Mn和In添加对SmCo7结构稳定性及磁矩影响的第一性原理计算

doi:10.11900/0412.1961.2020.00397

金属学报

2021, Vol. 57

Issue (7): 948-958 DOI: 10.11900/0412.1961.2020.00397

研究论文

本期目录 | 过刊浏览

Mn和In添加对SmCo₇结构稳定性及磁矩影响的第一性原理计算

毛斐, 吕皓, 唐法威, 郭凯, 刘东, 宋晓艳(

)

北京工业大学材料与制造学部新型功能材料教育部重点实验室北京 100124

First-Principle Calculation on the Effect of Mn and In on the Structural Stability and Magnetic Moment of SmCo₇ Alloys

MAO Fei, LU Hao, TANG Fawei, GUO Kai, LIU Dong, SONG Xiaoyan(

)

Key Laboratory of Advanced Functional Materials, Ministry of Education, Facaulty of Materials and Manufacturing, Beijing University of Technology, Beijing 100124, China

引用本文:

毛斐, 吕皓, 唐法威, 郭凯, 刘东, 宋晓艳. Mn和In添加对SmCo₇结构稳定性及磁矩影响的第一性原理计算[J]. 金属学报, 2021, 57(7): 948-958.
Fei MAO, Hao LU, Fawei TANG, Kai GUO, Dong LIU, Xiaoyan SONG. First-Principle Calculation on the Effect of Mn and In on the Structural Stability and Magnetic Moment of SmCo₇ Alloys[J]. Acta Metall Sin, 2021, 57(7): 948-958.

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摘要:

基于构建适用于第一性原理计算、原子比例准确为Sm∶Co = 1∶7的晶体结构模型，依据实验研究中得到的物相共存结果，对Mn和In掺杂的Sm-Co体系模型进行了系列计算分析。利用热力学计算方法，定量化研究了Mn和In在Sm-Co体系中优先占位特点及掺杂元素占位概率随温度的变化规律。通过Sm-Co合金掺杂体系的能量和电子结构计算，研究了Mn和In单掺杂SmCo₇体系的结构稳定性。基于计算结果揭示了Mn和In对掺杂合金体系中原子间相互作用的影响，阐明了提升体系结构稳定性的微观机制，并提出了Mn添加可增加SmCo₇合金的总磁矩，揭示了掺杂元素对SmCo₇合金饱和磁化强度的影响规律。

关键词 ： Sm-Co基永磁合金, 第一性原理计算, 元素掺杂, 结构稳定性, 磁矩

Abstract：

Among the rare-earth permanent magnetic materials, Sm-Co-based alloys exhibit superior magnetic properties at high temperatures. However, their high-temperature applications are limited by their relatively low saturation magnetization and structural stability. The stability and magnetic properties of these alloys can be enhanced by adding proper alloying elements. In the search for new permanent high-performance magnets, researchers have systematically investigated the structures and magnetic properties of variously doped Sm-Co phases. The present research investigates the structural stability and magnetic properties of Sm-Co based alloys using a crystal structure model of SmCo₇ with an accurate atomic ratio (Sm∶Co = 1∶7). To explain the coexisting multiphase phenomenon observed in experiments, Mn- and In-doped Sm-Co alloys were modeled by first-principles calculations. Systematic calculations were conducted on these models, and were combined with thermodynamics calculations to determine the preferred occupation sites of the doping elements and their change rule with temperature. Based on the calculated energy and electronic structures, the structural stabilities of the alloys were studied. The Mn and In dopants influenced the interactions among the Co atoms in the studied alloys. A microscopic mechanism of stability improvement in the SmCo₇-based alloys was then proposed. The magnetic-moment calculation showed that the Mn additive enhanced the total magnetic moment of the SmCo₇ alloys. This finding explains the effects of doping elements on the saturation magnetization of the SmCo₇ alloys.

Key words： Sm-Co-based permanent magnetic alloy first-principle calculation element doping structural stability magnetic moment

收稿日期: 2020-09-30

ZTFLH:

TG131

基金资助:国家重点研发计划项目(2018YFB0703902、2016YFB0700501、2016YFB0700503)

作者简介: 毛斐，女，1986年生，博士

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图1 Sm2Co17 R相转变为SmCo7的晶体结构示意图

图2 SmCo7超晶胞结构及与文献[17,23,24]报道的SmCo7近似结构模型示意图

图3 4种SmCo7晶体结构模型对应的XRD模拟结果与实验结果[24]的比较

表1 SmCo5和SmCo7超胞几何优化前后的晶格参数与实验值[15,29]对比

图4 掺杂元素Mn在SmCo7体系中3g、2c和2e晶位的形成能计算结果

图5 SmCo6.86Mn0.14体系中Mn在不同位点的占位概率随温度的变化

图6 Mn掺杂前后各体系的总态密度(DOS)及各原子的偏态密度(PDOS)(a) SmCo7 (b) SmCo6.86Mn0.14 (2c)(c) SmCo6.86Mn0.14 (3g) (d) SmCo6.86Mn0.14 (2e)

图7 Sm12Co60超晶胞结构及SmCo5、SmCo7和Sm2Co17模型在(001)平面投影示意图(a) Sm12Co60 supercell supercell structure(b) Sm12Co60 supercell supercell (Supercell structure model projected on the (001) plane)(c) SmCo5 unit cell (d) SmCo5 supercell(e) SmCo7 supercell (f) Sm2Co17 supercell

表2 计算的In掺杂SmCo5、SmCo7和Sm2Co17前后的晶格参数和晶胞体积

图8 In掺杂的SmCo5、SmCo7和Sm2Co17体系中In原子占据不同晶位的形成能计算结果

图9 掺杂元素In在不同体系中的占位概率随温度的变化(a) SmCo5 (b) SmCo7 (c) Sm2Co17

图10 掺杂Mn和In前后的SmCo5、SmCo7 和Sm2Co17超胞总磁矩(a) SmCo5 and SmCo7 supercells with or without Mn doping(b) SmCo5, SmCo7, and Sm2Co17 supercells with or without In doping at different sites

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