Oxidation Behavior of Valve Materials Used in Steam Turbine in Supercritical Water Environment

doi:10.11902/1005.4537.2024.393

Journal of Chinese Society for Corrosion and protection

2025, Vol. 45

Issue (5): 1219-1232 DOI: 10.11902/1005.4537.2024.393

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Oxidation Behavior of Valve Materials Used in Steam Turbine in Supercritical Water Environment

WANG Fenling¹, SHANG Limei¹, ZHANG Naiqiang², ZHU Zhongliang²(

)

1 State Key Laboratory of Clean & Efficient Turbomachinery Power Equipment-High Temperature Materials Research Institute, Dongfang Electric Corporation, Dongfang Turbing Corporation Limited, Deyang 618000, China
2 Key Laboratory of Power Station Energy Transfer, Conversion and System, Ministry of Education, North China Electric Power University, Beijing 102206, China

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WANG Fenling, SHANG Limei, ZHANG Naiqiang, ZHU Zhongliang. Oxidation Behavior of Valve Materials Used in Steam Turbine in Supercritical Water Environment. Journal of Chinese Society for Corrosion and protection, 2025, 45(5): 1219-1232.

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Abstract

The oxidation behavior of F91, nitrided F91 and F92 steels were performed in supercritical water (SCW) at 600-620 ℃/25 MPa. The oxidation kinetics, microstructure and phase composition of the oxide scale were analyzed using an electronic balance, SEM, XRD and XPS. The results show that the oxidation kinetics of F91, nitrided F91 and F92 steels deviate from the parabolic law. The oxide scale formed on the steels were a typical double-layer structure, consisting of an Fe-rich outer layer Fe₃O₄, Fe₂O₃, and a Cr-rich inner layer. Furthermore, MoO₃, Ni(OH)₂ and Cr₂O₃were also detected on the surface of the oxide scale. In addition, with the increase of oxidation time and temperature, the oxide scale undergoes severe warping-type peeling. The oxidation and peeling mechanisms of F91, nitrided F91 and F92 steels in supercritical water were also discussed.

Key words: nitridation oxidation supercritical water oxidation mechanism oxide film

Received: 10 December 2024 32134.14.1005.4537.2024.393

ZTFLH:

TK245

Fund: National Key Research and Development Project of China(2022YFB4100403)

Corresponding Authors: ZHU Zhongliang, E-mail: zhzl@ncepu.edu.cn

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https://www.jcscp.org/EN/10.11902/1005.4537.2024.393 OR https://www.jcscp.org/EN/Y2025/V45/I5/1219

Fig.1 Weight gains of F91 (a), nitrided F91 (b) and F92 (c) steels during exposure in SCW

Fig.2 SEM surface morphologies of F91 steel oxidized in SCW at 600 ℃ under 25 MPa for 100 h (a, b), 1000 h (c, d) and 3000 h (e, f)

Fig.3 SEM surface morphologies of F91 steel oxidized in SCW at 620 ℃ under 25 MPa for 100 h (a, b), 1000 h (c, d) and 3000 h (e, f)

Fig.4 SEM surface morphologies of nitrided F91 steel oxidized in SCW at 600 ℃ for 100 h (a, b), 1000 h (c, d) and 3000 h (e, f)

Fig.5 SEM surface morphologies of nitrided F91 steel oxidized in SCW at 620 ℃ for 100 h (a, b), 1000 h (c, d) and 3000 h (e, f)

Fig.6 SEM surface morphologies of F92 steel oxidized in SCW at 600 ℃ for 100 h (a, b), 1000 h (c, d) and 3000 h (e, f)

Fig.7 SEM surface morphologies of F92 steel oxidized in SCW at 620 ℃ for 100 h (a, b), 1000 h (c, d) and 3000 h (e, f)

Fig.8 Cross-sectional SEM images of F91 steel oxidized in SCW at 600 ℃ for 100 h (a, b), 1000 h (c, d) and 3000 h (e, f)

