SmCo<sub>5</sub>型中熵、高熵金属间化合物的结构与磁性

郭新鹏; 郭永权; 王京南; 殷林瀚

doi:10.6054/j.jscnun.2021036

SmCo₅型中熵、高熵金属间化合物的结构与磁性

doi: 10.6054/j.jscnun.2021036

华北电力大学能源动力与机械工程学院，北京 102206

基金项目:

国家重点研发项目 2018YFB0905600

详细信息

通讯作者:
郭永权，Email: yqguo@ncepu.edu.cn

中图分类号: TB34
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- 被引次数: 0
出版历程
- 收稿日期: 2020-02-18
- 网络出版日期: 2021-07-06
- 刊出日期: 2021-06-25

The Structure and Magnetic Properties of SmCo₅-type Medium- and High-entropy Intermetallic Compounds

School of Energy Power and Mechanical Engineering, North China Electric Power University, Beijing 102206, China

摘要

摘要: 以SmCo₅为原型，设计了3种中熵金属间化合物(Sm_1/3Ce_1/3Pr_1/3)Co₅、(Sm_1/3Ce_1/3Nd_1/3)Co₅、(Sm_1/3Pr_1/3Nd_1/3)Co₅和1种高熵金属间化合物(Sm_1/4Ce_1/4Pr_1/4Nd_1/4)Co₅，并采用原子半径差和混合焓预测了形成单相结构的可能性. 应用真空电弧熔炼技术成功制备了4种金属间化合物. 采用X射线衍射仪(XRD)、能谱仪(EDS) 和振动样品磁强计(VSM) 表征了样品的物相、成分和磁学性能. 结果表明：4种化合物均为单相，具有六方CaCu₅结构，空间群为P6/mmm，稀土原子占据1a位置；稀土位置上的原子浓度为等原子比；化合物的室温磁化行为遵循Langevin模型，磁化强度依赖于化合物的成分；磁价模型计算证实了化合物(Sm_1/3Ce_1/3Pr_1/3)Co₅、(Sm_1/3Ce_1/3Nd_1/3)Co₅和(Sm_1/4Ce_1/4Pr_1/4Nd_1/4)Co₅中的Ce为+4价，对磁矩没有贡献.
- 高熵 /
- SmCo₅ /
- 金属间化合物 /
- 单相 /
- 磁性
Abstract: Three medium-entropy intermetallic compounds (Sm_1/3Ce_1/3Pr_1/3)Co₅, (Sm_1/3Ce_1/3Nd_1/3)Co₅ and (Sm_1/3Pr_1/3Nd_1/3)Co₅ and a high-entropy intermetallic compound (Sm_1/4Ce_1/4Pr_1/4Nd_1/4)Co₅ were designed on the basis of SmCo₅. The possibility of forming single-phase structure was predicted using atomic size difference and mixing enthalpy. Four intermetallics were synthesized via the vacuum arc-melting technology. The X-ray diffractometer (XRD), the energy dispersive X-ray spectrometer (EDS) and the vibration sample magnetometer (VSM) were used to study the phase, chemical compositions and magnetic properties. The results show that four intermetallics are single-phase structures and crystalline in a hexagonal CaCu₅ structure with a space group of P6/mmm. The rare earth atoms occupy 1a site. The atomic concentration at the rare earth site is equiatomic ratio. The room temperature magnetizations follow the Langevin model. Magnetization depends on the composition of the compound. The magnetic valence model was employed to check the valence of Ce. The calculated results show that Ce is tetravalent in (Sm_1/3Ce_1/3Pr_1/3)Co₅, (Sm_1/3Ce_1/3Nd_1/3)Co₅ and (Sm_1/4Ce_1/4Pr_1/4Nd_1/4)Co₅ and makes no contribution to the magnetic moment.
- high-entropy /
- SmCo₅ /
- intermetallic compound /
- single phase /
- magnetic properties

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图 1 4种金属间化合物的XRD图谱

Figure 1. The XRD patterns of four intermetallic compounds

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图 2 (Sm_1/4Ce_1/4Pr_1/4Nd_1/4)Co₅的XRD精修图谱

Figure 2. The refined XRD pattern of (Sm_1/4Ce_1/4Pr_1/4Nd_1/4)Co₅

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图 3 4种金属间化合物粉末的SEM图

Figure 3. The SEM images of four intermetallic compounds

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图 4 4种金属间化合物粉末的EDS能谱

Figure 4. The EDS patterns of four intermetallic compounds

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图 5 (Sm, R)Co₅(R=Ce, Pr, Nd)化合物的室温(300 K)磁化曲线

Figure 5. The magnetization curves of (Sm, R)Co₅ (R=Ce, Pr, Nd) compounds at room temperature (300 K)

