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金属学报  2011, Vol. 47 Issue (3): 354-360    DOI: 10.3724/SP.J.1037.2010.00440
  论文 本期目录 | 过刊浏览 |
硼酸缓冲溶液中pH值和Cl-浓度对Cu腐蚀行为的影响
王长罡,  董俊华, 柯伟, 陈楠
中国科学院金属研究所金属腐蚀与防护国家重点实验室, 沈阳 110016
EFFCTS OF pH AND Cl CONCENTRATION ON THE CORROSION BEHAVIOR OF COPPER IN BORIC ACID BUFFER SOLUTION
WANG Changgang, DONG Junhua, KE Wei, CHEN Nan
State Key Laboratory for Corrosion and Protection, Institute of Metal Research, Chinese Academy of Sciences,
Shenyang 110016
引用本文:

王长罡 董俊华 柯伟 陈楠. 硼酸缓冲溶液中pH值和Cl-浓度对Cu腐蚀行为的影响[J]. 金属学报, 2011, 47(3): 354-360.
, , , . EFFCTS OF pH AND Cl CONCENTRATION ON THE CORROSION BEHAVIOR OF COPPER IN BORIC ACID BUFFER SOLUTION[J]. Acta Metall Sin, 2011, 47(3): 354-360.

全文: PDF(1038 KB)  
摘要: 在硼酸缓冲溶液中, 采用动电位极化、电化学阻抗谱(EIS)和半导体电容分析方法分别研究了Cu电极的极化行为及其表面人工Cu2O钝化膜的化学稳定性. 结果表明,低 pH值、高Cl$^{-}$浓度均造成Cu2O钝化膜的破坏和溶解. 高Cl-浓度时,Cu2O钝化膜的半导体性质由p型转变为n型, 使Cl-更容易进入钝化膜与Cu+络合, 并破坏钝化膜从而加速腐蚀. 高pH值、低Cl-浓度有利于Cu2O钝化膜稳定.
关键词 高放废物地质处置 Cu2O钝化膜 稳定性 电化学阻抗谱(EIS) Mott-Schottky方法    
Abstract:The strategy for disposal of high–level radioactive waste in china is to enclose the spent nuclear fuel in sealed metal canisters which are embedded in bentonite clay hundreds meters deep in the bed–rock. The choice of container material depends largely on the redox conditions and the aqueous environment of the repository. One of the choices for the fabrication of waste canisters is copper, for it is thermodynamically stable under the saline, anoxic conditions over the large majority of the container lifetime. For this advantage, some other countries (Canada, Sweden) have selected copper as the material of nuclear waste container. However, in the early aerobic phase of the geological disposal the corrosion of copper could take place, and the corrosion behavior of copper would be influenced by the complex chemical conditions of groundwater markedly. Regularly, in atmosphere environment the semiconductor passive film which is constructed by Cu2O would generate on the surface of copper. On the one hand, the Cu2O film could protect copper from corrosion. On the other hand, the formation of Cu2O film is necessary to maintain the propagation of crack during the stress corrosion cracking. Therefore, the study of the effect of water chemistry conditions on the stability of Cu2O passive film makes great sense for the general corrosion and stress corrosion cracking of copper. For copper and copper alloy, Cl is a highly aggressive ion. Lots of cases of failure and corrosion behavior of copper and copper alloy in Cl environment have been studied. The immersion of Cl would affect the semconductor properties of Cu2O, therefore, we focused on the effect of pH and Cl concentration on the corrosion behavior and semiconductor properties of Cu2O in this paper. The polarization behavior of Cu electrodes and the stability of passive film Cu2O in boric acid buffer solution have been investigated respectively by potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and semiconductor capacitance method (Mott–Schottky method). The results showed that the destruction and dissolutioof the passive film Cu2O happened in the conditions of low pH and high Cl concentration. The semconductor character of passive film changed from p–type into n–type in the solution with high Cl concentration, so that Cl is more likely to enter the passivfilm and take complex reaction wth Cu+, which could destroy thpassive film and accelerate corrosion. The passive film Cu2O is more steady in the condition of high pH and low Cl concentration.
Key wordsgeological disposal of high level radioactive waste    Cu2O passie film    tability    electrochemical impedance spectroscopy (EIS)    Mott–Schottky method
收稿日期: 2010-08-31     
基金资助:

国家自然科学基金资助项目51071160

作者简介: 王长罡, 男, 1985年生, 博士生
[1] Xu Q J, Wang W, Zhou G D. J Mater Prot, 2006; 39(7): 51

(徐群杰, 王伟, 周国定. 材料保护, 2006; 39(7): 51)

[2] Zhu X L, Lin L Y, Lei T Q. Acta Metall Sin, 1997; 33: 1256

(朱小龙, 林乐耘, 雷廷权. 金属学报, 1997; 33: 1256)

[3] Xu Q J, Zhu L J, Qi H, Cao W M, Zhou G D. Acta Metall Sin, 2008; 44: 1360

(徐群杰, 朱律均, 齐航, 曹为民, 周国定. 金属学报, 2008; 44: 1360)

[4] Smith J M, Wren J C, Dziemkowski M O, Shoesmith D W. J Electrochem Soc, 2007; 154: 431

[5] Ding J, Lin H C, Cao C N. Corros Sci Prot Technol, 2002; 14: 67

(丁杰, 林海潮, 曹楚南. 腐蚀科学与防护技术, 2002; 14: 67)

[6] Trachli B, Keddam M, Takenouti H, Srhiri A. Corros Sci, 2002; 44: 997

[7] Cicileo G, Rosales B, Varela F, Vilche J. Corros Sci, 1999; 41: 1359

[8] Valcarce M, De Sanchez S, Vazquez M. J Mater Sci, 2006; 41: 1999

[9] Srivastava A, Balasubramaniam R. Mater Charact, 2005; 55: 127

[10] Palit A, Pehkonen S. Corros Sci, 2000; 42: 1801

[11] Brizuela F, Procaccini R, Cere S, Vazquez M. J Appl Electrochem , 2006; 36: 583

[12] Bech–Nielsen G, Jaskula M, Chorkendorff, Larsen J. Electrochim Acta, 2002; 47: 4279

[13] Deslouis C, Tribollet B, Mengoli G, Musiani M M. J Appl Electrochem, 1988; 18: 374

[14] Deslouis C, Tribollet B, Mengoli G, Musiani M M. J Appl Electrochem, 1988; 18: 384

[15] Diard J P, Le Canut J M, Le Gorrec B, Montella C. Electrochim Acta, 1998; 43: 2485

[16] Li D G, Feng Y R, Bai Z Q, Zhu J W, Zheng M S. Electrochim Acta, 2007; 52: 7877

[17] Shinji F, Hiroaki T. Corros Sci, 2007; 49: 195
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