Abstract
Rare-earth (RE) rich intermetallics crystallizing in orthorhombic Ho6Co2Ga-type crystal structure exhibit peculiar magnetic properties that are not widely reported for their magnetic ordering, order of magnetic phase transition, and related magnetocaloric behavior. By tuning the type of RE element in RE6Co2Ga (RE = Ho, Dy or Gd) compounds, metamagnetic anti-to-paramagnetic (AF to PM) phase transitions could be tuned to ferro-to-paramagnetic (FM to PM) phase transitions. Furthermore, the FM ground state for Gd6Co2Ga is confirmed by density functional theory calculations in addition to experimental observations. The field dependence magnetocaloric and Banerjee’s criteria demonstrate that Ho6Co2Ga and Dy6Co2Ga undergo a first-order phase transition in addition to a second-order phase transition, whereas only the latter is observed for Gd6Co2Ga. The two extreme alloys of the series, Ho6Co2Ga and Gd6Co2Ga, show maximum isothermal entropy change (∣ΔS maxiso (5 T)∣) of 10.1 and 9.1 J kg−1K−1 at 26 and 75 K, close to H2 and N2 liquefaction, respectively. This outstanding magnetocaloric effect performance makes the RE6Co2Ga series of potential for cryogenic magnetic refrigeration applications.
摘要
具有**交Ho6Co2Ga型晶体结构的富稀土金属间化合物因其具备独特的磁性能而被关注, 但它们的磁有序、 磁相变类型以及磁热性能尚未见系统报道. 本文通过对RE6Co2Ga化合物中的稀土元素类型的调控, 实现了材料相变类型从反铁磁(AF)到顺磁(PM)的变磁调控为铁磁(FM)到顺磁(PM)的转变. 此外, 通过实验观察结合密度泛函理论(DFT)计算证明了Gd6Co2Ga的基态为铁磁态. 利用磁热效应的场依赖性关系结合Banerjee准则的判断标准研究表明, Ho6Co2Ga和Dy6Co2Ga同时具备二级相变和一级相变特征, 而在Gd6Co2Ga中只存在二级相变. 在0–5 T的磁场变化下, Ho6Co2Ga和Gd6Co2Ga的磁熵变分别在26和75 K附**达到最大值10.1和9.1 J kg−1 K−1, 而这两个温度分别接**于H2液化和N2液化温度. 优异的磁热性能使得RE6Co2Ga体系在低温磁制冷领域具有潜在的应用前景.
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Acknowledgements
This work was supported by the National Natural Science Foundation of China (52071197), the Science and Technology Commission of Shanghai Municipality (19ZR1418300 and 19DZ2270200), AEI/FEDER-UE (PID2019-105720RB-I00), US/JUNTA/FEDER-UE (US-1260179), and Consejería de Economía, Conocimiento, Empresas y Universidad de la Junta de Andalucía (P18-RT-746). Guo D would like to acknowledge the support provided by China Scholarship Council (CSC) of the Ministry of Education, China (202006890050).
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Author contributions Zhang Y and Law JY designed the idea of the research. Guo D and Zhang Y performed the experiments. Guo D and Moreno-Ramírez LM performed the data analysis. Romero-Muñiz C contributed to the DFT calculations and analysis. Guo D, Moreno-Ramírez LM, and Law JY prepared the manuscript. All the authors contributed to the general discussion and review and editing. Franco V and Zhang Y contributed to the conceptualization and supervision.
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Dan Guo is a PhD student at the School of Materials Science and Engineering, Shanghai University (SHU), China. She is now a visiting scholar sponsored by the China Scholarship Council at the University of Seville, Spain. Her research interests focus on magnetic properties and magnetocaloric effect of heavy rare-earth-based compounds.
Yikun Zhang is an associate professor at the School of Materials Science and Engineering, SHU (China) since 2016. She received her PhD degree in materials science from Northeastern University (China) in 2010. Her research focuses on designing and exploring low-temperature magnetic refrigeration materials.
Jia-Yan Law obtained her PhD degree from the School of Materials Science and Engineering, Nanyang Technological University, Singapore, in 2012. Currently, she is a postdoctoral researcher at the University of Seville, Spain, leading the research line “Functional High-Entropy Alloys”. In addition, her research interests include the development of magnetic and magnetocaloric materials, device and novel evaluation techniques as well as additive manufacturing.
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Guo, D., Moreno-Ramírez, L.M., Romero-Muñiz, C. et al. First- and second-order phase transitions in RE6Co2Ga (RE = Ho, Dy or Gd) cryogenic magnetocaloric materials. Sci. China Mater. 64, 2846–2857 (2021). https://doi.org/10.1007/s40843-021-1711-5
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DOI: https://doi.org/10.1007/s40843-021-1711-5