Martensitic transformation and magnetocaloric effect of rare earth-doped all-d-metal Ni37Co13Mn35Ti15-xRx (R=Er, Dy) alloy ribbons
LIU Meng1, CHEN Hanxiao1,2,3,*, WANG Zihan1,2, SHEN Bangpo1,2,3, XU Lei1,2, ZHANG Zhishuo1,2, HU Qiubo4, MA Shengcan1,2,3
1. Jiangxi Provincial Key Laboratory of Magnetic Metallic Materials and Devices, College of Rare Earths, Jiangxi University of Science and Technology , Ganzhou 341000, China; 2. National Rare Earth Functional Material Innovation Center/Guorui Scientific Innovation Rare Earth Functional Materials Co., Ltd, Ganzhou 341000, China; 3. School of Materials Science and Engineering, Faculty of Materials Metallurgy and Chemistry, Jiangxi University of Science and Technology, Ganzhou 341000, China; 4. Department of Mathematics and Physics, Luoyang Institute of Science and Technology, Luoyang 471000, China
Abstract：Amid the dual challenges of global warming and the energy crisis, magnetic refrigeration technology has emerged as a promising solution. Utilizing the magnetocaloric effect, this technology offers advantages such as high efficiency, energy conservation, and environmental friendliness, making it a potential alternative to conventional gas compression refrigeration. Among magnetocaloric materials, Heusler-type Ni-Mn-based alloys have attracted significant attention, primarily due to their tunable magnetic phase transitions and remarkable magnetocaloric effects. In this study, Heusler alloy Ni37Co13Mn35Ti15-xRx (x=0.3, 0.5, 0.7, 1.0) ribbons were prepared via the melt-spinning method, focusing on the effects of rare-earth Er and Dy doping on the martensitic transformation behavior and magnetocaloric properties. The results indicate that the martensitic transformation temperature (Tt) of the alloys initially increases and subsequently decreases with rising rare-earth content. Specifically, it rises significantly from 190 K (0.1 T) for the undoped Ni37Co13Mn35Ti15 to above room temperature, then declining back to the vicinity of room temperature at x=1.0. Overall, the Tt of Dy-doped samples are higher than those of Er-doped samples. Ni37Co13Mn35Ti14.5Dy0.5 exhibits the optimal magnetocaloric performance, its maximum magnetic entropy change is superior to that of the undoped sample, reaching 15.31 J/(kg·K) under a magnetic field change of 0-5 T. For the Ni37Co13Mn35Ti14Dy1, the peak of the magnetic entropy change shifts rapidly towards lower temperatures with increasing magnetic field, resulting in the widest refrigeration temperature window. Furthermore, clear lath-like martensitic microstructures are observed in Ni37Co13Mn35Ti14.5Dy0.5, providing important structural evidence for understanding the variations in its properties.
[1] GSCHNEIDNER K A, PECHARSKY V K, TSOKOL A O.Recent developments in magnetocaloric materials[J]. Reports on Progress in Physics, 2005, 68: 1479. [2] 郑新奇, 沈俊, 胡凤霞, 等. 磁热效应材料的研究进展[J]. 物理学报, 2016, 65(21): 7-40. ZHENG Xinqi, SHEN Jun, HU Fengxia, et al.Research progress in magnetocaloric effect materials[J]. Acta Physica Sinica, 2016, 65(21): 7-40. [3] 林源, 胡凤霞, 沈保根. 相变调控、磁热效应和反常热膨胀[J]. 