-Cu-P合金镀层随着热处理温度的增高，合金镀层的硬度先增加然后又将低，Ni-Cu-P合金镀层的最大硬度值和Ni-P合金镀层的最大硬度相差不多。
(5)通过采用红点法对化学沉积Ni-P、Ni-Cu-P合金镀层的孔隙率进行测试得出，Ni-P合金镀层的孔隙率比Ni-Cu-P合金镀层的孔隙率低。
In this paper, the electrodeposition technology of the Ni-P and Ni-Cu-P alloy coatings on the aluminum and silicon alloy substrate were studied. By means of XRD. SEM, DSC, IM6 electrochemistry workstation etc.. The morphology, structure, content and performances of the Ni-P and Ni-Cu-P alloy coating were analyzed. The deposition mechanism of electroless nickel on aluminum and silicon alloy was discussed tentatively and argued on copper by the action and influence of the coating performance. The main content of the experiments and the results included:
(1) By one dip nickel pretreatment, a compact and evengranular Ni-P and Ni-Cu-P alloy coating were deposited on the aluminum and silicon alloy substrate. By changing the content and condition of electroless bath, the technology and coating performance were studied. The optimal electroplating conditions and the influence of technology parameters were acquired.
(2) The analysis results of XRD indicated that the Ni-P and Ni-Cu-P alloy coatings were amorphous structure. The surface shape indicated that the copper could diminish the crystal. The DSC results made know that the crystal temperature of the Ni-P alloy coating was lower than the Ni-Cu-P alloy coating's.
(3) The results showed that the erode voltage of the Ni-P alloy coatings was lower than the Ni-Cu-P alloy coatings' by IM6 electrochemistry station in acid and alkali and salt solutions. At the same time, anodic polarization curves of Ni-Cu-P alloy coatings shifted to the positive direction relative to the Ni-P alloy coatings' in acid and alkali and salt solutions.
(4) By the MVK-H3 hardness instrument, the hardness of the two coatings increased, and then decreased with the heat treatment temperatures. And the maximal hardness of Ni-Cu-P the alloy coating was the same to the Ni-P alloy coating's.
(5) The testing results indicated that the hole rate of the Ni-P alloy coating was lower than the Ni-P alloy coating by hongdian means.
引文
1 姜晓霞，沈伟。化学镀理论及实践。[M]北京：国防工业出版社，2000，1～2
2 Werz.A.,Hebel.C.R.Seances.Acad.Sci. 1989.18(44):702-705; 1992.21(45): 149～151
3 Brenner A. and Ridell G.E.J.Res.Nat.Bur.Stand.1946.37.11～18
4 F. Pearlstein, R, F. Weightman and R.Wick,Met.Fin.,61(11),77(1963)
5 F.Pearlstein,R,F.Weightman,Electrochem.technol.,6,427(1968)
6 庄瑞舫．化学镀镍磷合金技术探讨(1)．材料保护．1997．30(9)：41～48
7 T. Osaka, H. Sawai, and N.Kasai,ibid.,32,615(1981)
8 T. Osaka, H. Sawai, and N.Kasai,ibid.,34,600(1983)
9 田上道弘，后腾正治。轻金属。1993．43(3)：281～285
10 J.Plis,D.J.Duqette.Crossion. 1985.41(12): 700～703
11 R.N. Duncan. Plating & Surface Finishing.1986.73(7):52～56
12 蒋大祥，吴辉煌．化学镀镍磷合金在浓NaOH溶液中的电化学腐蚀行为．应用化学．1996．16(3)：21-22
13 俞宏英，孙冬柏．基体的表面条件与镍磷合金镀层的耐蚀性．材料保护．1995．28(1)：9-10
14 刘定福．化学镀镍磷合金耐蚀性的影响因素．电镀环保．1999．19(2)：15-17
15 Lindsay J H. Electroless plating fundamentals and applications. Plating & Surface Finishing, 1993, 80(6): 22～23
16 Bayes M W. Electroless nickel in the'90s. Metal Finishing, 1990, 88(4): 27～29
17 Mandich N V, Krulik G A. A novel biogenic nickel source for electroless nickel plating. Metal Finishing, 1992, 90(3): 9～10
