预氧化处理对12Cr铁素体/马氏体钢耐Pb-Bi腐蚀性能的影响

doi:10.11900/0412.1961.2022.00267

金属学报

2024, Vol. 60

Issue (5): 639-649 DOI: 10.11900/0412.1961.2022.00267

研究论文

本期目录 | 过刊浏览

预氧化处理对12Cr铁素体/马氏体钢耐Pb-Bi腐蚀性能的影响

潘霞¹^,², 张洋鹏¹^,³(

), 董志宏¹, 陈胜虎¹^,³, 姜海昌¹^,³, 戎利建¹^,³

1 中国科学院金属研究所沈阳 110016
2 中国科学技术大学材料科学与工程学院沈阳 110016
3 中国科学院金属研究所中国科学院核用材料与安全评价重点实验室沈阳 110016

Effect of Pre-Oxidation Treatment on the Corrosion Resistance in Stagnant Liquid Pb-Bi Eutectic of 12Cr Ferritic/Martensitic Steel

PAN Xia¹^,², ZHANG Yangpeng¹^,³(

), DONG Zhihong¹, CHEN Shenghu¹^,³, JIANG Haichang¹^,³, RONG Lijian¹^,³

1 Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
2 School of Materials Science and Engineering, University of Science and Technology of China, Shenyang 110016, China
3 CAS Key Laboratory of Nuclear Materials and Safety Assessment, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China

引用本文:

潘霞, 张洋鹏, 董志宏, 陈胜虎, 姜海昌, 戎利建. 预氧化处理对12Cr铁素体/马氏体钢耐Pb-Bi腐蚀性能的影响[J]. 金属学报, 2024, 60(5): 639-649.
Xia PAN, Yangpeng ZHANG, Zhihong DONG, Shenghu CHEN, Haichang JIANG, Lijian RONG. Effect of Pre-Oxidation Treatment on the Corrosion Resistance in Stagnant Liquid Pb-Bi Eutectic of 12Cr Ferritic/Martensitic Steel[J]. Acta Metall Sin, 2024, 60(5): 639-649.

全文: PDF(3762 KB) HTML

摘要:

针对液态Pb-Bi共晶(LBE)冷却快堆开发了一种新型高硅12Cr铁素体/马氏体钢，为进一步增强其耐Pb-Bi腐蚀性能，提升燃料组件的安全性，采用预氧化法对其进行了表面防护处理，表征了预氧化膜的结构，分析了预氧化处理对12Cr铁素体/马氏体钢耐550℃饱和氧LBE的腐蚀性能的影响。结果表明，该钢在720℃、1%O₂ + 99%N₂气氛中预氧化1 h时形成的氧化膜主要是(Fe, Cr)₂O₃和MnCr₂O₄氧化物，此氧化膜可有效阻止钢中Fe元素的向外扩散和LBE中O元素的向内扩散，进而提升了材料的耐LBE腐蚀性能。但由于Mn较高的扩散速率和在LBE中较高的溶解度，预氧化膜中的Mn元素会逐渐扩散和溶解至LBE，导致部分氧化膜失效并形成局部腐蚀区，当LBE腐蚀1000 h后，合金表面的局部腐蚀区可达60%。本工作揭示了新型高硅12Cr铁素体/马氏体钢中预氧化膜的微观结构、保护效果和失效机制，为进一步提升其预氧化膜的有效性和稳定性指明了方向。

关键词 ： Pb-Bi共晶冷却快堆, 铁素体/马氏体钢, 表面处理, Pb-Bi腐蚀, 预氧化膜

Abstract：

Lead-cooled fast reactors using liquid lead or lead-bismuth eutectic (LBE) alloy coolants have attracted international attention due to their unique advantages in safety, economy, and sustainable development. The availability of suitable core materials is one of the key challenges restricting the development and application of the lead-cooled fast reactor technology. Ferritic/martensitic steel is one of the important candidates for nuclear reactor fuel cladding, but the dissolution of Cr and Ni occurs in it upon contact with high-temperature LBE, resulting in cladding failure. Adding Si can improve corrosion resistance, and based on this property, previous work developed a high-Si ferritic/martensitic steel for LBE alloy-cooled fast reactor. Recently, pre-oxidation treatment was proposed to further improve the corrosion performance of steel in contact with LBE. However, the structure of the oxide film formed after the pre-oxidation of 12Cr ferritic/martensitic steel, the effect on corrosion resistance, and the failure mechanism are not clear. In this study, a pre-oxidized film was formed on the steel surface and its structure was characterized. Steel corrosion experiments using oxygen-saturated LBE at 550^oC were also performed to analyze the influence of pre-oxidation treatment on the LBE alloy coolant corrosion resistance of steel. The results demonstrated that the oxide films formed when steel is pre-oxidized at 720^oC in 1%O₂ + 99%N₂ atmosphere for 1 h are mainly (Fe, Cr)₂O₃ and MnCr₂O₄ oxides. The oxide films can effectively prevent the outward diffusion of Fe in steel and the inward diffusion of O in LBE, thereby improving the corrosion resistance of steel to stagnant oxygen-saturated LBE alloy coolant at 550^oC. However, due to the high diffusion rate of Mn and its high solubility in LBE alloys, the Mn in the pre-oxidized film will gradually diffuse and dissolve into the LBE alloy, rendering subsequently a part of the oxide film ineffective and forming a localized corrosion zone. After 1000 h of Pb-Bi corrosion, the local corrosion area on the alloy surface can reach 60%. This study revealed the microstructure, protective effect, and failure mechanism of the pre-oxidized film on the surface of high-Si ferritic/martensitic steel, and suggested research directions for further improving the effectiveness and stability of the pre-oxidized film.

Key words： lead-bismuth eutectic cooled fast reactor ferritic/martensitic steel surface treatment Pb-Bi corrosion pre-oxidized film

收稿日期: 2022-05-31

ZTFLH:

TG142.7

基金资助:国家自然科学基金项目(51871218);辽宁省博士科研启动基金项目(2020-BS-006)

通讯作者: 张洋鹏，ypzhang@imr.ac.cn，主要从事核用结构材料研究

Corresponding author: ZHANG Yangpeng, associate professor, Tel: (024)23971985, E-mail: ypzhang@imr.ac.cn

作者简介: 潘霞，女，1998年生，硕士生

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图1 高真空电阻炉示意图

图2 静态Pb-Bi共晶(LBE)腐蚀装置示意图

图3 预氧化的12Cr铁素体/马氏体钢样品表面氧化膜的SEM像

图4 预氧化的12Cr铁素体/马氏体钢样品的XRD谱

图5 预氧化的12Cr铁素体/马氏体钢样品截面形貌及元素分布

图6 未预氧化和预氧化的12Cr铁素体/马氏体钢样品在550℃经饱和氧LBE腐蚀500和1000 h后腐蚀层截面形貌的SEM-BSE像

图7 未预氧化的12Cr铁素体/马氏体钢样品经550℃饱和氧LBE腐蚀500 h后腐蚀层形貌及元素分布

图8 预氧化的12Cr铁素体/马氏体钢样品经550℃饱和氧LBE腐蚀1000 h后腐蚀层的EPMA面扫描结果

图9 未预氧化和预氧化处理的12Cr铁素体/马氏体钢样品经550℃饱和氧LBE腐蚀500 h后的表面SEM-BSE像

图10 预氧化的12Cr铁素体/马氏体钢样品腐蚀机制示意图

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