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Non-equimolar (Hf,Zr,Ta,W)B2 high-entropy diborides enable superior oxidation resistance

具有优异抗氧化性的非等摩尔(Hf,Zr,Ta,W)B2高熵二硼化物

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Abstract

Developing superior oxidation resistance of high-entropy diborides is critical for extending their potential applications in harsh environments. Herein, we developed non-equimolar (Hf,Zr,Ta,W)B2 high-entropy diborides with superior oxidation resistance by adjusting W contents for the first time. The as-fabricated (Hf0.28Zr0.28Ta0.28W0.15)B2 samples are predicted to possess superior oxidation resistance at 1473–1773 K through the oxidation depth quantitative analysis obtained by machine learning, which is attributed to the reason that the moderate WO3 can effectively inhibit the volatilization of B2O3. Furthermore, a four-layered structure is found in the generated product layers at 1773 K, which is due to the preferential oxidation of Hf and Zr elements at low oxygen partial pressure and the different diffusion activation energies of oxide products. The preferential oxidation of Hf and Zr elements is further demonstrated by the computational phase stability diagrams, and oxygen adsorption energies and charge transfer between oxygen atoms and different metal adsorption sites via first-principles calculations. Such superior performance endows (Hf0.28Zr0.28Ta0.28W0.15)B2 with potential applications as ultrahigh-temperature structural materials.

摘要

开发具有优异抗氧化性能的高熵二硼化物对于扩展其在极端环境中的潜在应用至关重要. 本文通过调控W含量首次制备出了具有优异抗氧化性能的非等摩尔(Hf,Zr,Ta,W)B2高熵二硼化物. 采用机器学习对材料氧化深度进行了量化分析, 发现制备的(Hf0.28Zr0.28Ta0.28W0.15)B2样品在1473–1773 K温度范围内具有优异的抗氧化性能, 这主要是因为适量的WO3可以有效抑制B2O3的挥发. 此外, 由于Hf和Zr元素的优先氧化以及氧化产物的扩散激活能差异, 1773 K下生成的产物层形成了一个四层结构. 通过计算的相稳定性图以及氧原子与不同金属吸附位点之间的吸附能和电荷转移, 进一步证明了Hf和Zr元素的优先氧化. 具有优异抗氧化性能的非等摩尔(Hf0.28Zr0.28Ta0.28W0.15)B2高熵二硼化物在超高温结构材料领域具有潜在的应用前景.

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Acknowledgements

This work was supported by the National Key Research and Development Program of China (2022YFB3708600), the National Natural Science Foundation of China (52122204 and 51972116), and Guangzhou Basic and Applied Basic Research Foundation (202201010632).

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Authors and Affiliations

  1. School of Materials Science and Engineering, South China University of Technology, Guangzhou, 510641, China

    Zihao Wen  (文子豪), Hong Meng  (孟虹), Zhongyu Tang  (唐忠宇), Yiwen Liu  (刘译文) & Yanhui Chu  (褚衍辉)

  2. State Key Laboratory of Mechanical System and Vibration, Shanghai Jiao Tong University, Shanghai, 200240, China

    Shengda Jiang  (江晟达)

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  1. Zihao Wen  (文子豪)
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  2. Hong Meng  (孟虹)
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  3. Shengda Jiang  (江晟达)
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  5. Yiwen Liu  (刘译文)
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  6. Yanhui Chu  (褚衍辉)
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Contributions

Chu Y conceived and designed this work. Wen Z and Tang Z performed the experiments. Meng H, Jiang S, and Liu Y performed the theoretical calculations. Chu Y and Wen Z analyzed the data and wrote the manuscript. All authors commented on the manuscript.

Corresponding author

Correspondence to Yanhui Chu  (褚衍辉).

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Supplementary information

Supporting data are available in the online version of the paper.

Zihao Wen is currently a PhD student at South China University of Technology. His research interests focus on the oxidation of high-entropy non-oxide ceramics.

Yanhui Chu is currently a professor at South China University of Technology, Guangzhou, China. He received his PhD degree from Northwestern Polytechnical University in 2016. From Jan. 2014 to Sep. 2015, he worked as a visiting scholar at Harvard University. His current research interest mainly focuses on the design, modeling and fabrication of high-entropy ceramics.

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The authors declare that they have no conflict of interest.

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Wen, Z., Meng, H., Jiang, S. et al. Non-equimolar (Hf,Zr,Ta,W)B2 high-entropy diborides enable superior oxidation resistance. Sci. China Mater. 66, 3213–3222 (2023). https://doi.org/10.1007/s40843-023-2461-y

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