Numerical simulation of magnetism and magnetocaloric effect of Mn-Rich Ni-Mn-Ga alloy

WANG Bo; ZHANG Yufen; SHAO Hui; ZHANG Zeyu; HU Yong

doi:10.7498/aps.75.20251394

Abstract
This work investigates the magnetocaloric effect-based green magnetic refrigeration technology, with a focus on Ni-Mn-Ga Heusler alloy as a promising magnetic refrigerant candidate. To elucidate the role of Mn-rich composition in regulating the magnetic and magnetocaloric properties, a multi-scale computational approach integrating first-principles calculations and Monte Carlo simulations is adopted. This method enables a detailed analysis of how Mn atoms occupying Ni and Ga sites influence the microstructure, atomic magnetic moments, exchange interactions, and macroscopic magnetocaloric response of the alloy. The results indicate that Mn site occupancy critically affects the magnetic performance: the occupation of Ni sites reduces the total magnetic moment and Curie temperature, thereby reducing the magnetic entropy change; in contrast, Mn occupying Ga sites significantly enhances both the total magnetic moment and the magnetic entropy change. Notably, the Ni₈Mn₇Ga₁ alloy achieves a maximum magnetic entropy change of 2.32 J·kg^–1·K^–1 under a 2 T magnetic field, which significantly exceeds that of the stoichiometric Ni₈Mn₄Ga₄ alloy. Further electronic structure analysis reveals that Mn content variation modulates the density of states near the Fermi level and optimizes orbital hybridization and ferromagnetic exchange interactions, thus adjusting the magnetic phase transition behavior. Critical exponent analysis confirms that the magnetic interactions are inherently long-range and tend toward mean-field behavior with compositional changes. By establishing a clear “composition-structure-magnetism-magnetocaloric performance” relationship on an atomic scale, this work provides theoretical foundations for designing high-performance, low-hysteresis magnetic refrigeration materials.

Keywords:
Ni-Mn-Ga alloy /

magnetocaloric effect /

second-order magnetic phase transition /

Monte Carlo simulation
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图 1 带有特定成分占比的Ni-Mn-Ga三元合金的晶体结构模型, 其中Mn¹和Mn²分别代表原位和占据Ni或Ga位的Mn原子

Figure 1. Crystal structure models of Ni-Mn-Ga ternary alloys with specific composition ratios, where Mn¹ and Mn² represent Mn atoms of original sites and those occupying Ni or Ga sites, respectively.

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图 2 奥氏体相和马氏体相Ni_8–xMn_4+xGa₄(x = 0, 1, 2)和Ni₈Mn_4+yGa_4–y(y = 0, 1, 2, 3)合金总磁矩和Mn, Ni原子磁矩随成分的变化趋势

Figure 2. Total magnetic moment of alloy and magnetic moments of Mn and Ni atoms as a function of composition in austenitic and martensitic Ni_8–xMn_4+xGa₄ (x = 0, 1, 2) and Ni₈Mn_4+yGa_4–y (y = 0, 1, 2, 3) alloys.

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图 3 不同成分配比的奥氏体相Ni-Mn-Ga合金的总态密度和各元素态密度随能量的变化关系

Figure 3. Total density of states and partial density of states of each elements as a function of energy in austenitic Ni-Mn-Ga alloys.

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图 4 不同成分配比的马氏体相Ni-Mn-Ga合金的总态密度和各元素态密度随能量的变化关系

Figure 4. Total density of states and partial density of states of each elements as a function of energy in martensitic Ni-Mn-Ga alloys.

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图 5 在奥氏体相Ni_8–xMn_4+xGa₄(x = 0, 1, 2)和Ni₈Mn_4+yGa_4–y(y = 0, 1, 2, 3)合金中, Mn-Mn和Mn-Ni交换作用常数随原子间距的变化关系, 其中Mn¹和Mn²分别代表原位和占据Ni或Ga位的Mn原子, 原子间距以晶格常数a为单位

Figure 5. Exchange coupling constants between Mn-Mn and Mn-Ni as a function of distance in austenitic Ni_8–xMn_4+xGa₄ (x = 0, 1, 2)和Ni₈Mn_4+yGa_4–y (y = 0, 1, 2, 3) alloys, where Mn¹ and Mn² represent Mn atoms of original sites and those occupying Ni or Ga sites, respectively, and distance is given in units of lattice constant a.

