HCO3-和Cl-混合体系中Cu的点蚀行为研究
收稿日期: 2011-12-08
修回日期: 2012-06-07
网络出版日期: 2012-11-11
基金资助
国家自然科学基金资助项目51071160
RESEARCH ON PITTING CORROSION BEHAVIOR OF COPPER IN THE SOLUTION WITH HCO3- AND Cl-
Received date: 2011-12-08
Revised date: 2012-06-07
Online published: 2012-11-11
Supported by
Supported by National Natural Science Foundation of China (No.51071160)
在HCO3-和Cl-浓度不同的溶液中, 用循环极化的电化学测试方法和SEM, 对Cu的循环极化行为和点蚀表面形貌进行了研究. 结果表明, 该体系中Cu的腐蚀行为可概括为活性溶解型腐蚀、钝化型腐蚀、活性溶解型点蚀和钝化膜破裂型点蚀等4种类型; 在HCO3- 或Cl-单独存在环境中, Cu表面不发生点蚀, 只有Cl-和 HCO3-共同存在且起协同作用时, Cu表面才发生点蚀; 活性溶解型点蚀区域中, 点蚀敏感性随Cl-浓度的升高而增大, 而随HCO3- 浓度的升高先增大后减小; 钝化膜破裂型点蚀区域中, 点蚀敏感性随Cl-浓度的升高和HCO3-浓度的降低而增大.
王长罡 董俊华 柯伟 陈楠 李晓芳 . HCO3-和Cl-混合体系中Cu的点蚀行为研究[J]. 金属学报, 2012 , 48(11) : 1365 -1373 . DOI: 10.3724/SP.J.1037.2011.00773
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 down in the be-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, because it is thermodynamically stable under the saline, anoxic conditions over the large majority of the container lifetime. 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. Pitting corrosion of copper often takes place in power plants or air-conditioning condensate water. The corrosion environment usually contains HCO3-, SO42- and Cl-. In the early stage of geological disposal, if the aerobic water with HCO3- , SO42- and Cl- immersion repository, the pitting corrosion of copper may occur. Some researchers believed that SO42- and Cl- would promote the occurrence of pitting corrosion of copper, and HCO3- will lead to surface passivation and inhibit pitting. It is considered that in the solution with HCO3- and SO42-, HCO3- could firstly promote and then inhibit pitting. However, there is no systematic work about pitting in the solution with HCO3- and Cl-. In this work, the cycle polarization behavior and surface morphology of pitting on copper has been investigated in HCO3- and Cl- mixed solution, respectively by electrochemical cyclic polarization test and SEM. The results showed that the circular polarization curves of copper could be divided into four types. The pitting on the surface of copper occurs only in the environment with both Cl- and HCO3-. In the area of active dissolve pitting, the pitting susceptibility increased with the increase of concentration of Cl-, while it increased then decreased with the increase of the concentration of HCO3-. In the area of passive film rupture pitting area, pitting susceptibility increased with the increase of concentration of Cl- and with the decrease of the concentration of HCO3-.
Key words: high-level radioactive waste; Cu; pitting; cyclic polarization; HCO3-; Cl-
[1] Wang C G, Dong J H, Ke W, Chen N. Acta Metall Sin, 2011; 47: 354
(王长罡, 董俊华, 柯 \ \ 伟, 陈楠, 金属学报, 2011; 47: 354)
[2] Darren A, Lytle A, Mallikarjuna N, Nadagouda B. Corros Sci, 2010; 52: 1927
[3] Guo Y H, Wang J, Wang ZM, Liu S F, Su Y. Bull Mineral Petrol Geochem, 2007; 26: 607
(郭永海, 王 驹, 王志明, 刘淑芬, 苏 锐. 矿物岩石地球化学通报, 2007; 26: 607)
[4] Fujii T, Kodama T, Baba H. Corros Sci, 1984; 24: 901
[5] Drogowska M, Brossard L, M´enard H. Surf Coat Technol, 1988; 34: 383
[6] Drogowska M, Brossard L, M´enard H. J Electrochem Soc, 1992; 139: 39
[7] Duthil J P, Mankowski G, Giusti A. Corros Sci, 1996; 38: 1839
[8] Reda M R, Alhajji J N. Corrosion, 1996; 52: 232
[9] Cantor A F, Park J K, Vaiyavatjamai P. J Am Water Works Assoc, 2003; 95(5): 112
[10] Baba H, Kodama T, Fujii T. Trans Natl Res Inst Met, 1986; 28: 248
[11] Christy A G, Lowe A, Otieno–Alego V, Stoll M, Webster R D. J Appl Electrochem, 2004; 34: 225
[12] Edwards M, Ferguson J F, Reiber S H. J AmWaterWorksAssoc, 1994; 86(7): 74
[13] Sosa M, Patel S, Edwards M. Corrosion, 1999; 55: 1069
[14] Edwards M, Rehring J, Mayer T. Corrosion, 1994; 50: 366
[15] Cong H, Scully J R. J Electrochem Soc, 2010; 157: C200
[16] Nishikata A, Itagaki M, Tsuru T, Haruyama S. Corros Sci, 1990; 31: 287
[17] Jujii T. Trans Natl Res Inst Met, 1988; 30(2): 81
[18] Drogowska M, Brossard L, M´enard H. J Electrochem Soc, 1992; 139: 39
[19] Wang C G, Dong J H, Ke W, Chen N. Acta Metall Sin, 2012; 48: 85
(王长罡, 董俊华, 柯伟, 陈 楠. 金属学报, 2012; 48: 85)
[20] Abd El Meguid E A, Awad N K. Corros Sci, 2009; 51: 1134
[21] 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)
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