物理学报, 2023, 72(23): 246-268. LIN Yuan, HU Fengxia, SHEN Baogen.Phase transition regulation, magnetocaloric effect, and abnormal thermal expansion[J]. Acta Physica Sinica, 2023, 72(23): 246-268. [4] TEGUS O, BRÜCK E, BUSCHOW K H J, et al. Transition-metal-based magnetic refrigerants for room-temperature applications[J]. Nature, 2002, 415: 150-152. [5] SHEN B G, SUN J R, HU F X, et al.Recent progress in exploring magnetocaloric materials[J]. Advanced Materials, 2009, 21(45): 4545-4564. [6] ZHANG H, SHEN B G.Magnetocaloric effects in RTX intermetallic compounds (R=Gd-Tm, T=Fe-Cu and Pd, X= Al and Si)[J]. Chinese Physics B, 2015, 24(12): 127504. [7] KORTE B J, PECHARSKY V K, GSCHNEIDNER Jr.K A. The correlation of the magnetic properties and the magnetocaloric effect in (Gd1-xErx)NiAl alloys[J]. Journal of Applied Physics, 1998, 84(10): 5677-5685. [8] VON RANKE P J, PECHARSKY V K, GSCHNEIDNER Jr. K A. Influence of the crystalline electrical field on the magnetocaloric effect of DyAl2, ErAl2, and DyNi2[J]. Physical Review B, 1998, 58(18): 12110-12116. [9] WANG Y P, XIANG J S, ZHANG L, et al.Giant low-field cryogenic magnetocaloric effect in a polycrystalline EuB4O7 compound[J]. Journal of the American Chemical Society, 2024, 146(5): 3315-3322. [10] TANG Y C, LI S L, LIU S P, et al.Multi-model-driven prediction of magnetic phase transitions and magnetocaloric effects in NiMnFeCoBP high-entropy amorphous alloys[J]. Applied Physics Letters, 2025, 127(9): 092401. [11] MO Z J, JIANG J X, TIAN L, et al.Ferromagnetic Eu2SiO4 compound with a record low-field magnetocaloric effect and excellent thermal conductivity near liquid helium temperature[J]. Journal of the American Chemical Society, 2025, 147(17): 14684-14693. [12] BROWN G V.Magnetic heat pumping near room temperature[J]. Journal of Applied Physics, 1976, 47(8): 3673-3680. [13] HU F X, SHEN B G, SUN J R, et al.Influence of negative lattice expansion and metamagnetic transition on magnetic entropy change in the compound LaFe11.4Si1.6[J]. Applied Physics Letters, 2001, 78(23): 3675-3677. [14] ZHANG F Q, WU Z Y, GONG Y, et al.Atomic vacancy defect modulated giant magnetocaloric effect in multi-component MnCoNiGeSi based compounds[J]. Acta Materialia, 2025, 300:121508. [15] QIAO K M, CUI Z, HAO X W, et al.Giant room-temperature magnetocaloric effect MM′X alloys explored by machine learning[J]. Acta Materialia, 2025, 297: 121344. [16] 王家旭, 张一心, 马圣然, 等. Ni2Cu基Heusler合金的电子结构、弹性参数与马氏体相变的第一性原理研究[J]. 物理学报, 2025, 74(4): 218-228. WANG Jiaxu, ZHANG Yixin, MA Shengran, et al.First principles study of electronic structure, mechanical properties and possible martensitic transformation in Ni2Cu-based Heusler alloys[J]. Acta Physica Sinica, 2025,74(4): 218-228. [17] CHEN H D, LIU M Z, YU Z Y, et al.Enhanced heat transfer for thermomagnetic generation in low-grade waste heat harvesting[J]. Advanced Materials, 2025, 37(21): 2500544. [18] WEI Z Y, LIU E K, CHEN J H, et al.Realization of multifunctional shape-memory ferromagnets in all-d-metal Heusler phases[J]. Applied Physics Letters, 2015, 107(2): 022406. [19] WEI Z Y, LIU E K, LI Y, et al.Magnetostructural martensitic transformations with large volume changes and magneto-strains in all-d-metal Heusler alloys[J]. Applied Physics Letters, 2016, 109(7): 071904. [20] LIU Y, XIAO A D, YANG T Z, et al.Enhancing reversible entropy change of all-d-metal Ni37.5Co12.5Mn35Ti15 alloy by multiple external fields[J]. Scripta Materialia, 2022, 207: 114303. [21] 李晨博, 王子谦, 吴俊峰, 等. Ni-Cr-W体系热力学评估[J]. 