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摘要

自20世纪末以来, La-Co共替代的M型铁氧体备受关注, 已成为高性能永磁铁氧体的基础材料. Co ²⁺的未淬灭轨道矩被认为是增强铁氧体单轴各向异性的原因, 但其微观作用机理尚未完全解释清楚. 为了满足铁氧体材料日益增长的性能需求, 理解其磁各向异性增强机理至关重要, 并寻求从根源上的提升、低成本和高效的方法, 以制定开发高性能产品的指导原则. 本文综述了一系列研究工作, 旨在确定Co离子在晶格中的取代位置, 这是增强磁各向异性的关键. 这些研究为进一步提高永磁铁氧体的磁性能提供了重要的材料设计参考.

关键词:

Abstract

La-Co co-substituted M-type ferrite, which was first reported at the end of the 20th century, as the cornerstone of high-performance permanent magnet ferrites, has received increasing attention from researchers around the world. The unquenched orbital moments of Co ²⁺play a pivotal role in enhancing the uniaxial anisotropy of M-type ferrites. However, a comprehensive understanding of its microscopic mechanism remains elusive. In order to meet the increasing performance requirements of ferrite materials, it is imperative to clarify the mechanism behind the enhancement of magnetic anisotropy, and at the same time seek the guiding principles that are helpful to develop high-performance product quickly and economically. But its mechanism at a microscopic level has not been explained. This review comprehensively analyzes various studies aiming at pinpointing the crystal sites of Co substitution within the lattice. These investigations including neutron diffraction, nuclear magnetic resonance, and Mössbauer spectroscopy can reveal the fundamental origins behind the enhancement of magnetic anisotropy, thereby providing valuable insights for material design strategies aiming at further enhancing the magnetic properties of permanent magnet ferrites. The exploration of co-substitution sites has yielded noteworthy findings. Through careful examination and analysis, researchers have discovered the complex interplay between Co ions and the lattice structure, revealing the mechanisms of enhanced magnetic anisotropy. The current mainstream view is that Co ions tend to occupy more than one site, namely the 4 f ₁, 12 k, and 2 asites, all of which are located within the spinel lattice. However, there have also been differing viewpoints, implying that further exploration is needed to uncover the primary controlling factors influencing Co occupancy. It is worth noting that the identification of specific Co substitution sites, especially the spin-down tetrahedron 4 f ₁, has achieved targeted modifications, ultimately fine-tuning the magnetic properties with remarkable precision. Furthermore, the reviewed research emphasizes the pivotal role of crystallographic engineering in tailoring the magnetic characteristics of ferrite materials. By strategically manipulating Co substitution, researchers have utilized the intrinsic properties of the lattice to amplify magnetic anisotropy, thereby unlocking new avenues for the advancement of permanent magnet ferrites. In conclusion, the collective findings outlined in this review herald a promising trajectory for the field of permanent magnet ferrites. With a detailed understanding of Co-substitution mechanisms, researchers are preparing to open up new avenues for developing next-generation ferrite materials with enhanced magnetic properties.

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作者及机构信息

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通信作者:沈保根,shenbaogen@nimte.ac.cn

基金项目:国家自然科学基金基础科学中心项目(批准号: 52088101)、浙江省“鲲鹏计划”和宁波市顶尖人才科技项目资助的课题.

Authors and contacts

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Corresponding author:Shen Bao-Gen,shenbaogen@nimte.ac.cn

Funds:Project supported by the Basic Science Center Program of the National Science Foundation of China (Grant No. 52088101), the Kunpeng Plan of Zhejiang Province, China, and the Ningbo Top Talent Program, Zhejiang, China.

文章全文: translate this paragraph

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施引文献

下载: 全尺寸图片幻灯片

公司	国家	牌号	B_r/mT	H_cb/(kA·m^–1)	H_cJ/(kA·m^–1)	(BH)_max/(kJ·m^–3)
TDK^[23]	日本	FB13B	475	340	380	44.0
TDK^[23]		FB14H	470	355	430	43.1
日立金属^[31]		NMF-15	480	342	382	44.0
横店东磁^[27]	中国	DM4748	460	328	368	41.5
北矿磁材^[28]		BMS-9.3	420	318	398	33.5
江益磁材^[29]		JPM-12B	450	310	350	38.2
龙磁科技^[30]		SM13N	450	278	298	38.1

下载: 导出CSV

元素	Wyckoff晶位	氧配位数	晶位形状	磁矩方向
A	2d	12	—	—
Fe	2a	6	八面体	↑
	2b	5	双锥体	↑
	4f₁	4	四面体	↓
	4f₂	6	八面体	↓
	12k	6	八面体	↑

