Abstract
Non-equiatomic high-entropy alloys (HEAs), the second-generation multi-phase HEAs, have been recently reported with outstanding properties that surpass the typical limits of conventional alloys and/or the first-generation equiatomic single-phase HEAs. For magnetocaloric HEAs, non-equiatomic (Gd36Tb20Co20Al24)100−xFex microwires, with Curie temperatures up to 108 K, overcome the typical low temperature limit of rare-earth-containing HEAs (which typically concentrate lower than around 60 K). For alloys with x = 2 and 3, they possess some nanocrystals, though very minor, which offers a widening in the Curie temperature distribution. In this work, we further optimize the magnetocaloric responses of x = 3 microwires by microstructural control using the current annealing technique. With this processing method, the precipitation of nanocrystals within the amorphous matrix leads to a phase compositional difference in the microwires. The multi-phase character leads to challenges in rescaling the magnetocaloric curves, which is overcome by using two reference temperatures during the scaling procedure. The phase composition difference increases with increasing current density, whereby within a certain range, the working temperature span broadens and simultaneously offers relative cooling power values that are at least 2-fold larger than many reported conventional magnetocaloric alloys, both single amorphous phase or multi-phase character (amorphous and nanocrystalline). Among the amorphous rare-earth-containing HEAs, our work increases the working temperature beyond the typical <60 K limit while maintaining a comparable magnetocaloric effect. This demonstrates that microstructural control is a feasible way, in addition to appropriate compositional design selection, to optimize the magnetocaloric effect of HEAs.
摘要
第二代高熵合金(非等原子比)具备超越传统合金和第一代等原 子比单相高熵合金性能限制的优异性能. 对于磁热高熵合金, 非等原子 比(Gd36Tb20Co20Al24)100−xFex纤维的居里温度最高达108 K, 这克服了含 稀土高熵合金低温(即普遍工作温区在60 K以下)的限制. x = 2和3合金 含有微量纳米晶, 这使得合金具有宽化的居里温度分布. 本文使用电流 退火技术, 通过对微观结构调控进一步优化x = 3纤维的磁热性能. 电流 退火使纤维非晶基体沉淀析出纳米晶, 并造成两相间成分的差异. 缩放 过程中使用两个参考温度, 克服多相特征所造成的缩放磁热曲线的困 难. 两相成分差异随着电流密度的增加而增大, 在一定限度内, 成分差 异扩大纤维工作温区, 同时使相对制冷能力提升至许多传统磁热合金 (无论是单非晶相还是多相(非晶和纳米晶))的2倍以上. 相比于其他含 稀土高熵非晶合金, 本项工作显示出在温度限制(60 K)之上较好的磁热 性能. 这揭示了除适当的成分设计外, 微观结构调控是优化高熵合金磁 热性能的可行方法.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
Franco V, Blázquez JS, Ipus JJ, et al. Magnetocaloric effect: From materials research to refrigeration devices. Prog Mater Sci, 2018, 93: 112–232
Chaudhary V, Chen X, Ramanujan RV. Iron and manganese based magnetocaloric materials for near room temperature thermal management. Prog Mater Sci, 2019, 100: 64–98
Gschneidner Jr. KA, Pecharsky VK. Magnetocaloric materials. Annu Rev Mater Sci, 2000, 30: 387–429
Gottschall T, Skokov KP, Fries M, et al. Making a cool choice: The materials library of magnetic refrigeration. Adv Energy Mater, 2019, 9: 1901322
Guo D, Moreno-Ramírez LM, Romero-Muñiz C, et al. First- and second-order phase transitions in RE6Co2Ga (RE = Ho, Dy or Gd) cryogenic magnetocaloric materials. Sci China Mater, 2021, 64: 2846–2857
Feng JQ, Liu YH, Sui JH, et al. Giant refrigerant capacity in Gd-based amorphous/nanocrsytalline composite fibers. Mater Today Phys, 2021, 21: 100528
Liu JS, Qu GD, Wang XF, et al. Influence of Fe-doping amounts on magnetocaloric properties of Gd-based amorphous microfibers. J Alloys Compd, 2020, 845: 156190
Kuz’min MD. Factors limiting the operation frequency of magnetic refrigerators. Appl Phys Lett, 2007, 90: 251916