18 Cherkaoui M, Srhiri A, Chassaing E. Electroless deposition of Ni-Cu-P alloys. Plating & Surface Finishing, 1992, 79(11): 68～71
19 Nawafune H, Uegaki T, Mizumoto S, et al. Preparation and electrical resistance characteristics of electroless copper-nickel alloy deposits. Transactions of the Institute of Metal Finishing, 1998, 76(6): 231～234
20 Iwamatsu K. Electroless nickel polyalloy deposits. Metal Finishing, 1989, 87(5): 25～27
21 Wang Y W, Xiao C G, Deng Z G. Structure and corrosion resistance of electoless Ni-Cu-P. Plating & Surface Finishing, 1992, 79(3): 57～59
22 Lee S L, Liang H H. Structures and corrosion characteristics of electroless Ni-Mo-P alloy deposits. Plating & Surface Finishing, 1991, 78(2): 82～86
23 Lee S L, Liang H H. The structure and hardness of electroless Ni-Mo-P alloy deposits. Plating & Surface Finishing, 1992, 79(2): 56～59
24 税毅．Ni-P镀层研究现状及发展趋势．表面技术，2002，31(1)：1～3
25 李宁，袁国伟，黎德育．化学镀镍基合金理论与技术．哈尔滨：哈尔滨工业大学出版社，2000
26 董允，张廷森，林晓婢．现代表面技术．北京：机械工业出版社，2000
27 K H Hur, J H Jeong, D N Lee. Effect of Annealing on Magnetic Properties, Microstructure of Electroless Nickel-Copper-Phosphorus Alloy Deposits[J]. J Mater Sci, 1991, 26: 2037-2044
28 N Krasteva, V Fotty, S Armyanov, Thermal Stability of Ni-P and Ni-Cu-P Amorphous Alloys[J]. J Electrochem Soc, 1994, 141(10): 2864-2867
29 Hidemi Nawafune, Takashi Uegaki,et al. Preparation and Electrical Resistance Charateristics of Electroless Copper-Nickel Alloy deposits[J]. Trans. IMF, 1998, 76(6): 231-234
30 Y W Wang, C G Xiao, Z G Deng. Structure and Corrosion Resistance of Electroless Ni-Cu-P[J]. Plat Surf Finish,1992,79:57-59
31 G O Mallory, J B Ilajdu. Electroless Plating Fundermentals, Applications, Chap.1 [M]. Orlando, FL: AESF, 1990
32 G G Gawrilov. Chemical(Electroless)Nickel-Plating, Chap.6 and 7[M]. Great Britain: Portcullis Press Ltd, 1979
33 崔振铎．化学镀Ni-Cu-P工艺．材料保护，1998，(1)：15
34 Yang E, Doss S K, Peterson P. Electroless Ni-Cu-P alloy in an atmospheric gas chamber. Plating and Surface Finishing. 1998, 75(12): 74～75
35 Cherkaoui M, Srhiri A, Chassaing E. Electroless deposition of Ni-Cu-P alloy. Plating & Surface Finishing. 1992, 79(11): 67～70
36 董家梅，万德立等．钢铁件化学镀Ni-Cu-P合金工艺镀层性能．材料保护，2000，33(8)：16
37 叶栩青，罗守富，王永瑞．化学镀Ni-Cu-P合金工艺研究．腐蚀与防护，2000，21(3)：125～126
38 伍学高，李铭华．化学镀技术．成都：四川科技出版社，1983
39 李宁，屠振密．化学镀实用技术．北京：化学工业出版社，2004
40 Mallory G O, Hajdu J B. Electroless plating, American Electroplates and Surface Finishers Society, 1990
41 Alturd D. Electrochemical evaluation of electroless nickelplating, Proc 11th World Congress on Metal Finishing, Intertinish 84, Jernsalera, Israel, 1984
42 Takayuki Homma, Isao Komatsu, Amiko Tamaki, Hiromi Nakai. Molecular orbital study on the reaction mechanisms of electroless deposition processes. Electrochemical Acta, 2001, 47: 47～53bv
43 Laser, L.: Paper presented at Fachseminar Praxis-Forum, 1986.17-18
44 Goktepe M. and W. Riedel: Galvanotechnik,80(1989).2283-2287
45 Gammel, F. J., O. Tuscher and R. Suchentrunk: Galvanotechnik,75(1984).98-103 and 155-159
46 Miroyuki Satoh. Anodizing of Aluminum By Micro-Exploxive Air Agitation. Plating and finishing. 1990, 77(12): 76-81
47 Gawrilov G. G. Chemische(stromlose)Vemiskelung. Eugen G. Leuxe Verlag. Saulgau. 1974. 214-228