粉末冶金材料科学与工程, 2025, 30(3): 171-178. LI Chenbo, WANG Ziqian, WU Junfeng, et al.Thermodynamic assessment of Ni-Cr-W system[J]. Materials Science and Engineering of Powder Metallurgy, 2025, 30(3): 171-178. [22] 何山, 蔡高参, 潘昱枫. 钛合金粉末叶轮盘热等静压成形性能[J]. 粉末冶金材料科学与工程, 2024, 29(3): 172-180. HE Shan, CAI Gaoshen, PAN Yufeng.Hot isostatic pressing forming performance of titanium alloy powder impeller disc[J]. Materials Science and Engineering of Powder Metallurgy, 2024, 29(3): 172-180. [23] LIU K, MA S C, MA C C, et al.Martensitic transformation and giant magneto-functional properties in all-d-metal Ni-Co-Mn-Ti alloy ribbons[J]. Journal of Alloys and Compounds, 2019, 790: 78-92. [24] HUANG S Y, QIN L, LI Y, et al.The study of martensitic transformation and magnetocaloric effect in rare earth Y-doped all-d-metal Ni-Co-Mn-Ti Heusler alloys[J]. Materials Letters, 2021, 302: 130376. [25] ZHANG F Q, WESTRA K, SHEN Q, et al.The second-order magnetic phase transition and magnetocaloric effect in all-d-metal NiCoMnTi-based Heusler alloys[J]. Journal of Alloys and Compounds, 2022, 906: 164337. [26] XU F, ZHU C, WANG J, et al.Enhanced elastocaloric effect and mechanical properties of Gd-doped Ni-Co-Mn-Ti-Gd metamagnetic shape memory alloys[J]. Journal of Alloys and Compounds, 2023, 960: 170768. [27] KHAN A N, MORENO-RAMÍREZ L M, DÍAZ-GARCÍA Á, et al. All-d-metal Ni(Co)-Mn(X)-Ti (X=Fe or Cr) Heusler alloys: enhanced magnetocaloric effect for moderate magnetic fields[J]. Journal of Alloys and Compounds, 2023, 931: 167559. [28] ZHANG F Q, WU Z Y, WANG J L, et al.Impact of fast-solidification on all-d-metal NiCoMnTi based giant magnetocaloric Heusler compounds[J]. Acta Materialia, 2024, 265: 119595. [29] ZENG Q Q, DU Z W, HAN X L, et al.Observation of atomically displacive transformation out of the boundary-reconstructive phase competition[J]. Acta Materialia, 2024, 262: 119429. [30] LI B, LIU Z P, LI D, et al.Large reversible multicaloric effects over a broad refrigeration temperature range in Co and B co-doped Ni-Mn-Ti alloys[J]. Materials Science and Engineering A, 2024, 896:146260. [31] SUN S D, BAI J, GU J L, et al.Extraordinary mechanical properties and room-temperature magnetocaloric effects in spark plasma sintered all-d-metal Ni-Co-Mn-Ti alloy[J]. Journal of Alloys and Compounds, 2024, 976: 173406. [32] KHAN A N, DÍAZ-GARCÍA Á, MORENO-RAMÍREZ L M, et al. Tunable magnetocaloric effect towards cryogenic range by varying Mn:Ni ratio in all-d-metal Ni(Co)-Mn-Ti Heusler alloys[J]. Journal of Alloys and Compounds, 2024, 973: 172938. [33] CARON L, OU Z Q, NGUYEN T T, et al.On the determination of the magnetic entropy change in materials with first-order transitions[J]. Journal of Magnetism and Magnetic Materials, 2009, 321(21): 3559-3566. [34] RIETVELD H M.A profile refinement method for nuclear and magnetic structures[J]. Journal of Applied Crystallography, 1969, 2: 65-71. [35] XU K, LU X, LI X, et al.Enhancement of the mechanical strength in laser powder bed fused La/Ce-rich La-Ce-Fe-Co-Si magnetocaloric materials via crack healing[J]. Materials Characterization, 2025, 229: 115572. [36] SYNORADZKI K, NOWOTNY P, SKOKOWSKI P, et al.Magnetocaloric effect in Gd5(Si,Ge)4 based alloys and composites[J]. Journal of Rare Earths, 2019, 37(11): 1218-1223.
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