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图 6 在零外磁场作用下, 奥氏体相Ni_8–xMn_4+xGa₄(x = 0, 1, 2)和Ni₈Mn_4+yGa_4–y(y = 0, 1, 2, 3)合金的磁化强度和磁化率随温度的变化关系, 其中M_S为饱和磁化强度值; 居里温度随富Mn成分的变化关系

Figure 6. Magnetization and magnetic susceptibility as a function of temperature in austenitic Ni_8–xMn_4+xGa (x = 0, 1, 2) and Ni₈Mn_4+yGa_4–y (y = 0, 1, 2, 3) alloys under zero magnetic field, where M_S is the value of saturated magnetization; Curie temperature as a function of composition of excess Mn.

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图 7 在选定的外磁场作用下, 不同成分的奥氏体相Ni-Mn-Ga合金的磁化强度随温度的变化关系, 其中M_S为饱和磁化强度值

Figure 7. Magnetization of austenitic Ni-Mn-Ga alloys with different compositions as a function of temperature under selected magnetic fields, where M_S is the value of saturated magnetization.

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图 8 在选定的外磁场作用下, 不同成分的奥氏体相Ni-Mn-Ga合金的磁熵变随温度的变化关系

Figure 8. Magnetic entropy change of austenitic Ni-Mn-Ga alloys with different compositions as a function of temperature under selected magnetic fields.

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图 9 不同成分的Ni-Mn-Ga合金的最大磁熵变和相对冷却能力随外磁场的变化关系

Figure 9. Maximum magnetic entropy change and relative cooling power as a function of magnetic field in Ni-Mn-Ga alloys with different compositions.

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图 10 在Ni_8–xMn_4+xGa₄(x = 0, 1, 2)和Ni₈Mn_4+yGa_4–y(y = 0, 1, 2, 3)合金中, 计算的参数随成分的变化关系

Figure 10. Calculated parameters as a function of composition in Ni_8–xMn_4+xGa₄ (x = 0, 1, 2) and Ni₈Mn_4+yGa_4–y (y = 0, 1, 2, 3) alloys.

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表 1 不同富Mn成分下的奥氏体相和马氏体相Ni-Mn-Ga合金的晶格常数

Table 1. Crystal lattice constants of austenitic and martensitic Ni-Mn-Ga alloys with different Mn-rich compositions.

	Austenite			Martensite
	a/Å	b/Å	c/Å	a/Å	b/Å	c/Å
Ni₈Mn₄Ga₄ (x/y = 0)	5.809	5.809	5.809	5.322	5.322	6.919
Ni₇Mn₅Ga₄ (x = 1)	5.800	5.800	5.800	5.314	5.314	6.908
Ni₆Mn₆Ga₄ (x = 2)	5.785	5.785	5.785	5.300	5.300	6.891
Ni₈Mn₅Ga₃ (y = 1)	5.818	5.818	5.818	5.331	5.331	6.931
Ni₈Mn₆Ga₂ (y = 2)	5.828	5.828	5.828	5.340	5.340	6.942
Ni₈Mn₇Ga₁ (y = 3)	5.834	5.834	5.834	5.346	5.346	6.949