48 Doss S. K., Michaelsen J.D.Electroless Nickel Conference Ⅱ. 1982. 99—101
49 Gawrilov G. G., Chemical[Electroless]Nickel Plating Portcullis Press, Redhill, VK, 1997
50 Doss S. K. and J. D. Michaelsen: Paper Presented at Electroless Nickel Conference Ⅱ. 1998
51 T.H. James, J. Phys. chem 66(1962): 2416
52 Gutzeit G. Plating, 1959. 46. 1158—1164
53 Muller. K. Metalloberflache. 1960. 14. 65—102
54 何换杰，王永红．ZY—01高磷耐蚀化学镀镍工艺研究．电镀与环保．1998．18(1)．21—22
55 Wang Y. H., He H.J.ZY—01 high phosphorus content electroless nickel plating process. Electroplat & Finish. 1997.16(4).24-28
56 Kalantary M. R., Holbrook K.A. Plating & Surface Finishing.1992.55-81
57 Laser, L.: Paper presented at Fachseminar Praxis-Forum, 1986.17-18
58 Goktepe M. and W. Riedel: Galvanotechnik, 80(1989). 2283-2287
59 Gammel, F. J.,O. Tuscher and R. Suchentrunk: Galvanotechnik,75(1984).98-103 and 155-159
60 D. A. Jones. Principles and Prevention of Corrotion,Chap.2[M].New York: Macmillan Publishing Company, 1992
61 李宁，屠振密。化学镀实用技术。[M]北京：化学工业出版社，2003．366-370
62 姜晓霞，沈伟。化学镀理论及实践。[M]北京：国防工业出版社，2000。68-73，58-59
2 Werz.A.,Hebel.C.R.Seances.Acad.Sci. 1989.18(44):702-705; 1992.21(45): 149～151
3 Brenner A. and Ridell G.E.J.Res.Nat.Bur.Stand.1946.37.11～18
4 F. Pearlstein, R, F. Weightman and R.Wick,Met.Fin.,61(11),77(1963)
5 F.Pearlstein,R,F.Weightman,Electrochem.technol.,6,427(1968)
6 庄瑞舫．化学镀镍磷合金技术探讨(1)．材料保护．1997．30(9)：41～48
7 T. Osaka, H. Sawai, and N.Kasai,ibid.,32,615(1981)
8 T. Osaka, H. Sawai, and N.Kasai,ibid.,34,600(1983)
9 田上道弘，后腾正治。轻金属。1993．43(3)：281～285
10 J.Plis,D.J.Duqette.Crossion. 1985.41(12): 700～703
11 R.N. Duncan. Plating & Surface Finishing.1986.73(7):52～56
12 蒋大祥，吴辉煌．化学镀镍磷合金在浓NaOH溶液中的电化学腐蚀行为．应用化学．1996．16(3)：21-22
13 俞宏英，孙冬柏．基体的表面条件与镍磷合金镀层的耐蚀性．材料保护．1995．28(1)：9-10
14 刘定福．化学镀镍磷合金耐蚀性的影响因素．电镀环保．1999．19(2)：15-17
15 Lindsay J H. Electroless plating fundamentals and applications. Plating & Surface Finishing, 1993, 80(6): 22～23
16 Bayes M W. Electroless nickel in the'90s. Metal Finishing, 1990, 88(4): 27～29
17 Mandich N V, Krulik G A. A novel biogenic nickel source for electroless nickel plating. Metal Finishing, 1992, 90(3): 9～10
18 Cherkaoui M, Srhiri A, Chassaing E. Electroless deposition of Ni-Cu-P alloys. Plating & Surface Finishing, 1992, 79(11): 68～71
19 Nawafune H, Uegaki T, Mizumoto S, et al. Preparation and electrical resistance characteristics of electroless copper-nickel alloy deposits. Transactions of the Institute of Metal Finishing, 1998, 76(6): 231～234
20 Iwamatsu K. Electroless nickel polyalloy deposits. Metal Finishing, 1989, 87(5): 25～27
21 Wang Y W, Xiao C G, Deng Z G. Structure and corrosion resistance of electoless Ni-Cu-P. Plating & Surface Finishing, 1992, 79(3): 57～59
22 Lee S L, Liang H H. Structures and corrosion characteristics of electroless Ni-Mo-P alloy deposits. Plating & Surface Finishing, 1991, 78(2): 82～86
23 Lee S L, Liang H H. The structure and hardness of electroless Ni-Mo-P alloy deposits. Plating & Surface Finishing, 1992, 79(2): 56～59
24 税毅．Ni-P镀层研究现状及发展趋势．表面技术，2002，31(1)：1～3
25 李宁，袁国伟，黎德育．化学镀镍基合金理论与技术．哈尔滨：哈尔滨工业大学出版社，2000
26 董允，张廷森，林晓婢．现代表面技术．北京：机械工业出版社，2000
27 K H Hur, J H Jeong, D N Lee. Effect of Annealing on Magnetic Properties, Microstructure of Electroless Nickel-Copper-Phosphorus Alloy Deposits[J]. J Mater Sci, 1991, 26: 2037-2044
