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

doi:10.11900/0412.1961.2022.00267

Acta Metall Sin

2024, Vol. 60

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

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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

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PAN Xia, ZHANG Yangpeng, DONG Zhihong, CHEN Shenghu, JIANG Haichang, RONG Lijian. Effect of Pre-Oxidation Treatment on the Corrosion Resistance in Stagnant Liquid Pb-Bi Eutectic of 12Cr Ferritic/Martensitic Steel. Acta Metall Sin, 2024, 60(5): 639-649.

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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

Received: 31 May 2022

ZTFLH:

TG142.7

Fund: National Natural Science Foundation of China(51871218);Doctoral Start-up Project of Liaoning Province Natural Science Foundation(2020-BS-006)

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

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	PAN Xia
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	DONG Zhihong
	CHEN Shenghu
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	RONG Lijian

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https://www.ams.org.cn/EN/10.11900/0412.1961.2022.00267 OR https://www.ams.org.cn/EN/Y2024/V60/I5/639

Fig.1 Schematic of the high vacuum resistance furnace

Fig.2 Schematic of stagnant lead-bismuth eutectic (LBE) corrosion device

Fig.3 Low (a) and high (b) magnified SEM images of the pre-oxidized 12Cr ferritic/martensitic steel sample

Fig.4 XRD spectrum of the pre-oxidized 12Cr ferritic/martensitic steel sample

Fig.5 Cross-sectional SEM image and EDS mappings of the pre-oxidized 12Cr ferritic/martensitic steel sample

Fig.6 Cross-sectional SEM-BSE images of 12Cr ferritic/martensitic steel samples without (a, b) and with (c, d) pre-oxidation treatment after exposure for 500 h (a, c) and 1000 h (b, d) to stagnant oxygen-saturated LBE at 550^oC (Insets in Figs.6a and c show the high magnified images of oxide scale zone. IOZ—internal oxidation zone)

Fig.7 Cross-sectional SEM image and corresponding line scanning of 12Cr ferritic/martensitic steel sample without pre-oxidation treatment after exposure for 500 h to stagnant oxygen-saturated LBE at 550^oC

Fig.8 EPMA analyses of the cross section of the pre-oxidized 12Cr ferritic/martensitic steel sample after exposure for 1000 h to stagnant oxygen-saturated LBE at 550^oC

Fig.9 SEM-BSE surface images of 12Cr ferritic/martensitic steel samples without (a) and with (b-d) pre-oxidation treatment after exposure for 500 h to stagnant oxygen-saturated LBE at 550^oC (Inset in Fig.9a shows the EDS of the corrosion products)

Fig.10 Schematics of the corrosion mechanism of the pre-oxidized 12Cr ferritic/martensitic steel sample
(a) initial pre-oxidized film
(b, c) pre-oxidized film is being corroded
(d) a localized corrosion zone is formed

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