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Acta Metall Sin  2021, Vol. 57 Issue (8): 989-999    DOI: 10.11900/0412.1961.2020.00451
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Oxide Scale Formation on Ultrafine-Grained Ferritic-Martensitic Steel During Pre-Oxidation and Its Effect on the Corrosion Performance in Stagnant Liquid Pb-Bi Eutectic
CHEN Shenghu(), RONG Lijian
CAS Key Laboratory of Nuclear Materials and Safety Assessment, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
Cite this article: 

CHEN Shenghu, RONG Lijian. Oxide Scale Formation on Ultrafine-Grained Ferritic-Martensitic Steel During Pre-Oxidation and Its Effect on the Corrosion Performance in Stagnant Liquid Pb-Bi Eutectic. Acta Metall Sin, 2021, 57(8): 989-999.

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Abstract  

Liquid lead and lead-bismuth eutectic (LBE) are considered primary candidate materials for coolant in advanced lead fast reactors, and also, for coolant and spallation target in accelerator-driven systems because of their favorable thermal-physical and chemical properties. However, liquid lead and LBE exhibit substantial structural material corrosion, which is considered one of the critical challenges in the liquid lead or LBE application. Among the effective methods to reduce the corrosive effect, careful control of the oxygen content dissolved in the liquid introduces a protective oxide layer on the surface of the structural material. Ferritic-martensitic steels with (9%-12%)Cr (mass fraction) have been considered promising structural materials in the advanced lead fast reactor and accelerator-driven system. Oxide scale with duplex structure is formed on the (9%-12%)Cr ferritic-martensitic steels in oxygen-containing LBE, but the oxide scale grows rapidly enough to cause the substrate recession. Recently, pre-oxidation treatment was proposed to further improve the corrosion performance in LBE. As reported, grain refinement promoted the formation of oxide scale without chemical modification. However, grain refinement effects on the oxide scale formation of (9%-12%)Cr ferritic-martensitic steels are not clear, and the effect of oxide scale through pre-oxidation treatment on the corrosion performance in LBE is rarely reported. In this study, the oxide scale formation behavior during pre-oxidation in air at 650oC on the 9Cr2WVTa ferritic-martensitic steel after different cold rotary-swaging deformation rates was analyzed using SEM, XRD, EPMA, and XPS, and the effect of pre-oxide scale on the corrosion performance in stagnant oxygen-saturated LBE was further investigated. The results demonstrated that the high-temperature oxidation resistance in air was enhanced by increasing the diameter reduction. A slight improvement in oxidation resistance was observed after 63% deformation, while significant enhancement in oxidation resistance was present in ultrafine-grained sample fabricated by 94% deformation. The oxide particle size was slightly reduced in the sample produced after 63% deformation during air oxidation compared with the tempered sample, but (Fe, Cr)2O3 oxide particles were formed on both samples. The size of oxide particles was significantly reduced and Mn-riched oxide (MnCr2O4 and Mn2O3) was promoted in the ultrafine-grained sample. The presence of Mn-riched oxide with good stability improved the oxide scale compactness. The compact oxide scale on the ultrafine-grained sample using pre-oxidation treatment at 650oC for 20 h effectively suppressed the corrosive attack of LBE and the outward diffusion of Fe through the pre-oxide scale after exposure for 500 h to stagnant oxygen-saturated LBE at 550oC. The higher solubility of Mn in LBE promoted the dissolution of the Mn-riched pre-oxide scale. The gradual dissolution of Mn in pre-oxide scale and corrosive attack by LBE led to the breakdown of the pre-oxide scale, which was supported by the formation of a continuous corrosion product layer after exposure for 2000 h to stagnant oxygen-saturated LBE.

Key words:  ultrafine-grained ferritic-martensitic steel      cold rotary-swaging deformation      pre-oxidation      Pb-Bi corrosion      diffusion     
Received:  09 November 2020     
ZTFLH:  TG174  
Fund: National Natural Science Foundation of China(51871218);Youth Innovation Promotion Association CAS(2018227);Natural Science Foundation of Liaoning Province(2020-MS-010);Nuclear Material Innovation Fund of National Defense Technology Industry Nuclear Material Technology Innovation Center(ICNM-2020-ZH-18)
About author:  CHEN Shenghu, associate professor, Tel: (024)23971981, E-mail: chensh@imr.ac.cn

URL: 

https://www.ams.org.cn/EN/10.11900/0412.1961.2020.00451     OR     https://www.ams.org.cn/EN/Y2021/V57/I8/989

Fig.1  SEM (a-c) and TEM (d-f) images of 9Cr2WVTa ferritic-martensitic steels after cold rotary-swaging deformation rates of 0 (a, d), 63% (b, e), and 94% (c, f)
Fig.2  Weight gain curves of 9Cr2WVTa ferritic-martensitic steels after cold rotary-swaging deformation rates of 0, 63%, and 94% oxidized in air at 650oC up to 500 h
Fig.3  SEM surface morphologies of 9Cr2WVTa ferritic-martensitic steels after cold rotary-swaging deformation rates of 0 (a-c), 63% (d-f), and 94% (g-i) oxidized in air at 650oC for 20 h (a, d, g), 100 h (b, e, h), and 500 h (c, f, i)
Fig.4  XRD spectra of 9Cr2WVTa ferritic-martensitic steel after cold rotary-swaging deformation rates of 0, 63%, and 94% oxidized in air at 650oC for 500 h
Fig.5  XPS depth profiles of 9Cr2WVTa ferritic-martensitic steels after cold rotary-swaging deformation rates of 0 (a), 63% (b), and 94% (c) oxidized in air at 650oC for 20 h
Fig.6  Back scattered electron (BSE) cross-sectional morphologies of cold rotary-swaged 9Cr2WVTa ferritic-martensitic steels at deformation rate of 94% without (a, b) and with (c, d) pre-oxidation treatment after exposure for 500 h (a, c) and 2000 h (b, d) to stagnant oxygen-saturated LBE at 550oC (Inset in Fig.6a shows the high magnification image of oxide scale)
Fig.7  EPMA analyses of the cross section of cold rotary-swaged 9Cr2WVTa ferritic-martensitic steel at deformation rate of 94% with pre-oxidation treatment after exposure for 2000 h to stagnant oxygen-saturated LBE at 550oC
Fig.8  XRD peaks of (110) (a), (200) (b), (211) (c), and (220) (d) of 9Cr2WVTa ferritic-martensitic steel after cold rotary-swaging deformation rates of 0, 63%, and 94%
Fig.9  SEM surface morphologies of cold rotary-swaged 9Cr2WVTa ferritic-martensitic steel at deformation rate of 94% with pre-oxidation treatment after exposure for 500 h (a) and 2000 h (b) to stagnant oxygen-saturated LBE at 550oC (Inset in Fig.9a shows the EDS spectrum of the corrosion product)
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