Fig.9 Cross-sectional SEM image of F91 steel oxidized in SCW at 620 ℃ for 100 h (a, b), 1000 h (c, d) and 3000 h (e, f)

Fig.10 Depth profiles of various elements in the oxide scales formed on F91 steel after oxidation in SCW at 600 ℃-100 h (a), 600 ℃-1000 h (b), 600 ℃-3000 h (c), 620 ℃-100 h (d), 620 ℃-1000 h (e) and 620 ℃-3000 h (f)

Fig.11 Cross-sectional SEM images of nitrided F91 steel oxidized in SCW at 600 ℃ for 100 h (a, b), 1000 h (c, d) and 3000 h (e, f)

Fig.12 Cross-sectional SEM image of nitrided F91 steel oxidized in SCW at 620 ℃ for 100 h (a, b), 1000 h (c, d) and 3000 h (e, f)

Fig.13 Depth profiles of various elements in the oxide scales formed on nitrided F91 steel after oxidation in SCW at 600 ℃-100 h (a), 600 ℃-1000 h (b), 600 ℃-3000 h (c), 620 ℃-100 h (d), 620 ℃-1000 h (e) and 620 ℃-3000 h (f)

Fig.14 Cross-sectional SEM images of F92 steel oxidized in SCW at 600 ℃ for 100 h (a, b), 1000 h (c, d) and 3000 h (e, f)

Fig.15 Cross-sectional SEM images of F92 steel oxidized in SCW at 620 ℃ for 100 h (a, b), 1000 h (c, d) and 3000 h (e, f)

Fig.16 Depth profiles of various elements in the oxide scales formed on F92 steel after oxidation in SCW at 600 ℃-100 h (a), 600 ℃-1000 h (b), 600 ℃-3000 h (c), 620 ℃-100 h (d), 620 ℃-1000 h (e) and 620 ℃-3000 h (f)

Fig.17 X-ray diffraction patterns of F91 steel (a), nitrided F91 (b) and F92 (c) steels after oxidation in SCW at 600 and 620 ℃ for different time

Fig.18 XPS full spectrum of the oxide scale of F91 steel oxidized in SCW for 3000 h at 600 ℃ (a), and fine peaks of Mo 3d (b), Ni 2p (c), Fe 2p (d), and O 1s (e)

Fig.19 XPS full spectrum of the oxide scale of F91 steel oxidized in SCW for 3000 h at 620 ℃ (a), and fine peaks of Mo 3d (b), Fe 2p (c), and O 1s (d)

Fig.20 XPS full spectrum of the oxide scale of nitrided F91 steel oxidized in SCW for 3000 h at 600 ℃ (a), and fine peaks of Cr 2p (b), Fe 2p (c), Ni 2p (d), and O 1s (e)

Fig.21 XPS full spectrum of the oxide scale of nitrided F91 steel oxidized in SCW for 3000 h at 620 ℃ (a), and fine peaks of Fe 2p (b) and O 1s (c)

Fig.22 XPS full spectrum of the oxide scale of F92 steel oxidized in SCW for 3000 h at 600 ℃ (a), and fine peaks of Mo 3d (b), Fe 2p (c), Cr 2p (d), and O 1s (e)

Fig.23 XPS full spectrum of the oxide scale of F92 steel oxidized in SCW for 3000 h at 620 ℃ (a), and fine peaks of Mo 3d (b), Fe 2p (c), and O 1s (d)

Table1 Binding energies corresponding to XPS characteristic peaks of tested various elements

Table 2 Thicknesses of oxide scales formed on F91 steel during oxidation in SCW at different temperatures for different time (μm)

Table 3 Thicknesses of oxide scales formed on nitrided F91 steel during oxidation in SCW under the different conditions of temperature and time

Table 4 Thicknesses of oxide scales formed on F92 steel during oxidation in SCW at different temperatures for different time

Fig.24 X-ray diffraction pattern of nitrided F91 steel

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