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[1]	Dong Y, Coleman M, Miller S A 2021 Annu. Rev. Environ. Resour. 46 59 Google Scholar
[2]	Zimm C, Jastrab C, Sternberg A, Pecharsky V K, Gschneidner Jr K A, Osborne M, Anderson I 1998 Adv. Cryog. Eng. 43 1759
[3]	Pecharsky V K, Gschneidner Jr K A 1997 Phys. Rev. Lett. 78 4494 Google Scholar
[4]	Provenzano V, Shapiro A J, Shull R D 2004 Nature (London) 429 853 Google Scholar
[5]	Tegus O, Brück E, Buschow K H J, de Boer R D 2002 Nature (London) 415 150 Google Scholar
[6]	郑新奇, 沈俊, 胡凤霞, 孙继荣, 沈保根 2016 物理学报 65 217502 Google Scholar Zheng X Q, Shen J, Hu F X, Sun J R, Shen B G 2016 Acta Phys. Sin. 65 217502 Google Scholar
[7]	李瑞, 沈俊, 张志鹏, 李振兴, 莫兆军, 高新强, 海鹏, 付琪 2024 物理学报 73 037501 Google Scholar Li R, Shen J, Zhang Z P, Li Z X, Mo Z J, Gao X Q, Hai P, Fu Q 2024 Acta Phys. Sin. 73 037501 Google Scholar
[8]	Tickle R, James R D 1999 J. Magn. Magn. Mater. 195 627 Google Scholar
[9]	Chen J, Hana Z, Qiana B, Zhang P, Wang D, Duc Y 2011 J. Magn. Magn. Mater. 323 248 Google Scholar
[10]	Sharma V K, Chattopadhyay M K, Kumar R, Ganguli T, Tiwari P, Roy S B 2007 J. Phys. Condens. Matter 19 496207 Google Scholar
[11]	Hu F X, Shen B G, Sun J R, Cheng Z H, Rao G H, Zhang X X 2001 Appl. Phys. Lett. 78 3675 Google Scholar
[12]	Fujieda S, Fujita A, Fukamichi K 2002 Appl. Phys. Lett. 81 1276 Google Scholar
[13]	Shen Q, van Rooij F, Zhang Z, Hao W, Dugulan A I, van Dijk N, Brück E, Li L 2026 J. Mater. Sci. Technol. 254 196 Google Scholar
[14]	Na Y Z, Wang Z X, Kong Z, Xie Y, Zhang Y K 2025 J. Rare Earth https://doi.org/10.1016/j.jre.2025.09.044
[15]	Campos A, Rocco D, Carvalho A, Caron L, Coelho A, Gama S, Silva L, Gandra F, Santos A, Cardoso L, von Ranke P J, Oliveira N A 2006 Nat. Mater. 5 802 Google Scholar
[16]	Gschneidner Jr K A, Pecharsky V V, Tsokol A O 2005 Rep. Prog. Phys. 68 1479 Google Scholar
[17]	Gshneidner Jr K A, Pecharsky V V 2008 Int. J. Refrig. 31 945 Google Scholar
[18]	Planes A, Mañosa L, Acet M 2009 J. Phys. Condens. Matter 21 233201 Google Scholar
[19]	Franco V, Blázquez J S, Ingalge B, Conde A 2012 Ann. Rev. Mater. Res. 42 305 Google Scholar
[20]	de Oliveira N A, von Ranke P J, Troper A 2014 Int. J. Refrig. 37 237 Google Scholar
[21]	Dunand D C, Mullner P 2011 Adv. Mater. 23 216 Google Scholar
[22]	Webster P J, Ziebeck K R A, Town S L, Peak M S 1984 Philos. Magn. 49 295 Google Scholar
[23]	Entel P, Dannenberg A, Siewert M, Herper H C, Gruner M E, Buchelnikov V D, Chernenko V A 2011 Mater. Sci. Forum 684 1 Google Scholar
[24]	Datta S, Dheke S S, Panda S K, Rout S N, Das T, Kar M 2023 J. Alloys Compd. 968 172251 Google Scholar
[25]	Fabbrici S, Porcari G, Cugini F, Solzi M, Kamarad J, Arnold Z, Cabassi R, Albertini F 2014 Entropy 16 2204 Google Scholar
[26]	Schleicher B, Klar D, Ollefs K, Diestel A, Walecki D, Weschke E, Schultz L, Nielsch K, Fähler S, Wende H, Gruner M E 2017 J. Phys. D: Appl. Phys. 50 465005 Google Scholar
[27]	Diestel A, Niemann R, Schleicher B, Nielsch K, Fähler S 2018 Energy Technol. 6 1463 Google Scholar
[28]	Schröter M, Herper H C, Grünebohm A 2022 J. Phys. D: Appl. Phys. 55 025002 Google Scholar
[29]	Fu S, Gao J, Wang K, Ma L, Zhu J 2024 Intermetallics 169 108276 Google Scholar
[30]	Mendonça A A, Ghivelder L, Bernardo P L, Cohen L F, Gomes A M 2023 J. Alloys Compd. 938 168444 Google Scholar
[31]	Sarkar S K, Babu P D, Biswas A, Siruguri V, Krishnan M 2016 J. Alloys Compd. 670 281 Google Scholar