Vuarnoz D, Kawanami T. Numerical analysis of a reciprocating active magnetic regenerator made of gadolinium wires. Appl Thermal Eng, 2012, 37: 388–395
Cantor B, Chang ITH, Knight P, et al. Microstructural development in equiatomic multicomponent alloys. Mater Sci Eng-A, 2004, 375–377: 213–218
Yeh JW, Chen SK, Lin SJ, et al. Nanostructured high-entropy alloys with multiple principal elements: Novel alloy design concepts and outcomes. Adv Eng Mater, 2004, 6: 299–303
Zhang W, Liaw PK, Zhang Y. Science and technology in high-entropy alloys. Sci China Mater, 2018, 61: 2–22
Zhang Y. High-Entropy Materials. Singapore: Springer, 2019
Lu SF, Ma L, Wang J, et al. Effect of configuration entropy on magnetocaloric effect of rare earth high-entropy alloy. J Alloys Compd, 2021, 874: 159918
Lu SF, Ma L, Rao GH, et al. Magnetocaloric effect of high-entropy rare-earth alloy GdTbHoErY. J Mater Sci-Mater Electron, 2021, 32: 10919–10926
Li Z, Pradeep KG, Deng Y, et al. Metastable high-entropy dual-phase alloys overcome the strength-ductility trade-off. Nature, 2016, 534: 227–230
Ma Y, Wang Q, Zhou X, et al. A novel soft-magnetic B2-based multiprincipal-element alloy with a uniform distribution of coherent body-centered-cubic nanoprecipitates. Adv Mater, 2021, 33: 2006723
Kurniawan M, Perrin A, Xu P, et al. Curie temperature engineering in high entropy alloys for magnetocaloric applications. IEEE Magn Lett, 2016, 7: 1–5
Perrin A, Sorescu M, Burton MT, et al. The role of compositional tuning of the distributed exchange on magnetocaloric properties of high-entropy alloys. J Miner Metal Mater Soc, 2017, 69: 2125–2129
Yin H, Law JY, Huang Y, et al. Design of Fe-containing GdTbCoAl high-entropy-metallic-glass composite microwires with tunable Curie temperatures and enhanced cooling efficiency. Mater Des, 2021, 206: 109824
Luo L, Shen HX, Bao Y, et al. Magnetocaloric effect of melt-extracted high-entropy Gd19Tb19Er18Fe19Al25 amorphous microwires. J Magn Magn Mater, 2020, 507: 166856
Law JY, Díaz-García Á, Moreno-Ramírez LM, et al. Increased magnetocaloric response of FeMnNiGeSi high-entropy alloys. Acta Mater, 2021, 212: 116931
Law JY, Moreno-Ramírez LM, Díaz-García Á, et al. MnFeNiGeSi high-entropy alloy with large magnetocaloric effect. J Alloys Compd, 2021, 855: 157424
Law JY, Franco V. Pushing the limits of magnetocaloric high-entropy alloys. APL Mater, 2021, 9: 080702
Zhang YK, Wu BB, Guo D, et al. Magnetic properties and promising cryogenic magneto-caloric performances of Gd20Ho20Tm20Cu20Ni20 amorphous ribbons. Chin Phys B, 2021, 30: 017501
Pang CM, Yuan CC, Chen L, et al. Effect of Yttrium addition on magnetocaloric properties of Gd-Co-Al-Ho high entropy metallic glasses. J Non-Cryst Solids, 2020, 549: 120354
Li LW, Xu C, Yuan Y, et al. Large refrigerant capacity induced by tablelike magnetocaloric effect in amorphous Er0.2Gd0.2Ho0.2Co0.2Cu0.2 ribbons. Mater Res Lett, 2018, 6: 413–418
Xue L, Shao LL, Luo Q, et al. Gd25RE25Co25Al25 (RE = Tb, Dy and Ho) high-entropy glassy alloys with distinct spin-glass behavior and good magnetocaloric effect J Alloys Compd, 2019, 790: 633–639
Zhang YK, Zhu J, Li S, et al. Achievement of giant cryogenic refrigerant capacity in quinary rare-earths based high-entropy amorphous alloy. J Mater Sci Tech, 2022, 102: 66–71
Law JY, Franco V Magnetocaloric composite materials In: Brabazon D (Ed.). Encyclopedia of Materials: Composites. Vol. 2. Oxford: Elsevier, 2021, 461–472
