晶粒度与介质中Cl-浓度对铜表面钝化膜的影响
Effects of Grain Size and Concentration of Cl- in Solution on Properties of Passive Film on Cu
摘 要
采用电化学方法以及Mott-schottky理论, 研究了两种不同晶粒大小的铜在不同Cl-浓度溶液中的钝化膜形成过程和机理, 计算了不同Cl-浓度溶液中铜在0.2 V、0.4 V两种电位下阳极氧化后钝化膜中的载流子密度。结果表明: 铜在不同条件下表面氧化膜的Mott-schottky曲线线性斜率为负, 呈现P型半导体的性质, 膜中的多数载流子为空穴。随着铜晶粒度的增大和阳极钝化电位的升高, 铜表面钝化膜中的受主密度NA降低; 随着介质溶液中的Cl-浓度的升高, 钝化膜中的受主密度NA不断增大。
晶粒度
Cl-
钝化膜
Mott-Schottky 分析
Cu
grian size
Cl-
passive film
Mott-Schottky analysis
Abstract
The formation process and mechanism of passive film on Cu with two different grain sizes in solutions with different Cl- concentrations were studied by electrochemical methods and Mott-Schottky theory. The carrier density in the passive film formed at two oxidation potentials (0.2 V, 0.4 V) in the solutions with different Cl- concentrations was calculated. The results indicated that under different conditions, the Mott-Schottky plots of the oxide films on the surface of Cu were linear with a negative slop and showed the behavior of P-type semiconductor. The majority carriers in the passive film were holes. With the increase of the grain size of Cu and the increase of anodic passivation potential, the acceptor density (NA) in the passive film formed on the surface of Cu reduced. When the concentration of Cl- in the medium solution increased, the acceptor density (NA) in the passive film increased.
中图分类号 TG174
所属栏目 试验研究
基金项目 国家自然科学基金资助项目(No.50571059, 50615024); 教育部新世纪优秀人才支持计划资助项目(No.NCET-07-0536); 教育部创新团队计划资助项目(No.IRT0739)
收稿日期 2011/9/29
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备注钟庆东,博士生导师,
引用该论文: ZHU Zhen-yu,WANG Yi,ZHONG Qing-dong,WU Hong-yan,DU Hai-long,SHENG Min-qi,ZHOU Qiong-yu. Effects of Grain Size and Concentration of Cl- in Solution on Properties of Passive Film on Cu[J]. Corrosion & Protection, 2012, 33(6): 513
被引情况:
【1】孟新静,周琼宇,钟庆东, "硼酸缓冲溶液pH对黄铜表面钝化膜电化学性能的影响",腐蚀与防护 35, 632-636(2014)
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【3】Khoviv A M,Nazarenko I N,Churikov A A. An ellipsometric study of the oxidation of thin copper films in oxygen[J]. Inorganic Materials,2001,37(5):473-475.
【4】Wang Q J,et al. Semi-conductive properties of passive films formed on copper in chromate solutions. Thin Solid Films[J]. 2009,517:1995-1999.
【5】Liu L,Li Y,Wang F. Influence of grain size on the corrosion behavior of a Ni-based superalloy nanocrystalline coating in NaCl acidic solution[J]. Electrochimica Acta,2008,53(5):2453-2462.
【6】Sikora E,Macdonald D D. Nature of the passive film on nickel[J]. Electrochimica Acta,2002,48(1):69-77.
【7】Ye W,Li Y,Wang F H. Effects of nanocrystallization on the corrosion behavior of 309 stainless steel[J]. Electrochimica Acta,2006,51(21):4426.
【8】Song Y K,Mansfeld F. Corrosion protection of electroga1vanized steel by a cerium-based conversion coating[J]. Corrosion,2006,62(12):1067-1073.
【9】Belo M D C,Hakiki N E,Ferreira M G S. Semiconducting properties of passive films formed on nickel-base alloys type alloy 600:influence of the alloying elements[J]. Electrochimica Acta,1999,44:2473-2481.
【10】Sikora J,Sikora E,Macdonald D D. The electronic structure of the passive film on tungsten[J]. Electrochimica Acta,2000,45(12):1875-1883.
【11】Fredlein R A,Bard A J. Semiconductor electrodesem dash 21. The characterization and behavior of n-type Fe2O3 electrodes in acetonitrile solutions[J]. Journal of the Electrochemical Society,1979,126(6):1892-1991.
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【13】Alves V A,Brett C M A. Characterisation of passive films formed on mild steels in bicarbonate solution by EIS. Electrochimica Acta,2002,47(13/14):2081-2091.
【14】Kang J,Yang Y,Jiang X,et al. Semiconducting properties of passive films formed on electroplated Ni and Ni-Co alloys. Corrosion Science,2008,50(12):3576-3580.
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