Abstract
Anomalous phase separation in metallic glasses is a longstanding issue that has been controversial since it was first implied in 1969 due to the influence of microstructure artifacts and the lack of direct large-scale (over nanoscale) evidence. This study confirms an ultralarge scale anomalous glass phase separation phenomenon in a Cr-Fe-Co-Ni-Zr high-entropy metallic glass in which any pair of atomic components has a nonpositive heat of mixing using interferencefree visible-light, atomic force, scanning electron, and double spherical aberration-corrected atomic resolution analytical electron microscopes. The second glassy phase separated from the glassy matrix has an ultralarge size of tens of micrometers, which can be controlled by the cooling rate during sample preparation. A mechanism of before-monotectic-like liquid immiscibility is introduced to interpret the phenomenon, which helps understand the anomalous phase separation in metallic glasses and in other fields, such as liquid-liquid phase separation in cells.
摘要
金属玻璃中的反常相分离是一个长期未解决的问题, 由于受到 微观结构假象以及缺乏直接的大尺度(超过纳米尺度)证据的影响, 自 从1969年首次被提出以来一直备受争议. 本研究综合应用无干扰可见 光显微镜、原子力显微镜、扫描电子显微镜和双球差校正原子分辨 分析电镜, 在具有负混合热的Cr-Fe-Co-Ni-Zr高熵金属玻璃体系中确 认了一种超大尺度上的反常玻璃相分离现象. 分离的第二相具有数十 微米的尺度并且可由冷却速率调控. 引入类似偏晶前的液体不混融机 制来解释反常相分离, 这一机制不仅有利于理解金属玻璃中的反常相 分离行为, 而且也有助于理解其他领域的相分离行为, 比如细胞中的 液-液相分离行为.
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Acknowledgements
This work was financially supported by the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB30000000), the National Natural Science Foundation of China (52192600, 11790291, 61888102, 61999102, 52001220, and 51822107), the National Key Research and Development Plan (2018YFA0703603), and the Natural Science Foundation of Guangdong Province (2019B030302010). We thank Da-Wei Ding, De-Qian Zhao, Wei-Wei Wu, and Rui Zhao for their assistance in experiments.
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Bai HY supervised the project. Huang Y designed and performed the experiments. Weng ST, Jiang HY, Liu XZ and Wang XF helped with the Cs-TEM tests and analysis. Liu ZP conducted the DFT calculation and AIMD simulation. Wang YT, Shen LQ, Sun BY and Yang F helped with the SEM, AFM, nanoindentation and XRD tests and analysis. Huang Y and Bai HY analyzed the data. Sun YH, Lu Z, Sun BA, and Wang ZJ assisted in data interpretation and experiment instruction. Huang Y and Bai HY wrote and revised the manuscript.
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Supporting data are available in the online version of the paper.
Yao Huang is currently a PhD candidate at the Institute of Physics, Chinese Academy of Science (IOP, CAS). He received his bachelor’s degree (majored in materials science and engineering) from the Institute of Powder Metallurgy, Central South University in 2018. His PhD research focuses on the phase behavior and applications of metals/alloys, especially the melts and metallic glasses.
Hai-Yang Bai received her PhD degree from the IOP, CAS in 1991. She is currently a researcher and doctoral supervisor of the IOP, CAS. Her research interests include (1) low-temperature physical properties of metastable materials (e.g., nanomaterials, new bulk amorphous materials, and composite functional materials), including thermal, electrical, magnetic, and mechanical properties; (2) the relationship between the structure and properties of metastable materials; (3) the relationship between structure evolution and properties of metastable materials; and (4) the microscopic mechanism of special properties and effects of metastable materials.
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Huang, Y., Weng, ST., Jiang, HY. et al. Ultralarge-scale anomalous phase separation discovered in a Cr-Fe-Co-Ni-Zr high-entropy metallic glass system. Sci. China Mater. 66, 335–342 (2023). https://doi.org/10.1007/s40843-022-2106-3
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DOI: https://doi.org/10.1007/s40843-022-2106-3