Doblas D, Moreno-Ramírez LM, Franco V, et al. Nanostructuring as a procedure to control the field dependence of the magnetocaloric effect. Mater Des, 2017, 114: 214–219
Sánchez-Pérez M, Moreno-Ramírez LM, Franco V, et al. Influence of nanocrystallization on the magnetocaloric properties of Ni-based amorphous alloys: Determination of critical exponents in multiphase systems. J Alloys Compd, 2016, 686: 717–722
Liu JS, Huang MF, Wu MJ, et al. Effect of current annealing treatment on magnetic properties of Gd-Al-Co-Fe metallic microfibers. J Alloys Compd, 2021, 855: 157231
Zhong XC, Mo HY, Huang XW, et al. Effects of crystallization treatment on the structure and magnetic properties of Gd65Fe25Zn10 alloy ribbons for magnetic refrigeration. J Alloys Compd, 2018, 730: 493–500
Belliveau HF, Yu YY, Luo Y, et al. Improving mechanical and magnetocaloric responses of amorphous melt-extracted Gd-based micro-wires via nanocrystallization. J Alloys Compd, 2017, 692: 658–664
Li FC, Liu T, Zhang JY, et al. Amorphous-nanocrystalline alloys: Fabrication, properties, and applications. Mater Today Adv, 2019, 4: 100027
Wang CX, Wu ZY, Feng XM, et al. The effects of magnetic field annealing on the magnetic properties and microstructure of Fe80Si9B11 amorphous alloys. Intermetallics, 2020, 118: 106689
Fan XZ, He XW, Nutor RK, et al. Effect of stress on crystallization behavior in a Fe-based amorphous ribbon: An in situ synchrotron radiation X-ray diffraction study. J Magn Magn Mater, 2019, 469: 349–353
Liu JS, Shen HX, Xing DW, et al. Optimization of GMI properties by AC Joule annealing in melt-extracted Co-rich amorphous wires for sensor applications. Phys Status Solidi A, 2014, 211: 1577–1582
Yuan Y, Wu Y, Tong X, et al. Rare-earth high-entropy alloys with giant magnetocaloric effect. Acta Mater, 2017, 125: 481–489
Franco V, Conde A. Scaling laws for the magnetocaloric effect in second order phase transitions: From physics to applications for the characterization of materials. Int J Refrig, 2010, 33: 465–473
Yin H, Huang Y, Daisenberg D, et al. Atomic structure evolution of high entropy metallic glass microwires at cryogenic temperature. Scripta Mater, 2019, 163: 29–33
Houssa R, Franco V, Conde A. Microstructure and magnetic properties of a FeSiB-CuNb alloy submitted to Joule heating. J Magn Magn Mater, 1999, 203: 199–201
Kaeswurm B, Franco V, Skokov KP, et al. Assessment of the magnetocaloric effect in La,Pr(Fe,Si) under cycling. J Magn Magn Mater, 2016, 406: 259–265
Franco V, Blázquez JS, Conde A. Field dependence of the magnetocaloric effect in materials with a second order phase transition: A master curve for the magnetic entropy change. Appl Phys Lett, 2006, 89: 222512
Franco V, Caballero-Flores R, Conde A, et al. The influence of a minority magnetic phase on the field dependence of the magnetocaloric effect. J Magn Magn Mater, 2009, 321: 1115–1120
Díaz-García Á, Law JY, Gebara P, et al. Phase deconvolution of multiphasic materials by the universal scaling of the magnetocaloric effect. J Miner Metal Mater Soc, 2020, 72: 2845–2852
Díaz-García Á, Law JY, Moreno-Ramírez LM, et al. Deconvolution of overlapping first and second order phase transitions in a NiMnIn Heusler alloy using the scaling laws of the magnetocaloric effect. J Alloys Compd, 2021, 871: 159621
Cao GY, Wang QX, Liu JS, et al. Enhanced magnetic entropy change and refrigeration capacity of La(Fe,Ni)11.5Si1.5 alloys through vacuum annealing treatment. J Alloys Compd, 2019, 800: 363–371
Franco V, Blázquez JS, Conde A The influence of Co addition on the magnetocaloric effect of Nanoperm-type amorphous alloys J Appl Phys, 2006, 100: 064307