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图 6 块状样品在室温下的磁滞回线

Figure 6. The hysteresis loops of bulk samples at room temperature

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图 7 粉末样品在室温下的磁滞回线

Figure 7. The hysteresis loops of powder samples at room temperature

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表 1 (Sm_1/4Ce_1/4Pr_1/4Nd_1/4)Co₅衍射峰的指标化结果

Table 1. The index results of diffraction peaks in compound (Sm_1/4Ce_1/4Pr_1/4Nd_1/4)Co₅

晶面	2θ实验值	2θ计算值
100	20.518	20.518
001	22.241	22.251
101	30.459	30.447
110	35.959	35.934
200	41.740	41.733
111	42.680	42.674
002	45.420	45.402
201	47.820	47.795
112	59.238	59.215
211	61.220	61.218
202	63.343	63.360
300	64.563	64.591
301	69.221	69.231
103	74.543	74.553
220	76.200	76.186
注：M(15)=109，F(15)=58.

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表 2 (Sm, R)Co₅(R=Ce, Pr, Nd) 化合物的晶格参数、品质因子与可信度因子

Table 2. The lattice parameters, quality factors and credibility factors of (Sm, R)Co₅ (R=Ce, Pr, Nd) compounds

晶格参数	a/nm	c/nm	V/nm³	M	F
(Sm_1/3Ce_1/3Pr_1/3)Co₅	0.498 6(7)	0.399 2(7)	0.085 98	181	81
(Sm_1/3Ce_1/3Nd_1/3)Co₅	0.498 7(3)	0.299 0(5)	0.085 96	177	98
(Sm_1/3Pr_1/3Nd_1/3)Co₅	0.500 4(4)	0.397 6(5)	0.086 25	105	55
(Sm_1/4Ce_1/4Pr_1/4Nd_1/4)Co₅	0.499 4(2)	0.399 1(9)	0.086 23	109	58

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表 3 (Sm, R)Co₅ (R=Ce, Pr, Nd)化合物的Rietveld精修结果

Table 3. The Rietveld refined results of (Sm, R)Co₅ (R=Ce, Pr, Nd) compounds

晶格参数	(Sm_1/3Ce_1/3Pr_1/3)Co₅	(Sm_1/3Ce_1/3Nd_1/3)Co₅	(Sm_1/3Pr_1/3Nd_1/3)Co₅	(Sm_1/4Ce_1/4Pr_1/4Nd_1/4)Co₅
a/nm	0.498 51	0.498 45	0.500 82	0.499 25
c/nm	0.399 31	0.399 02	0.397 84	0.399 08
V/nm³	0.085 94	0.085 85	0.086 42	0.086 14
1a(0, 0, 0)	Sm	Sm	Sm	Sm
	Ce	Ce	—	Ce
	Pr	—	Pr	Pr
	—	Nd	Nd	Nd
2c(1/3, 2/3, 0)	Co	Co	Co	Co
3g(1/2, 0, 1/2)	Co	Co	Co	Co
R_p/%	6.190	7.515	7.556	6.705
R_wp/%	8.044	9.660	10.028	8.585
s	1.558	1.561	1.363	1.376
注：空间群为P6/mmm.

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表 4 (Sm, R)Co₅ (R=Ce, Pr, Nd)化合物的成分分析结果

Table 4. The results of composition analysis of (Sm, R) CO₅ (R=Ce, Pr, Nd) compounds

元素	(Sm_1/3Ce_1/3Pr_1/3)Co₅	(Sm_1/3Ce_1/3Nd_1/3)Co₅	(Sm_1/3Pr_1/3Nd_1/3)Co₅	(Sm_1/4Ce_1/4Pr_1/4Nd_1/4)Co₅
Sm	5.57	5.62	5.76	3.94
Ce	5.39	5.43	—	4.17
Pr	5.72	—	5.49	3.97
Nd	—	5.73	5.38	4.01
Co	83.32	83.22	83.36	83.91

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表 5 (Sm, R)Co₅ (R=Ce, Pr, Nd)化合物的计算磁矩

Table 5. The calculated moments of (Sm, R)Co₅ (R=Ce, Pr, Nd) compounds

化合物	μ_B实验值	Ce³⁺的计算结果			Ce⁴⁺的计算结果
化合物	μ_B实验值	μ_B计算值	N_sp^↑	误差/%	μ_B计算值	N_sp^↑	误差/%
(Sm_1/3Ce_1/3Pr_1/3)Co₅	6.24	7.02	0	12.50	6.30	0	0.96
(Sm_1/3Ce_1/3Nd_1/3)Co₅	6.37	7.04	0	10.52	6.33	0	0.63
(Sm_1/3Pr_1/3Nd_1/3)Co₅	8.74	8.60	0.1	1.60	8.60	0.1	1.60
(Sm_1/4Ce_1/4Pr_1/4Nd_1/4)Co₅	6.88	7.33	0	6.54	6.80	0	1.16

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