脉冲电镀镍及其性能的研究
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摘要
镍具有较高的硬度和耐蚀性,在机械、化工、医药及微电子等领域得到广泛应用。为满足科技发展对材料许多特殊性能的要求,复合镀、脉冲电镀镍等得到广泛的研究。与直流电镀相比单脉冲电镀和双脉冲电镀可以细化晶粒,致密镀层,减少孔隙率,从而改善镀层的外观和材料表面的功能,增强抗蚀性。
本文以瓦特镍镀液为基础,加入添加剂A(5g/L)、添加剂B(0.2g/L)、pH值2.5-3.0和施镀温度50±2℃。分别采用双脉冲电镀、单脉冲电镀和直流电镀工艺制备镍镀层,并探讨了工艺参数对镀层性能的影响；利用电化学方法研究三种工艺条件下所得镍镀层在3.5%NaCl、1mol/L HCl及1mol/L H_2SO_4溶液中的腐蚀行为；运用扫描电子显微镜和X射线衍射仪对所获得镀镍层的表面形貌和微观结构进行研究。
结果表明,脉冲参数对镀层在腐蚀介质中的耐蚀性能影响较大,在3.5%NaCl、1mol/L HCl和1mol/L H_2SO_4三种腐蚀介质中,单脉冲和双脉冲电沉积镍镀层的自腐蚀电流小,电阻大,耐蚀性能优于直流电沉积镍镀层。与直流电镀相比,单脉冲条件下和双脉冲条件下得到的镍镀层晶体颗粒更加细小,致密,镀层光亮性更好。三者均为立方面心结构,但晶体生长的择优取向各不相同,直流镀层在(222)晶面存在择优取向,单脉冲条件下和双脉冲条件下得到的镍镀层在(111)晶面存在择优取向。最佳的单脉冲电镀的电镀工艺为：脉冲电镀条件为平均电流密度为0.75 A/dm2,占空比为5%,温度为45℃～50℃,pH值2.5-3.0。双脉冲电镀工艺条件为：正向导通时间为10ms、正向关段时间为90ms、正向工作时间为400ms、正向平均电流密度为0.7A/dm2、反向导通时间为2ms、反向关断时间为7ms、反向工作时间5ms、反向平均电流密度为0.04A/dm2。
Nickel has the high degree of hardness and the corrosion resistance, which in domains machinery, chemical industry, pharmaceutical industry, micro-electron and so on obtains the wide-spread application. In order to satisfy the technological progress to the material many special performance's requests, the compound plates and the pulse nickel coating has obtained the extensive research. Compared with DC electro-deposition, the monopulse electro-deposition and the double pulse electro-deposition can get the refined grain, compact coating, reduces the hole, which compares with the direct current electro-deposition, thus improves coating outward appearance and material surface function and enhances corrosion resistance.
In this paper, based on Watts nickel plating bath add additive A (5g/L),additive B (0.2g/L), pH2.5～3.0 and the plating temperature 50±2℃. Respectively use double-pulse plating, monopulse plating and DC plating process for preparation of nickel plating, and explores the process parameters on coating properties.Corrosion resistance of Ni plating in 1mol/L HCl is discussed through electrochemical polarization. The corrosion behavior of the Nickel plating, obtained by these three kinds of processing, in 3.5% NaCl, 1mol/L HCl and 1mol/L H2SO4 solution was analyzed by electrochemical mathods, the surface morphology and microstructure of nickel plating was investigated by scanning electron microscopy (SEM) and X-ray diffraction.
The results showed that the effect of monopulse parameters on corrosion resistanceof deposit is great.3.5% NaCl, 1mol/L HCl and 1mol/L H_2SO_4 three kinds of corrosive media, monopulse and double pulse electro-deposition has smaller self corrosion current, large resistance. Compared with DC Nickel Coating; the monopulse and double pulse electro-deposited nickel coating are denser. Though they are all face-centered cubic structures, the growth's crystal orientation is various. The direct current electro-deposition nickel coating has growth's crystal orientation (200), while nomopulseelectro-deposition nickel coating and double pulse electro-deposition nickel coating has growth's crystal orientation (111). Nickel coating obtained by single-pulse and double pulse electro-deposition, compared with that obtained by the DC plating has good corrosion resistance, even a small crystal particles, lower porosity, more brightness.
The optimal conditions for pulse plating process is that average current density is 0.75 A/dm~2, pulse duty cycle is 5%, temperature is 45～50℃, pH is 2.5～3.0. The best conditions for double pulse plating process by orthogonal experiments is forward working-time is 10ms, forward closing-time is 90ms, forward working-time is 400ms; forward current density is 2A/dm~2; reverse working-time is 2ms; reverse closing-time is 7ms; reverse working-time is 5ms; reverse current density is 0.04 A/dm2.