Law JY, Franco V, Moreno-Ramírez LM, et al. A quantitative criterion for determining the order of magnetic phase transitions using the magnetocaloric effect Nat Commun, 2018, 9: 2680
Franco V, Law JY, Conde A, et al. Predicting the tricritical point composition of a series of LaFeSi magnetocaloric alloys via universal scaling J Phys D-Appl Phys, 2017, 50: 414004
Moreno-Ramírez LM, Blázquez JS, Franco V, et al. Magnetocaloric response of amorphous and nanocrystalline Cr-containing Vitroperm-type alloys J Magn Magn Mater, 2016, 409: 56–61
Franco V, Conde A, Pecharsky VK, et al. Field dependence of the magnetocaloric effect in Gd and (Er1−xDyx)Al2: Does a universal curve exist? Europhys Lett, 2007, 79: 47009
Zou LM, Li YH, Yang C, et al. Effect of Fe content on glass-forming ability and crystallization behavior of a (Ti69.7Nb23.7Zr4.9Ta1.7)100−xFex alloy synthesized by mechanical alloying J Alloys Compd, 2013, 553: 40–47
Zhang LC, Xu J, Ma E. Mechanically alloyed amorphous Ti50(Cu0.45 Ni0.55)44−xAlxSi4B2 alloys with supercooled liquid region. J Mater Res, 2002, 17: 1743–1749
Zhang LC, Xu J Glass-forming ability of melt-spun multicomponent (Ti, Zr, Hf)-(Cu, Ni, Co)-Al alloys with equiatomic substitution. J Non-Cryst Solids, 2004, 347: 166–172
Franco V, Conde A, Romero-Enrique JM, et al. Field dependence of the adiabatic temperature change in second order phase transition materials: Application to Gd J Appl Phys, 2009, 106: 103911
Fu H, Zhang XY, Yu HJ, et al. Large magnetic entropy change of Gd-based ternary bulk metallic glass in liquid-nitrogen temperature range Solid State Commun, 2008, 145: 15–17
Du J, Zheng Q, Li YB, et al. Large magnetocaloric effect and enhanced magnetic refrigeration in ternary Gd-based bulk metallic glasses J Appl Phys, 2008, 103: 023918
Hui XD, Xu ZY, Wang ER, et al. Excellent magnetocaloric effect in Er60Al18Co22 bulk metallic glass. Chin Phys Lett, 2010, 27: 117502
Hui XD, Xu ZY, Wu Y, et al. Magnetocaloric effect in Er-Al-Co bulk metallic glasses Chin Sci Bull, 2011, 56: 3978–3983
Li JW, Law JY, Huo JT, et al. Magnetocaloric effect of Fe-RE-B-Nb (RE = Tb, Ho or Tm) bulk metallic glasses with high glass-forming ability J Alloys Compd, 2015, 644: 346–349
Li JW, Law JY, Ma HR, et al. Magnetocaloric effect in Fe-Tm-B-Nb metallic glasses near room temperature J Non-Cryst Solids, 2015, 425: 114–117
Moreno LM, Blázquez JS, Ipus JJ, et al. Magnetocaloric effect of Co62Nb6Zr2B30 amorphous alloys obtained by mechanical alloying or rapid quenching. J Appl Phys, 2014, 115: 17A302
Yuan F, Li Q, Shen BL. The effect of Fe/Al ratio on the thermal stability and magnetocaloric effect of Gd55FexAl45-x (x = 15–35) glassy ribbons. J Appl Phys, 2012, 111: 07A937
Law JY, Franco V, Ramanujan RV. The magnetocaloric effect of partially crystalline Fe-B-Cr-Gd alloys. J Appl Phys, 2012, 111: 113919
Mo HY, Zhong XC, Jiao DL, et al. Table-like magnetocaloric effect and enhanced refrigerant capacity in crystalline Gd55Co35Mn10 alloy melt spun ribbons. Phys Lett A, 2018, 382: 1679–1684
Wang ZW, Yu P, Cui YT, et al. Near room temperature magnetocaloric effect of a Gd48Co52 amorphous alloy. J Alloys Compd, 2016, 658: 598–602
Zhang LL, Bao MD, Zheng Q, et al. Magnetocaloric effect in high Gd content Gd-Fe-Al based amorphous/nanocrystalline systems with enhanced Curie temperature and refrigeration capacity. AIP Adv, 2016, 6: 035220
Belyea DD, Lucas MS, Michel E, et al. Tunable magnetocaloric effect in transition metal alloys. Sci Rep, 2015, 5: 15755
