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本文基于磁热效应的绿色磁制冷技术, 并以Ni-Mn-Ga Heusler合金为对象, 系统地探索其作为磁制冷工质的潜力. 为阐明富Mn成分对合金磁性与磁热性能的调控机制, 采用第一性原理计算与蒙特卡罗模拟相结合的多尺度方法, 重点分析Mn原子分别占据Ni与Ga位时, 对合金微观结构、原子磁矩、交换作用及宏观磁热行为的影响. 结果表明, Mn占位方式对磁性能具有关键调控作用: Mn占据Ni位会降低总磁矩与居里温度, 并减小磁熵变; 而Mn占据Ga位则显著提升总磁矩与磁熵变, 其中Ni8Mn7Ga1合金在2 T磁场下的最大磁熵变高达2.32 J·kg–1·K–1, 远高于化学计量比Ni8Mn4Ga4合金. 态密度与交换作用分析进一步表明, Mn含量变化可调控其在费米能级附近的电子结构, 优化轨道杂化与铁磁交换作用, 影响磁相变行为. 临界指数分析显示合金中磁相互作用具有长程特性, 并随成分变化趋近于平均场行为. 本工作从微观层面建立了“成分-结构-磁性-磁热性能”之间的构效关系, 为设计高性能、低滞后磁制冷材料提供了理论依据.
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关键词:
- Ni-Mn-Ga合金 /
- 磁热效应 /
- 二级磁相变 /
- 蒙特卡罗模拟
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.
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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
Fig. 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.
图 2 奥氏体相和马氏体相Ni8–xMn4+xGa4(x = 0, 1, 2)和Ni8Mn4+yGa4–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
Fig. 2. Total magnetic moment of alloy and magnetic moments of Mn and Ni atoms as a function of composition in austenitic and martensitic Ni8–xMn4+xGa4 (x = 0, 1, 2) and Ni8Mn4+yGa4–y (y = 0, 1, 2, 3) alloys.
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
Fig. 3. Total density of states and partial density of states of each elements as a function of energy in austenitic Ni-Mn-Ga alloys.
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
Fig. 4. Total density of states and partial density of states of each elements as a function of energy in martensitic Ni-Mn-Ga alloys.
图 5 在奥氏体相Ni8–xMn4+xGa4(x = 0, 1, 2)和Ni8Mn4+yGa4–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
Fig. 5. Exchange coupling constants between Mn-Mn and Mn-Ni as a function of distance in austenitic Ni8–xMn4+xGa4 (x = 0, 1, 2)和Ni8Mn4+yGa4–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.
图 6 在零外磁场作用下, 奥氏体相Ni8–xMn4+xGa4(x = 0, 1, 2)和Ni8Mn4+yGa4–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MS为饱和磁化强度值; 居里温度随富Mn成分的变化关系
Fig. 6. Magnetization and magnetic susceptibility as a function of temperature in austenitic Ni8–xMn4+xGa (x = 0, 1, 2) and Ni8Mn4+yGa4–y (y = 0, 1, 2, 3) alloys under zero magnetic field, where MS is the value of saturated magnetization; Curie temperature as a function of composition of excess Mn.
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MS为饱和磁化强度值
Fig. 7. Magnetization of austenitic Ni-Mn-Ga alloys with different compositions as a function of temperature under selected magnetic fields, where MS is the value of saturated magnetization.
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
Fig. 8. Magnetic entropy change of austenitic Ni-Mn-Ga alloys with different compositions as a function of temperature under selected magnetic fields.
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
Fig. 9. Maximum magnetic entropy change and relative cooling power as a function of magnetic field in Ni-Mn-Ga alloys with different compositions.
图 10 在Ni8–xMn4+xGa4(x = 0, 1, 2)和Ni8Mn4+yGa4–y(y = 0, 1, 2, 3)合金中, 计算的参数随成分的变化关系
Fig. 10. Calculated parameters as a function of composition in Ni8–xMn4+xGa4 (x = 0, 1, 2) and Ni8Mn4+yGa4–y (y = 0, 1, 2, 3) alloys.
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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