下载: 导出CSV

样品	作者和年份	国家	检测方法	Co²⁺占位
样品	作者和年份	国家	检测方法	2a	2b	4f₁	4f₂	12k
多晶	Pieper等, 2002^[100]	澳大利亚	⁵⁷Fe-NMR			●	●
	Pieper等, 2002^[101]	澳大利亚	⁵⁷Fe,¹³⁹La和⁵⁹Co-NMR			▲	●
	Moral等, 2002^[102]	法国	⁵⁷Fe-Mössbauer, Raman	●			●
	Le Breton等, 2002^[103]	法国	⁵⁷Fe-Mössbauer	●	▲		●
	Wiesinger等, 2002^[104]	澳大利亚	⁵⁷Fe-Mössbauer,⁵⁷Fe和⁵⁹Co-NMR	●		▲	●
	Lechevallier等, 2003^[97]	法国	⁵⁷Fe-Mössbauer	●			●
	Lechevallier等, 2004^[105]	法国	⁵⁷Fe-Mössbauer	●			●
	Choi等, 2006^[106]	韩国	⁵⁷Fe-Mössbauer		●		●	●
	Kobayashi等, 2011^[107]	日本	Neutron Diffraction, EXAFS, XMCD	●		●		●
	Kouřil, 2013^[109]	捷克	⁵⁷Fe-NMR	●	▲	●	▲	▲
	Wu等, 2015^[110]	中国	Raman, XPS	●		●		●
	Ohtsuka等, 2016^[111]	日本	TEM-EDXS	●		●		●
	Mahadevan等, 2020^[112]	印度	⁵⁷Fe-Mössbauer, Raman	●	●		●
单晶	Nagasawa等, 2016^[113]	日本	⁵⁷Fe-Mössbauer			▲	▲
	Oura等, 2018^[114]		⁵⁷Fe-Mössbauer, XES	●		●
	Sakai等, 2018^[115]		⁵⁷Fe和⁵⁹Co-NMR	●		●		●
	Nakamura等, 2019^[116]		⁵⁹Co-NMR	●		●		●
	Nagasawa等, 2020^[117]		外场作用下的⁵⁷Fe-Mössbauer			●

下载: 导出CSV

样品	制备方法	替代浓度		5 K时的磁各向异性场H_A/kOe
样品	制备方法	x	y	5 K时的磁各向异性场H_A/kOe
Sr_1–xLa_xFe_12–yCo_yO₁₉^[140]	Na₂O助熔剂法生长的单晶	0	0	17.50
		0.055	0.032	17.22
		0.139	0.077	19.46
		0.242	0.108	18.62
		0.289	0.152	21.57
		0.367	0.212	24.36
		0.511	0.161	22.17
		0.472	0.266	25.57
Sr_1–xLa_xFe_12–yCo_yO₁₉^[142]	高氧压移动溶剂浮区法生长的单晶	0.2	0.2	21.77
Sr_1–xLa_xFe_12–yCo_yO₁₉^[142]	高氧压移动溶剂浮区法生长的单晶	0.4	0.4	27.96
Sr_1–xLa_xFe_12–yCo_yO₁₉^[143]	高氧压固相反应法合成的多晶	0.21	0.21	21.18
		0.30	0.30	21.76
		0.39	0.39	24.41
		0.41	0.41	27.06
		0.72	0.72	34.12
		0.93	0.93	42.35
		1.00	1.00	56.76
Ca_13–n–xLa_xFe_n–yCo_yO₁₉ (n= 11.87—11.93, 根据不同Co替代量而改变)^[144]	CaO助熔剂法生长的单晶	0.52	0.07	15.26
		0.52	0.10	17.35
		0.56	0.17	23.15
		0.48	0.16	25.65
		0.59	0.27	28.31
		0.37	0.17	26.89
		0.56	0.36	31.54
Na_axLa_xFe_n–yCo_yO₁₉(a= 0.25—0.41, n= 11.84—11.97, 根据不同Co 替代量而改变)^[145]	Na₂O助熔剂法生长的单晶	0.82	0.12	25.72
		0.79	0.21	25.61
		0.83	0.31	29.61

下载: 导出CSV

模型	2a	2b	4f₁	4f₂	12k
1	—	—	1.00	—	—
2	—	—	—	—	1.00
3	0.35	—	0.65	—	—
4	0.31	—	—	—	0.69
5	—	—	0.88	0.12	—
6	—	—	0.47	—	0.53
7	0.22	—	0.38	—	0.40

下载: 导出CSV

类别	高自旋	低自旋
类别	高自旋	八面体	四面体	双锥体
Co²⁺(d⁷)	3/2	1/2	—	1/2
Co³⁺(d⁶)	2	0	1	1

下载: 导出CSV

记号	中心频率/MHz	局域场大小/T	相对丰度
S1	86	8.6	0.73
S2	307	30.6	0.16
S3	386	38.5	0.11
S4	529	52.7	＜0.002

下载: 导出CSV

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