Vorobiov S, Pylypenko O, Bereznyak Y, et al. Magnetic properties, magnetoresistive, and magnetocaloric effects of AlCrFeCoNiCu thin-film high-entropy alloys prepared by the co-evaporation technique. Appl Phys A, 2021, 127: 179
Na SM, Lambert PK, Kim H, et al. Thermomagnetic properties and magnetocaloric effect of FeCoNiCrAl-type high-entropy alloys. AIP Adv, 2019, 9: 035010
Liang L, Hui X, Wu Y, et al. Large magnetocaloric effect in Gd36Y20Al24Co20 bulk metallic glass. J Alloys Compd, 2008, 457: 541–544
Luo Q, Schwarz B, Mattern N, et al. Giant irreversible positive to large reversible negative magnetic entropy change evolution in Tb-based bulk metallic glass. Phys Rev B, 2010, 82: 024204
Acknowledgements
The authors acknowledge the financial support from the National Natural Science Foundation of China (51827801, 51871076, 52171154, and 51801044), and the 66th China Postdoctoral Science Foundation (2019M661275). Franco V and Law JY acknowledge the funding from 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). Yin H acknowledges the fellowship from China Scholarship Council (CSC, 201906120183) for Visiting PhD Student program.
Funding
Funding note Open Access funding provided thanks to the CRUE-CSIC agreement with Springer Nature.
Author information
Authors and Affiliations
Contributions
Author contributions Yin H, Huang Y, and Shen H conceived the ideas and designed the study; Yin H and Shen H prepared the microwires; Yin H and Jiang S did the PPMS measurements; Yin H did the DSC measurements; Yin H performed the SEM measurements; Guo S performed the TEM characterization; Yin H, Huang Y, Law JY, and Franco V analyzed the data; Yin H and Law JY wrote the manuscript. All authors reviewed and commented on the manuscript and approved the final version of the paper.
Corresponding authors
Ethics declarations
Conflict of interest The authors declare that they have no conflict of interest.
Additional information
Supplementary information Supporting data are available in the online version of the paper.
Hangboce Yin is a PhD student, pursuing double PhD degree from Harbin Institute of Technology (HIT, China) and University of Seville (Spain). His research focuses on the microstructures, magnetic properties, and magnetocaloric effect of rare-earth-containing high-entropy alloys.
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 of “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 the additive manufacturing.
Hongxian Shen received his PhD degree in Material Processing Engineering from HIT in 2017. Now he is an assistant professor at HIT. His research interests focus on material design and magnetic properties of rare-earth-based amorphous, medium-entropy and high-entropy alloy microwires.
Yongjiang Huang obtained his PhD degree from HIT, China in 2008. His interests mainly focus on bulk metallic glasses and their composites, high-entropy alloys, and additive manufacturing of advanced metallic materials.
Rights and permissions
Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made.
The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder.
To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.
About this article
Cite this article
Yin, H., Law, J.Y., Huang, Y. et al. Enhancing the magnetocaloric response of high-entropy metallic-glass by microstructural control. Sci. China Mater. 65, 1134–1142 (2022). https://doi.org/10.1007/s40843-021-1825-1
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s40843-021-1825-1