[32]	Zhang X, Qian M, Zhang Z, Wei L, Geng L, Sun J 2016 Appl. Phys. Lett. 108 052401 Google Scholar
[33]	Gràcia-Condal A, Planes A, Mañosa L, Wei Z, Guo J, Soto-Parra D, Liu J 2022 Phys. Rev. Mater. 6 084403 Google Scholar
[34]	Liu Y, Zhang X, Xing D, Shen H, Chen D, Liu J, Sun J 2014 J. Alloys Compd. 616 184 Google Scholar
[35]	Liu Y, Luo L, Zhang X, Shen H, Liu J, Sun J, Zu N 2019 Intermetallics 112 106538 Google Scholar
[36]	Qian M, Zhang X, Wei L, Martin P, Sun J, Geng L, Scott T B, Peng H X 2018 Sci. Rep. 8 16574 Google Scholar
[37]	Qian M, Zhang X, Jia Z, Wan, X, Geng L 2018 Mater. Des. 148 115 Google Scholar
[38]	Zhang Y C, Franco V, Wang Y F, Peng H X, Qin F X 2022 J. Alloys Compd. 918 165664 Google Scholar
[39]	Chiu W T, Sratong-on P, Chang T F M, Tahara M, Sone M, Chernenko V, Hosoda H 2023 J. Mater. Res. Technol. 23 131 Google Scholar
[40]	Zhang Y C, Gao Y, Franco V, Yin H B C, Peng H X, Qin F X 2023 Sci. Chin. -Mater. 66 3670 Google Scholar
[41]	Hu F X, Shen B G, Sun J R 2000 Appl. Phys. Lett. 76 3460 Google Scholar
[42]	Pasquale M, Sasso C P, Lewis L H, Giudici L, Lograsso T, Schlagel D 2005 Phys. Rev. B 72 094435 Google Scholar
[43]	Miroshkina O N, Sokolovskiy V V, Zagrebin M A, Taskaev S V, Buchelnikov V D 2020 Phys. Solid State 62 785 Google Scholar
[44]	Brown P J, Crangle J, Kanomata T, Matsumoto M, Neumann K U, Ouladdiaf B, Ziebeck K R A 2002 J. Phys. Condens. Matter 14 10159 Google Scholar
[45]	Hafner J 2000 Acta Mater. 48 71 Google Scholar
[46]	Kresse G, Furthmüller J 1996 Phys. Rev. B 54 11169 Google Scholar
[47]	Kresse G, Hafner J 1993 Phys. Rev. B 47 558 Google Scholar
[48]	Perdew J P, Burke K, Ernzerhof M 1996 Phys. Rev. Lett. 77 3865 Google Scholar
[49]	Perdew J P, Wang Y 1992 Phys. Rev. B 45 13244 Google Scholar
[50]	Blöchl P E 1994 Phys. Rev. B 50 17953 Google Scholar
[51]	Monkhorst H J, Pack J D 1976 Phys. Rev. B 13 5188 Google Scholar
[52]	Ebert H, Dreysee H 1999 The Use of the LMTO Method (Lecture Notes in Physics) (Berlin: Springer) 535 pp 191–246
[53]	Ebert H 2005 The Munich SPR-KKR Package (Version 8.6) SPRKKR 8.6 Manual
[54]	Minár J, Perlov A, Ebert H, Hashizume H 2005 J. Phys. Condens. Matter 17 5785 Google Scholar
[55]	Zhang C, Zhang Z, Wang D, Hu Y 2024 Appl. Phys. Lett. 124 082407 Google Scholar
[56]	Liechtenstein A I, Katsnelson M I, Antropov V P, Gubanov V A 1987 J. Magn. Magn. Mater. 67 65 Google Scholar
[57]	Phan M H, Yu S C 2007 J. Magn. Magn. Mater. 308 325 Google Scholar
[58]	Pecharsky V K, Gschneidner K A 2000 Annu. Rev. Mater. Sci. 30 387 Google Scholar
[59]	Hu Y, Wang Y, Li Z, Chi X, Lu Q, Hu T, Liu Y, Du A, Shi F 2018 Appl. Phys. Lett. 113 133902 Google Scholar
[60]	Hu Y, Hu T, Chi X, Wang Y, Lu Q, Yu L, Li R, Liu Y, Du A, Li Z, Shi F 2019 Appl. Phys. Lett. 114 023903 Google Scholar
[61]	Hao F, Hu Y 2020 Appl. Phys. Lett. 117 063902 Google Scholar
[62]	Zhang J, Hu Y 2021 Appl. Phys. Lett. 119 213903 Google Scholar
[63]	Oesterreicher H, Parker F T 1984 J. Appl. Phys. 55 4334 Google Scholar
[64]	Franco V, Blázquez J S, Conde A 2006 Appl. Phys. Lett. 89 222512 Google Scholar
[65]	Franco V, Conde A, Sidhaye D, Prasad B L V, Poddar P, Srinath S, Phan M H, Srikanth H 2010 J. Appl. Phys. 107 09A902 Google Scholar
[66]	Liu Y, Petrovic C 2018 Phys. Rev. B 97 174418 Google Scholar

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