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Acta Metall Sin  2020, Vol. 56 Issue (10): 1366-1376    DOI: 10.11900/0412.1961.2020.00035
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Corrosion Behaviors and Mechanisms of ODS Steel Exposed to Static Pb-Bi Eutectic at 600 and 700 ℃
BAO Feiyang1,2, LI Yanfen1,2,3(), WANG Guangquan2,4, ZHANG Jiarong2, YAN Wei1,2,3, SHI Quanqiang2,3, SHAN Yiyin1,2,3, YANG Ke1,2, XU Bin5, SONG Danrong5, YAN Mingyu5, WEI Xuedong5
1 School of Materials Science and Engineering, University of Science and Technology of China, Shenyang 110016, China
2 Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
3 Key Laboratory of Nuclear Materials and Safety Assessment, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
4 Nano Science and Technology Institute, University of Science and Technology of China, Suzhou 215000, China
5 Nuclear Power Institute of China, Chengdu 610005, China
Cite this article: 

BAO Feiyang, LI Yanfen, WANG Guangquan, ZHANG Jiarong, YAN Wei, SHI Quanqiang, SHAN Yiyin, YANG Ke, XU Bin, SONG Danrong, YAN Mingyu, WEI Xuedong. Corrosion Behaviors and Mechanisms of ODS Steel Exposed to Static Pb-Bi Eutectic at 600 and 700 ℃. Acta Metall Sin, 2020, 56(10): 1366-1376.

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Abstract  

With good neutron properties, anti-irradiation performances, heat transfer properties and inherent safety characteristics, liquid lead or Pb-Bi eutectic (LBE) has been a primary candidate coolant for accelerator driven system and advanced nuclear reactors. However, corrosion of structural materials is a critical challenge in the use of liquid lead and LBE in high temperature nuclear reactors. Therefore, research on corrosion compatibility of structural materials with LBE at elevated temperatures is of great significance. In this work, the long-term corrosion experiments in static LBE for a oxide dispersion strengthened (ODS) steel were carried out at 600 and 700 ℃. The temperature effects on different corrosion behaviors were studied by the analyses of XRD, SEM and EDS, and the underlying mechanisms were clarified. After exposing to LBE at 600 ℃ for up to 2000 h, a typical double-layer oxide scale with the thickness of about 10 μm was formed on the surface of ODS steel, which was composed of outer layers of Pb-Fe-O and Fe3O4 and inner layer of Fe-Cr-Al spinal. In addition, a thin Al-rich layer was also formed under the inner layer. Due to the protective effect of the relatively dense inner layer and the Al-rich layer, ODS steel showed excellent resistance to LBE corrosion at 600 ℃ with a significantly lower corrosion rate. On the contrary, when exposed to LBE at 700 ℃ , the structure and thickness of the oxide scale formed on the surface of the ODS steel were obviously different. After exposure for 100 h, a dense protective Al2O3 oxide layer with a thickness of about 500 nm was formed, greatly reducing the corrosion rate. With the corrosion time prolonging to 500 h at 700 ℃, most of Al2O3 layer was still remained. However, a few of nodular-like oxides were formed originated from local weak areas, which broken off the continuity of protective Al2O3 and led to deeper corrosion by LBE.

Key words:  advanced nuclear energy system      Pb-Bi eutectic (LBE)      oxide dispersion strengthened (ODS) steel      high temperature corrosion      oxide scale     
Received:  21 January 2020     
ZTFLH:  TG172  
Fund: Nuclear Power Technology Innovation Center Project of Nuclear Power Institute of China(HDLCXZX-2019-HD-15-01);National Natural Science Foundation of China(U1832206);"Excellent Scholar Funding" initialed by Institute of Metal Research, Chinese Academy of Science(JY7A7A111A1)

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https://www.ams.org.cn/EN/10.11900/0412.1961.2020.00035     OR     https://www.ams.org.cn/EN/Y2020/V56/I10/1366

Fig.1  Schematic of corrosion test equipment (LBE—lead-bismuth eutectic)
Fig.2  XRD spectra of ODS steel exposed to static LBE at 600 ℃ (a) and 700 ℃ (b) for different time (PF—plumboferrite)
Fig.3  SEM images of surface scale formed on ODS steel exposed to static LBE at 600 ℃ for 100 h (a), 500 h (b), 1000 h (c) and 2000 h (d) (Insets show the corresponding high magnified morphologies)
Fig.4  SEM images of surface scale formed on ODS steel after exposed to static LBE at 600 ℃ for 100 h
(a) a representative area (b) regular octahedral particles area marked as "b" in Fig.4a
PositionMass fraction / % (atomic fraction / %)Compound
CrAlOFePb

Area 1

(bamboo leaf-like oxide)

--18.91 (52.49)51.90 (41.26)29.19 (6.25)PbO·xFe2O3

Area 2

(octahedral particle)

1.00 (0.66)-26.24 (56.40)68.62 (42.26)4.14 (0.69)Fe3O4

Area 3

(matrix)

12.52 (11.56)6.20 (11.02)4.78 (14.34)72.24 (62.09)4.27 (0.99)Al-riched matrix
Table 1  EDS analyses of the surface oxides of ODS steel exposed to static LBE at 600 ℃ for 100 h in Fig.4
Fig.5  Low and high magnified SEM images of the surface scale formed on ODS steel exposed to static LBE at 700 ℃ for 100 h (a, b) and 500 h (c~f) (Figs.5e and f are high magnified SEM images for the nodular area marked as "e" and flat area marked as "f" in the Fig.5d, respectively)
PositionMass fraction / % (atomic fraction / %)Compound
CrAlOFePb

Area 1

(nodule)

-1.31 (2.49)14.97 (45.10)52.30 (45.13)31.34 (7.29)PbO·xFe2O3

Area 2

(particle)

9.73 (6.31)19.32 (24.13)17.72 (37.72)53.23 (32.16)-Al2O3

Area 3

(flaky oxide)

1.15 (0.70)23.92 (27.79)30.40 (59.54)12.79 (7.18)31.73 (4.8)PbAl2O4
Table 2  EDS analyses of the surface oxides of ODS steel exposed to static LBE at 700 ℃ for 500 h in Figs.5e and f
Fig.6  Low (a, c, e, g) and high (b, d, f, h) magnified SEM images of cross-section oxide scale formed on ODS steel exposed to static LBE at 600 ℃ for 100 h (a, b), 500 h (c, d), 1000 h (e, f) and 2000 h (g, h)
Fig.7  EDS analyses of cross-section oxide scale formed on ODS steel exposed to static LBE at 600 ℃ for 500 h
Color online
Fig.8  Low (a, c) and high (b, d) magnified SEM images of cross-section oxide scale formed on ODS steel exposed to static LBE at 700 ℃ for 100 h (a, b) and 500 h (c, d)
Fig.9  EDS analyses of cross-section oxide scale formed on ODS steel exposed to static LBE at 700 ℃ for 500 h
Color online
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