28 N Krasteva, V Fotty, S Armyanov, Thermal Stability of Ni-P and Ni-Cu-P Amorphous Alloys[J]. J Electrochem Soc, 1994, 141(10): 2864-2867
29 Hidemi Nawafune, Takashi Uegaki,et al. Preparation and Electrical Resistance Charateristics of Electroless Copper-Nickel Alloy deposits[J]. Trans. IMF, 1998, 76(6): 231-234
30 Y W Wang, C G Xiao, Z G Deng. Structure and Corrosion Resistance of Electroless Ni-Cu-P[J]. Plat Surf Finish,1992,79:57-59
31 G O Mallory, J B Ilajdu. Electroless Plating Fundermentals, Applications, Chap.1 [M]. Orlando, FL: AESF, 1990
32 G G Gawrilov. Chemical(Electroless)Nickel-Plating, Chap.6 and 7[M]. Great Britain: Portcullis Press Ltd, 1979
33 崔振铎．化学镀Ni-Cu-P工艺．材料保护，1998，(1)：15
34 Yang E, Doss S K, Peterson P. Electroless Ni-Cu-P alloy in an atmospheric gas chamber. Plating and Surface Finishing. 1998, 75(12): 74～75
35 Cherkaoui M, Srhiri A, Chassaing E. Electroless deposition of Ni-Cu-P alloy. Plating & Surface Finishing. 1992, 79(11): 67～70
36 董家梅，万德立等．钢铁件化学镀Ni-Cu-P合金工艺镀层性能．材料保护，2000，33(8)：16
37 叶栩青，罗守富，王永瑞．化学镀Ni-Cu-P合金工艺研究．腐蚀与防护，2000，21(3)：125～126
38 伍学高，李铭华．化学镀技术．成都：四川科技出版社，1983
39 李宁，屠振密．化学镀实用技术．北京：化学工业出版社，2004
40 Mallory G O, Hajdu J B. Electroless plating, American Electroplates and Surface Finishers Society, 1990
41 Alturd D. Electrochemical evaluation of electroless nickelplating, Proc 11th World Congress on Metal Finishing, Intertinish 84, Jernsalera, Israel, 1984
42 Takayuki Homma, Isao Komatsu, Amiko Tamaki, Hiromi Nakai. Molecular orbital study on the reaction mechanisms of electroless deposition processes. Electrochemical Acta, 2001, 47: 47～53bv
43 Laser, L.: Paper presented at Fachseminar Praxis-Forum, 1986.17-18
44 Goktepe M. and W. Riedel: Galvanotechnik,80(1989).2283-2287
45 Gammel, F. J., O. Tuscher and R. Suchentrunk: Galvanotechnik,75(1984).98-103 and 155-159
46 Miroyuki Satoh. Anodizing of Aluminum By Micro-Exploxive Air Agitation. Plating and finishing. 1990, 77(12): 76-81
47 Gawrilov G. G. Chemische(stromlose)Vemiskelung. Eugen G. Leuxe Verlag. Saulgau. 1974. 214-228
48 Doss S. K., Michaelsen J.D.Electroless Nickel Conference Ⅱ. 1982. 99—101
49 Gawrilov G. G., Chemical[Electroless]Nickel Plating Portcullis Press, Redhill, VK, 1997
50 Doss S. K. and J. D. Michaelsen: Paper Presented at Electroless Nickel Conference Ⅱ. 1998
51 T.H. James, J. Phys. chem 66(1962): 2416
52 Gutzeit G. Plating, 1959. 46. 1158—1164
53 Muller. K. Metalloberflache. 1960. 14. 65—102
54 何换杰，王永红．ZY—01高磷耐蚀化学镀镍工艺研究．电镀与环保．1998．18(1)．21—22
55 Wang Y. H., He H.J.ZY—01 high phosphorus content electroless nickel plating process. Electroplat & Finish. 1997.16(4).24-28
56 Kalantary M. R., Holbrook K.A. Plating & Surface Finishing.1992.55-81
57 Laser, L.: Paper presented at Fachseminar Praxis-Forum, 1986.17-18
58 Goktepe M. and W. Riedel: Galvanotechnik, 80(1989). 2283-2287
59 Gammel, F. J.,O. Tuscher and R. Suchentrunk: Galvanotechnik,75(1984).98-103 and 155-159
60 D. A. Jones. Principles and Prevention of Corrotion,Chap.2[M].New York: Macmillan Publishing Company, 1992
61 李宁，屠振密。化学镀实用技术。[M]北京：化学工业出版社，2003．366-370
62 姜晓霞，沈伟。化学镀理论及实践。[M]北京：国防工业出版社，2000。68-73，58-59