High-temperature elemental segregation induced structure degradation in high-entropy fluorite oxide

Yixuan Hu; Mariappan Anandkumar; Yumeng Zhang; Joydip Joardar; Atul Suresh Deshpande; Xiaodong Wang; Kolan Madhav Reddy

doi:10.26599/JAC.2024.9220854

Journal of Advanced Ceramics 2024, 13(3): 310-322 https://doi.org/10.26599/JAC.2024.9220854

Research Article |

Open Access | Issue | Published: 12 March 2024

High-temperature elemental segregation induced structure degradation in high-entropy fluorite oxide

Show Author's Information Hide Author's Information Yixuan Hu^¹, Mariappan Anandkumar^², Yumeng Zhang^¹, Joydip Joardar^³, Atul Suresh Deshpande^², Xiaodong Wang^¹, Kolan Madhav Reddy^¹(

)

1School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China

2Department of Materials Science and Metallurgical Engineering, Indian Institute of Technology Hyderabad, Sangareddy 502285, India

3International Advanced Research Centre for Powder Metallurgy and New Materials (ARCI), Hyderabad 500005, India

Keywords:

phase transition, high-temperature stability, elemental segregation, high-entropy fluorite oxides (HEFOs)

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Hu Y, Anandkumar M, Zhang Y, et al. High-temperature elemental segregation induced structure degradation in high-entropy fluorite oxide. Journal of Advanced Ceramics, 2024, 13(3): 310-322. https://doi.org/10.26599/JAC.2024.9220854

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Abstract

Fluorite-structured oxides constitute an important category of oxides with a wide range of high-temperature applications. Following the concept of high entropy, high-entropy fluorite oxides (HEFOs) have showcased intriguing high-temperature application potential. However, unlocking this potential necessitates an assessment of their long-term stability under high-temperature conditions. In this study, we conducted a prolonged heat treatment at 1000 ℃ on typical HEFO, specifically (CeHfZrGdLa)O_x. After 100 h, high-intensity X-ray diffraction (XRD) revealed a transition from a single-phase fluorite to a multi-phase configuration. Further investigation by analytical electron microscoy (AEM) demonstrated that this degradation resulted from facilitated element diffusion and consequent escalating chemical fluctuation at high temperatures, leading to spontaneous segregation and separation of Ce and La elements, forming Ce-rich, La-poor, and La-rich phases. Notably, the La-rich phase spontaneously transformed from a fluorite structure (space group $F m \bar{3} m$ ) to a bixbyite structure (space group $I a \bar{3}$ ) at elevated temperatures, resulting in the appearance of superstructure reflection in XRD profiles and electron diffraction patterns. Despite the intricate phase decomposition, the energy band gap showed minimal variation, suggesting potential property stability of (CeHfZrGdLa)O_x across a broad range of compositions. These findings offer valuable insights into the future applications of HEFOs.

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High-temperature elemental segregation induced structure degradation in high-entropy fluorite oxide

Show Author's information Hide Author's Information Yixuan Hu^¹, Mariappan Anandkumar^², Yumeng Zhang^¹, Joydip Joardar^³, Atul Suresh Deshpande^², Xiaodong Wang^¹, Kolan Madhav Reddy^¹(

)

1School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China

2Department of Materials Science and Metallurgical Engineering, Indian Institute of Technology Hyderabad, Sangareddy 502285, India

3International Advanced Research Centre for Powder Metallurgy and New Materials (ARCI), Hyderabad 500005, India

Abstract

Keywords: phase transition, high-temperature stability, elemental segregation, high-entropy fluorite oxides (HEFOs)

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Acknowledgements

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Publication history

Received: 25 November 2023

Revised: 09 January 2024

Accepted: 18 January 2024

Published: 12 March 2024

Issue date: March 2024

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant Nos. 52150610487 and 51850410501). The authors acknowledge the help of Dr. Linlin Ma for UV–Vis spectra from the Instrumental Analytical Center of Shanghai Jiao Tong University.

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This is an open access article under the terms of the Creative Commons Attribution 4.0 International License (CC BY 4.0, http://creativecommons.org/licenses/by/4.0/).