NiCu低合金钢在含Cl<sup>-</sup>的除氧NaHCO<sub>3</sub>溶液中的腐蚀行为研究

doi:10.11900/0412.1961.2014.00349

金属学报

2015, Vol. 51

Issue (4): 440-448 DOI: 10.11900/0412.1961.2014.00349

本期目录 | 过刊浏览

NiCu低合金钢在含Cl^-的除氧NaHCO₃溶液中的腐蚀行为研究

卢云飞(

), 阳靖峰, 董俊华, 柯伟

中国科学院金属研究所材料环境腐蚀研究中心, 沈阳 110016

THE CORROSION BEHAVIOUR OF NiCu LOW ALLOY STEEL IN A DEAERATED BICARBONATE SOLUTION CONTAINING Cl^- IONS

LU Yunfei(

), YANG Jingfeng, DONG Junhua, KE Wei

Environmental Corrosion Research Center of Materials, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016

引用本文:

卢云飞, 阳靖峰, 董俊华, 柯伟. NiCu低合金钢在含Cl^-的除氧NaHCO₃溶液中的腐蚀行为研究[J]. 金属学报, 2015, 51(4): 440-448.
Yunfei LU, Jingfeng YANG, Junhua DONG, Wei KE. THE CORROSION BEHAVIOUR OF NiCu LOW ALLOY STEEL IN A DEAERATED BICARBONATE SOLUTION CONTAINING Cl^- IONS[J]. Acta Metall Sin, 2015, 51(4): 440-448.

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摘要:

对NiCu低合金钢在模拟深层地下水环境, 即除氧0.1 mol/L NaHCO₃+0.1 mol/L NaCl溶液中, 原位监测其在长时间浸泡条件下的开路电位变化曲线及阻抗谱的演化, 研究电极表面的腐蚀演化规律, 并与相同条件下低碳钢的腐蚀行为进行比较. 结果表明, NiCu低合金钢在本实验溶液中的耐蚀性要显著优于低碳钢, 尤其是其耐局部腐蚀的能力更优. 合金元素Ni富集在内锈层中, 可能以NiFe₂O₄的形式存在, 而合金元素Cu的富集不明显, 可能的存在形式为CuFeO₂.

关键词 ：低合金钢, 锈层, HCO₃^-, Cl^-

Abstract：

The corrosion behaviour of low alloy steel containing Ni and Cu was studied because it is a promising candidate canister material for the disposal of high-level radioactive waste (HLW) in China. Due to the intensely radioactive nature of HLW, the waste has to be prevented from reaching the biosphere for many tens of thousands of years. Deep geological disposal is now considered to be the most preferable option for isolating HLW and it relies on series of natural and engineered barriers, e.g. a metallic canister. However, as soon as the waste package is settled, groundwater would seep back slowly through the outer barriers and ultimately arrive at the surface of the canister. Accordingly, there comes the groundwater-induced dissolution of the canister and subsequent transport of radionuclides through the barriers. That is to say, the effectiveness of radionuclide retention and isolation depends mostly and finally on the corrosion resistance of metallic canisters in deep groundwater environments. In this work, the test solution is deaerated 0.1 mol/L NaHCO₃+0.1 mol/L NaCl, simulating the deep groundwater environment. The evolution of corrosion of NiCu low alloy steel in the test solution was investigated by electrochemical measurements. XRD was used to illustrate the composition of formed corrosion products. SEM was used to observe the electrode surface morphology and the cross section of the rust layer. The electrochemical results showed that low alloy steel has a lower corrosion rate and is less prone to localized corrosion than low carbon steel. In order to understand the mechanism of alloying elements, EDS and EPMA were used to analyse the distribution of alloying elements cross-sectional. XPS and E-pH diagram were used to estimate the possible existence form of alloying elements. By means of EDS and EPMA, it was founded that Ni is concentrated in the inner rust layer while the enrichment of Cu is not so obvious. XRD, XPS and E-pH results indicated that Ni and Cu are existed in the form of NiFe₂O₄ and CuFeO₂ respectively.

Key words： low alloy steel rust HCO₃^- Cl^-

ZTFLH:

TF777.1

基金资助:*国家自然科学基金资助项目51471175

作者简介: null

卢云飞, 女, 1987年生, 博士生

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表1 NiCu低合金钢和Q235低碳钢的化学成分

图1 NiCu低合金钢和低碳钢[10]在实验溶液中的极化曲线和开路电位随浸泡时间的变化曲线

图2 NiCu低合金钢和低碳钢在实验溶液中浸泡不同时间后的阻抗谱

图3 电位突变前后对应的等效电路图

表2 实验材料在浸泡初期的电化学阻抗谱拟合结果

图4 NiCu低合金钢在实验溶液中浸泡28 d去除表面锈层后的表面腐蚀形貌

表3 实验材料在浸泡后期的电化学阻抗谱拟合结果

图5 NiCu低合金钢在实验溶液中浸泡28 d后产物的XRD谱

图6 NiCu低合金钢的截面腐蚀形貌以及针对合金元素分布的EDS线扫结果和EPMA面扫结果

图7 NiCu钢在实验溶液中浸泡28 d后的内锈层产物中合金元素的XPS分析结果

图8 Fe-Ni-Cu-H2O 体系在25 ℃条件下的电位-pH图

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