本文以瓦特镍镀液为基础,加入添加剂A(5g/L)、添加剂B(0.2g/L)、pH值2.5-3.0和施镀温度50±2℃。分别采用双脉冲电镀、单脉冲电镀和直流电镀工艺制备镍镀层,并探讨了工艺参数对镀层性能的影响；利用电化学方法研究三种工艺条件下所得镍镀层在3.5%NaCl、1mol/L HCl及1mol/L H_2SO_4溶液中的腐蚀行为；运用扫描电子显微镜和X射线衍射仪对所获得镀镍层的表面形貌和微观结构进行研究。
结果表明,脉冲参数对镀层在腐蚀介质中的耐蚀性能影响较大,在3.5%NaCl、1mol/L HCl和1mol/L H_2SO_4三种腐蚀介质中,单脉冲和双脉冲电沉积镍镀层的自腐蚀电流小,电阻大,耐蚀性能优于直流电沉积镍镀层。与直流电镀相比,单脉冲条件下和双脉冲条件下得到的镍镀层晶体颗粒更加细小,致密,镀层光亮性更好。三者均为立方面心结构,但晶体生长的择优取向各不相同,直流镀层在(222)晶面存在择优取向,单脉冲条件下和双脉冲条件下得到的镍镀层在(111)晶面存在择优取向。最佳的单脉冲电镀的电镀工艺为：脉冲电镀条件为平均电流密度为0.75 A/dm2,占空比为5%,温度为45℃～50℃,pH值2.5-3.0。双脉冲电镀工艺条件为：正向导通时间为10ms、正向关段时间为90ms、正向工作时间为400ms、正向平均电流密度为0.7A/dm2、反向导通时间为2ms、反向关断时间为7ms、反向工作时间5ms、反向平均电流密度为0.04A/dm2。
Nickel has the high degree of hardness and the corrosion resistance, which in domains machinery, chemical industry, pharmaceutical industry, micro-electron and so on obtains the wide-spread application. In order to satisfy the technological progress to the material many special performance's requests, the compound plates and the pulse nickel coating has obtained the extensive research. Compared with DC electro-deposition, the monopulse electro-deposition and the double pulse electro-deposition can get the refined grain, compact coating, reduces the hole, which compares with the direct current electro-deposition, thus improves coating outward appearance and material surface function and enhances corrosion resistance.
In this paper, based on Watts nickel plating bath add additive A (5g/L),additive B (0.2g/L), pH2.5～3.0 and the plating temperature 50±2℃. Respectively use double-pulse plating, monopulse plating and DC plating process for preparation of nickel plating, and explores the process parameters on coating properties.Corrosion resistance of Ni plating in 1mol/L HCl is discussed through electrochemical polarization. The corrosion behavior of the Nickel plating, obtained by these three kinds of processing, in 3.5% NaCl, 1mol/L HCl and 1mol/L H2SO4 solution was analyzed by electrochemical mathods, the surface morphology and microstructure of nickel plating was investigated by scanning electron microscopy (SEM) and X-ray diffraction.
The results showed that the effect of monopulse parameters on corrosion resistanceof deposit is great.3.5% NaCl, 1mol/L HCl and 1mol/L H_2SO_4 three kinds of corrosive media, monopulse and double pulse electro-deposition has smaller self corrosion current, large resistance. Compared with DC Nickel Coating; the monopulse and double pulse electro-deposited nickel coating are denser. Though they are all face-centered cubic structures, the growth's crystal orientation is various. The direct current electro-deposition nickel coating has growth's crystal orientation (200), while nomopulseelectro-deposition nickel coating and double pulse electro-deposition nickel coating has growth's crystal orientation (111). Nickel coating obtained by single-pulse and double pulse electro-deposition, compared with that obtained by the DC plating has good corrosion resistance, even a small crystal particles, lower porosity, more brightness.
The optimal conditions for pulse plating process is that average current density is 0.75 A/dm~2, pulse duty cycle is 5%, temperature is 45～50℃, pH is 2.5～3.0. The best conditions for double pulse plating process by orthogonal experiments is forward working-time is 10ms, forward closing-time is 90ms, forward working-time is 400ms; forward current density is 2A/dm~2; reverse working-time is 2ms; reverse closing-time is 7ms; reverse working-time is 5ms; reverse current density is 0.04 A/dm2.
引文
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[6]王鸿建.电镀工艺学.哈尔滨：哈尔滨工业大学出版社,1995.
[7]Nisit Tantavichet, Mark D. Pritzker.Low and High-Frequency Pulse Current and Pulse Reverse Plating of Copper. Journal of The Electrochemical Society,2003,150(10):665-677.
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[10]张景双,翟淑芳,屠振密.脉冲镀金层耐磨性能的研究.电镀与环保,2002,22(3)：5-7.
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[12]黄萍,张静.印制电路组件三防涂覆工艺研究.电子电工技术,2007,28(6)：324-326.
[13]范宏义.微电化学中反向脉冲电镀镍和镍合金.材料保护,2002,35(8)：65-65.
[14]邢丕峰,赵鹏骥.316不锈钢滤板上钯银合金的脉冲电镀.高技术通讯,1997,62(5)：51-54
[15]DietzM H, Anders A, Kneppe H, et al. Doublepulse technique as an electrochem ical tool for controling the preparation of metallic nanoparticles.Electrochem icaActa.2002,48(4):377-386.
[16]张欢,郭忠诚.脉冲电沉积Ni-W-P合金工艺的研究.材料保护,2004,37(1)：36-43.
[17]郭鹤桐,张三元.复合镀层.天津：天津大学出版社,1991.
[18]白晓军.Ni-PTFE及Ni-(CF)n复合镀层的研究及应用.电镀与环保,1993,13(4)：8-10.
[19]Otero E, Pardo A, Perosanz F J etal. Surface modification of several steels after their exposure at high temperature to oxygen and sulfur mixtures. Surface and CoatingsTechnology,1995,35(6): 76-77.
[20]Electrodeposition of Zn Mn Alloys Using Pulse Plating. Journal of The Electrochemical Society, 2003,150(11):772-776.
[21]Miller B, Ferkel H. Propertiesof nanocrystalline Ni/Al2O3composites.ZMetallkd,1999,11(90): 868-869.
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