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金属学报  2017, Vol. 53 Issue (1): 83-89    DOI: 10.11900/0412.1961.2016.00142
  本期目录 | 过刊浏览 |
1 东北大学材料各向异性与织构教育部重点实验室 沈阳 110819
2 东北大学秦皇岛分校资源与材料学院 秦皇岛 066004
3 河北省电介质与电解质功能材料实验室 秦皇岛 066004
A First-Principles Study on Crystal Structure, Phase Stability and Magnetic Properties of Ni-Mn-Ga-Cu Ferromagnetic Shape Memory Alloys
Jing BAI1,2,3(),Ze LI2,Zhen WAN2,Xiang ZHAO1
1 Key Laboratory for Anisotropy and Texture of Materials (Ministry of Education), Northeastern University, Shenyang 110819, China
2 School of Resources and Materials, Northeastern University at Qinhuangdao, Qinhuangdao 066004, China
3 Hebei Provincial Laboratory for Dielectric and Electrolyte Functional Materials, Qinhuangdao 066004, China
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关键词 铁磁形状记忆合金第一性原理计算相稳定性磁性能    

Ni-Mn-Ga ferromagnetic shape memory alloys (FSMAs) have attracted great attention for more than two decades, due to their large magnetic shape memory effect that originates from the rearrangement of martensitic variants under an external magnetic field. Over the past decade, accumulated knowledge on the properties of Ni-Mn-Ga Heusler alloys has allowed people to foresee the possibility of employing these alloys in device applications. However, the low operating temperatures and high brittleness remain the major drawbacks for the industrial application. Consequently, there has been growing interest in the modification of Ni-Mn-Ga alloys by adding a fourth element to increase transformation temperatures and to improve ductility. A recent study shows that the ductility has been effectively improved in Cu-doped Ni-Mn-Ga alloy under the situation of single phase via strengthening grain boundaries. In addition, the crystal structure, martensitic transformation, magnetic properties, high temperature magnetoplasticity and magnetocaloric effect have been reported in Ni-Mn-Ga-Cu alloys. Experimental results have shown that the martensitic transformation temperature (Tm) is drastically increased and the Curie temperature (TC) slightly decreased with Cu addition. As already known, the alloying elements affect both the crystal and electronic structures and hence the stability of austenite and martensite phases. Therefore, knowledge of the effects of Cu addition is of great importance to understand the composition dependence of Tm and TC. First-principles calculation results on Ni8Mn4-xGa4Cux (x=0, 0.5, 1, 1.5 and 2) ferromagnetic shape memory alloys of this research draw following conclusions. The added Cu atom preferentially occupies the Mn site. The formation energy results indicate that ferromagnetic austenite is more stable than the paramagnetic one. The ferromagnetic state becomes instable and paramagnetic state becomes more stable when Mn is gradual substituted by Cu. The evaluated TC decreases with increasing Cu content that is derived from the decrease of total energy difference between the paramagnetic and the ferromagnetic austenite. The experimentally observed decrease of Tm is originated from the decrease of total energy difference between the austenite and the non-modulated martensite. The difference between the up and down DOS is reduced with the increasing Cu content that gives rise to the decrease of the total magnetic moments. The purpose of this work is to explore the influence of Cu addition on crystal structure, Tm, TC and electronic structures of Ni8Mn4-xGa4Cux (x=0, 0.5, 1, 1.5 and 2) alloys by first-principles calculations, aiming at providing theoretical data and directions for developing high performance FSMAs.

Key wordsferromagnetic shape memory alloy,    first-principle calculation,    phase stability,    magnetic property
收稿日期: 2016-04-18     
基金资助:资助项目 国家自然科学基金项目Nos.51301036和51431005,国家高技术研究发展计划项目No.2015AA034101,中央高校基本科研业务费专项资金项目No.N130523001及河北省自然科学基金项目No.E2013501089资助


白静,李泽,万震,赵骧. Ni-Mn-Ga-Cu铁磁形状记忆合金的晶体结构、相稳定性和磁性能的第一性原理研究[J]. 金属学报, 2017, 53(1): 83-89.
Jing BAI, Ze LI, Zhen WAN, Xiang ZHAO. A First-Principles Study on Crystal Structure, Phase Stability and Magnetic Properties of Ni-Mn-Ga-Cu Ferromagnetic Shape Memory Alloys. Acta Metall Sin, 2017, 53(1): 83-89.

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图1  Ni2MnGa的晶体结构示意图
图2  Ni8Mn4-xGa4Cux (x=0、0.5、1、1.5和2)合金顺磁性奥氏体相和铁磁性奥氏体相的形成能
Etot / eV ΔE1 / eV
TC / K
ΔE2 / eV
Paramagnetic austenite Ferromagnetic austenite Non-modulated martensite
0 -91.2143 -95.4713 -95.5339 4.2570 365 0.0626
0.5 -89.1821 -92.8067 -92.8845 3.6247 311 0.0778
1 -87.1279 -90.1651 -90.2773 3.0372 260 0.1122
1.5 -85.0584 -87.5453 -87.6700 2.4869 213 0.1247
2 -82.9336 -84.9459 -85.1345 2.0123 173 0.1886
表2  Ni8Mn4-xGa4Cux (x=0、0.5、1、1.5和2)合金顺磁和铁磁奥氏体及非调制马氏体的基态总能量
图3  电子自旋总态密度图
x Phase a / nm c / nm c/a Magnetic moment
10-23 Am2
0 Cub. 0.5794 (5.823[26]) 3.7319 (3.8673[31], 3.9600[32])
Tet. 0.3845 (3.852[30]) 0.6568 (6.580[30]) 1.708 (1.708[30]) 3.7625
0.5 Cub. 0.5787 3.2895
Tet. 0.3821 0.6641 1.738 3.3071
1 Cub. 0.5782 2.8824
Tet. 0.3814 0.6623 1.736 2.8694
1.5 Cub. 0.5775 2.4418
Tet. 0.3803 0.6648 1.748 2.3843
2 Cub. 0.5764 2.0171
Tet. 0.3782 0.6672 1.764 1.8585
表1  Ni8Mn4-xGa4Cux (x=0、0.5、1、1.5和2)合金立方奥氏体和四方非调制马氏体的平衡晶格常数及总磁矩
图4  Ni8Mn3Ga4Cu1 (X1)合金的自旋分波态密度图
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