Oxidation Behavior of Self-passivated W-Cr-Zr Alloys as the First Wall Candidate Material

doi:10.11901/1005.3093.2024.211

Chinese Journal of Materials Research

2025, Vol. 39

Issue (5): 343-352 DOI: 10.11901/1005.3093.2024.211

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Oxidation Behavior of Self-passivated W-Cr-Zr Alloys as the First Wall Candidate Material

WU Yucheng¹^,²(

), ZUO Tong¹, TAN Xiaoyue¹^,², ZHU Xiaoyong¹^,², LIU Jiaqin³^,⁴

^1.School of Materials Science and Engineering, Hefei University of Technology, Hefei 230009, China
^2.National-Local Joint Research Center of Nonferrous Metals and Processing Technology, Hefei 230009, China
^3.Institute of Industry and Equipment, Hefei University of Technology, Hefei 230009, China
^4.Anhui Advanced Composite Material Design and Application Engineering Center, Hefei 230051, China

Cite this article:

WU Yucheng, ZUO Tong, TAN Xiaoyue, ZHU Xiaoyong, LIU Jiaqin. Oxidation Behavior of Self-passivated W-Cr-Zr Alloys as the First Wall Candidate Material. Chinese Journal of Materials Research, 2025, 39(5): 343-352.

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Abstract

Self-passivating tungsten alloy (SPTA) inhibits the further oxidation by forming dense oxide scale on its surface. Therefore, the use of self-passivating tungsten alloys as the first wall candidate material for nuclear fusion is a material solution proposed to address the safety hazards that may arise in the event of loss-of-coolant accident in future nuclear fusion devices. The compact oxide scale formed on the surface of self-passivating tungsten alloys requires the participation of passivating elements, and their oxidation behavior is related to its composition and structure. Herein, an alloy W87.6-Cr11.4-Zr1.0 (in mass fraction) was prepared by mechanical alloying and field assisted sintering technology, then its oxidation behavior was assessed intermittently at 1000 ^oC in a flowing gas mixture Ar+20%O₂ (volume fraction). The surface roughness, morphology and phase composition of the W-Cr-Zr alloy before and after oxidation were characterized by 3D laser measurement microscopy, scanning electron microscope (SEM) and X-ray diffraction instrument (XRD), and the influence of oxide scale structure on the subsequent oxidation behavior of W-Cr-Zr alloy was investigated. The results show that the larger the surface roughness, the more cracks of the oxide scale formed in the initial oxidation stage. In the subsequent oxidation process, cracks act as the short-circuit channel for inward migration of oxygen to accelerate the oxidation of the underneath alloy substrate, thus having a large linear oxidation rate. The top layer of the oxide scale formed by the oxidation of W-Cr-Zr alloy is Cr₂WO₆ with high temperature stability, and the inner layer is WO_2.83 with easy sublimation. After the removal of the Cr₂WO₆ layer, a relatively loose Cr₂WO₆ layer can still grow in the subsequent oxidation process along with the severe oxidation of the matrix and the rapid sublimation of WO_2.83, which has certain protectiveness for the substrate. Therefore, to adjust or control the microstructure and oxidation behavior of the tungsten alloy is of great reference value for material selection and operation safety of nuclear fusion device components.

Key words: metallic materials nuclear fusion W-Cr-Zr alloy self-passivating tungsten alloy initial surface layer oxidation behavior

Received: 16 May 2024

ZTFLH:

TL34

Fund: Funds for International Cooperation and Exchange of National Natural Science Foundation of China(52020105014);National Key Research and Development Program of China(2022YFE03140001);National “Clean Energy New Materials and Technology” Subject Innovation and Intelligence Base Project (111 Project, No.B18018)

Corresponding Authors: WU Yucheng, Tel: (0551)62905985, E-mail: ycwu@hfut.edu.cn

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https://www.cjmr.org/EN/10.11901/1005.3093.2024.211 OR https://www.cjmr.org/EN/Y2025/V39/I5/343

Fig.1 Microstructure of W-Cr-Zr alloy before oxidation (a), the surface morphology of sample after different surface treatment (b~e) and the corresponding linear roughness (f)

Fig.2 Surface morphology of W-Cr-Zr alloy with different surface roughness after oxidation at 1000 ^oC for 2 min
(a) R_a = 0.64 μm, (b) R_a = 0.51 μm, (c) R_a = 0.41 μm, (d) R_a = 0.24 μm

Fig.3 Oxidation behavior curves of W-Cr-Zr alloy with different surfaces roughness when oxidation at 1000 ^oC (a) and the curve of linear oxidation rate as function of surface roughness (b)

Fig.4 XRD patterns of W-Cr-Zr alloy with different surfaces roughness after oxidation at 1000 ^oC for 20 h

Fig.5 Surface morphology of W-Cr-Zr alloy with different surface roughness after oxidation at 1000 ^oC for 20 h
(a) R_a = 0.64 μm, (b) R_a = 0.51 μm, (c) R_a = 0.41 μm, (d) R_a = 0.24 μm

Fig.6 Cross section of oxide scale of W-Cr-Zr alloy with different roughness surfaces after oxidation at 1000 ^oC for 20 h (a~d), the relationship between the thickness of oxide scale and surface roughness of samples before oxidation (e) and the surface roughness of oxide scales (f)

Fig.7 Mass change curves of W-Cr-Zr alloy oxidation at 1000 ^oC (red line) and continuous oxidation after remove the surface oxide (blue line)

Fig.8 XRD patterns of W-Cr-Zr alloy after oxidation 40 h, remove top surface layer and continuous oxidation 40 h

Fig.9 Surface morphology of W-Cr-Zr alloy after oxidation 40 h (a, b), after removing the top surface oxide layer (c, d) and then continuous oxidation 40 h (e, f)

Fig.10 Cross section of W-Cr-Zr alloy after oxidation 40 h (a), then oxidation 40 h, and the responding surface scanning energy spectra of W, Cr and O (b)

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