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中国腐蚀与防护学报  2014, Vol. 34 Issue (6): 523-531    DOI: 10.11092/1005.4537.2013.144
  本期目录 | 过刊浏览 |
组分调制Cu/Ni多层膜的合金化及其合金化镀层的耐蚀特性
骆立立, 费敬银(), 王磊, 林西华, 王少兰
西北工业大学理学院 西安 710129
Alloying of Compositionally Modulated Cu/Ni Multilayer Films and Corrosion Performance of Cu-Ni Alloy Coatings
LUO Lili, FEI Jingyin(), WANG Lei, LIN Xihua, WANG Shaolan
Faculty of Science,Northwestern Polytechnical University, Xi'an 710129, China
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摘要: 

采用双槽电沉积方法制备出了Cu/Ni多层膜。探讨了调制波长、热处理条件等对Cu/Ni多层膜合金化行为影响的规律,并借助于SEM和XRD等对Cu/Ni多层膜及其合金化镀层的结构与组成进行了分析表征。结果表明,利用Cu/Ni多层膜合金化方法可以制备出组织均一、成分均匀的Cu-Ni合金镀层,且多层膜调制波长的减小、热处理时间的延长及保温温度的升高均有利于Cu/Ni多层膜的合金化。此外,利用电化学综合测试技术对合金镀层的耐蚀行为进行了评估。结果表明,合金化后的Cu-Ni合金镀层比相应条件下的纯Cu镀层、Ni镀层具有更正的自腐蚀电位、更低的极化电流密度以及更小的腐蚀速率。
关键词 ： Cu/Ni多层膜,  合金化,  电沉积,  耐蚀性    
Abstract：

Cu/Ni multilayered films were prepared by a two step electrodeposition method. The influence of the modulation wavelength and heat treatment condition on the alloying of Cu/Ni multilayered films were studied by means of SEM and XRD. The results showed that the Cu-Ni alloy coatings with well homogeneity in microstructure and composition can be prepared by the alloying of Cu/Ni multilayered films; the alloying process would be favored with the decreasing modulation wavelength as well as the increasing temperature and time of heat-treatment. Besides, the corrosion performance of coatings of copper, nickel and Cu-Ni alloy were comparatively evaluated by immersion test in NaCl solution. The results showed that the Cu-Ni alloy coatings exhibited much positive corrosion potential, smaller polarized current density and lower corrosion rate rather than the pure copper and nickel coatings.
Key words： Cu/Ni multilayer film    the alloying    electrodeposition    corrosion resistance
    
ZTFLH:  TQ153  
作者简介: null

骆立立，男，1989年生，硕士生，研究方向为金属基组分调制多层膜的性能
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骆立立
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引用本文:

骆立立, 费敬银, 王磊, 林西华, 王少兰. 组分调制Cu/Ni多层膜的合金化及其合金化镀层的耐蚀特性[J]. 中国腐蚀与防护学报, 2014, 34(6): 523-531.
Lili LUO, Jingyin FEI, Lei WANG, Xihua LIN, Shaolan WANG. Alloying of Compositionally Modulated Cu/Ni Multilayer Films and Corrosion Performance of Cu-Ni Alloy Coatings. Journal of Chinese Society for Corrosion and protection, 2014, 34(6): 523-531.

链接本文:

https://www.jcscp.org/CN/10.11092/1005.4537.2013.144      或      https://www.jcscp.org/CN/Y2014/V34/I6/523

Composition and operating condition Copper bath Nickel bath
CuSO45 H2O, gL-1 90 ---
NiSO46 H2O, gL-1 --- 250
H2SO4 (98%), mgL-1 200 ---
Tri-ammonium citrate, gL-1 --- 50
Ammonia solution (25%~28%), mLL-1 --- 110
T, ℃ 20~30 55~65
Ic, mAcm-2 10 10
Agitation Magnetic stirrer Magnetic stirrer
Anode Copper Platinised titanium mesh
表1  镀铜液和镀镍液的组分及工艺参数
图1  不同调制波长的Cu/Ni多层膜的表面形貌
图2  不同调制波长的Cu/Ni多层膜的截面形貌
Influencing
factor 		Level
1 2 3 4
A: λ / μm 1 2 4 ---
B: Temperature / ℃ 300 500 700 900
C: Time / h 1 3 8 ---
表2  影响热处理的因子及因子水平
图3  表头设计
Column Influencing factor and level Slope of
number A: λ / μm B: Time / h C: Temperature / ℃ line
1 1 3 300 5.44
2 1 1 500 4.06
3 1 1 700 2.02
4 1 3 900 0.46
5 1 1 300 7.15
6 1 8 500 2.10
7 1 8 700 1.72
8 1 1 900 1.68
9 2 1 300 8.25
10 2 3 500 4.05
11 2 3 700 2.47
12 2 1 900 2.42
13 4 8 300 10.49
14 4 3 500 8.93
15 4 3 700 2.72
16 4 8 900 0.90
表3  正交实验内容及结果
图4  不同调制波长的Cu/Ni多层膜在700 ℃下热处理3 h后的截面形貌
图5  调制波长对Cu/Ni多层膜合金化的影响趋势
图6  调制波长为2 μm的Cu/Ni多层膜在不同温度下热处理3 h后的断面形貌
图7  保温温度对Cu/Ni多层膜合金化的影响趋势
图8  调制波长为2 μm的Cu/Ni多层膜在700 ℃下经不同时间热处理后的断面形貌
图9  热处理时间对Cu/Ni多层膜合金化的影响趋势
Sources of
variance 		Sum of square of deviations Degrees of
freedom 		Average
squares 		F Statistical
significance
A SA= 8.75 2 4.38 0.86 non-significance
B SB= 1.60 2 0.80 0.16 non-significance
C SC= 85.05 3 28.35 5.56 *
E SE= 35.67 7 5.10 --- ---
表4  方差分析
图10  合金化Cu-Ni多层膜的表面形貌和断面形貌
图11  Cu/Ni多层膜合金化前后的XRD谱
No. Coating
system 		pH (3.5%
NaCl) 		Ecorr (vs SCE)
mV
1 Cu 3 -204.2
2 Ni 3 -256.2
3 Alloyed Cu-Ni CMMF 3 -190.8
4 Cu 7 -195.1
5 Ni 7 -188.8
6 Alloyed Cu-Ni CMMF 7 -189.8
7 Cu 11 -130.2
8 Ni 11 -249.0
9 Alloyed Cu-Ni CMMF 11 -108.3
表5  不同镀层的自腐蚀电位
图12  Cu镀层在不同pH值3.5%NaCl溶液中的极化曲线
图13  Ni镀层在不同pH值3.5%NaCl溶液中的极化曲线
图14  Cu-Ni合金镀层在不同pH值3.5%NaCl溶液中的的极化曲线
No. Coating
system 		pH (3.5%
NaCl) 		Corrosion
rate / mma-1
1 Cu 3 0.2416
2 Ni 3 0.3359
3 Alloyed Cu-Ni CMMF 3 0.1782
4 Cu 7 0.0835
5 Ni 7 0.0434
6 Alloyed Cu-Ni CMMF 7 0.0410
7 Cu 11 0.0112
8 Ni 11 0.0165
9 Alloyed Cu-Ni CMMF 11 0.0019
表6  不同镀层的腐蚀速率
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