Ti掺杂Nd<sub>2</sub>Fe<sub>14</sub>B/α-Fe纳米双相复合永磁体晶化动力学

邓晨华; 于忠海; 王宇涛; 孔森; 周超; 杨森

doi:10.7498/aps.72.20221479

摘要

纳米双相复合稀土永磁材料, 利用硬磁相高磁晶各向异性和软磁相高饱和磁化强度的优点, 通过铁磁交换耦合作用获得优异的磁性能. 但是如何解决软硬磁双相纳米微结构不匹配的问题, 控制软硬磁相同时达到理想的纳米尺度复合是关键. 本文研究了掺杂合金元素Ti对熔体快淬法制备的Nd₂Fe₁₄B/α-Fe快淬薄带晶化过程的影响. 结果表明, 掺杂合金元素Ti能影响Nd₂Fe₁₄B/α-Fe交换耦合磁体整个晶化动力学过程, 使α-Fe相的晶化激活能升高, 抑制其从非晶相中析出. 同时, 降低1∶7亚稳相的晶化激活能, 起到稳定亚稳相的作用. 而且随着晶化温度的进一步提高, α-Fe和Nd₂Fe₁₄B两相由1∶7亚稳相分解产生, 从而有效避免了α-Fe相的优先析出. 显微组织观察表明, 掺杂Ti的样品晶粒细小、分布均匀, 平均晶粒尺寸在20 nm左右, 没有特别大的α-Fe粒子出现. 当Ti的掺杂量原子百分数为1.0%时, 获得了最佳磁性能(BH)_max = 12 MG·Oe (1 G = 10^–4 T, 1 Oe = 79.57795 A/m).

关键词:

Abstract

Nanocomposite magnet consisting of a fine mixture of magnetically hard and soft phase has received much attention for potential permanent magnet development. One of the important requirements for alloys to exhibit excellent magnetic properties is a nanocrystalline grain size. The soft and hard magnetic phases can simultaneously achieve ideal nanoscale composites. The effect of Ti additions in the amorphous crystallization process of the exchange-coupled nanocomposite Nd₂Fe₁₄B/α-Fe magnet prepared by melt spinning is investigated. The results show that Ti can change the crystallization kinetics of the NdFeB melt-spun ribbons. The Ti can increase the activation energy of α-Fe and contrarily reduce the activation energy of a metastable 1∶7 phase, so the growth speed of α-Fe decreases and the metastable 1∶7 phase can stably precipitate from the amorphous phase. When the annealing temperature increases, a metastable 1∶7 phase is decomposed into the α-Fe phase and the Nd₂Fe₁₄B phase. The microstructure observation shows that the grains of the alloys doped with Ti are fine and uniform, with an average grain size of about 20 nm, and no particularly large α-Fe particles appear. The optimal magnetic property is (BH)_max = 12 MG·Oe (1 G = 10^–4 T, 1 Oe = 79.57795 A/m) when Ti addition is 1.0%.

Keywords:

作者及机构信息

1.
太原师范学院化学与材料学院, 晋中　030619

2.
西安交通大学物理学院, 西安　710049

通信作者: 杨森, yangsen@mail.xjtu.edu.cn

基金项目: 国家重点研发计划(批准号: 2021YFB3803003)、国家自然科学基金(批准号: 52002266, 91963111)和中国博士后科学基金(批准号: 2020M673384)资助的课题.

Authors and contacts

1.
School of Chemistry and Materials, Taiyuan normal University, Jinzhong 030619, China

2.
School of Physics, Xi’an Jiaotong University, Xi’an 710049, China

Corresponding author: Yang Sen, yangsen@mail.xjtu.edu.cn

Funds: Project supported by the National Key R&D Program of China (Grant No. 2021YFB3803003), the National Natural Science Foundation of China (Grant Nos. 52002266, 91963111), and the China Postdoctoral Science Foundation (Grant No. 2020M673384).

文章全文

参考文献

[1]	Zeng H, Li J, Liu J P, Wang Z L, Sun S 2002 Nature 420 395 Google Scholar
[2]	Liu Z, He J, Ramanujan R V 2021 Mater. Des. 209 110004 Google Scholar
[3]	Quesada A, Granados-Miralles C, López-Ortega A, Erokhin S, Lottini E, Pedrosa J, Bollero A, Aragón A M, Rubio-Marcos F, Stingaciu M, Bertoni G, Fernández C de J, Sangregorio C, Fernández J F, Berkov D, Christensen M 2016 Adv. Electron. Mater. 2 1500365 Google Scholar
[4]	庞利佳, 孙光飞, 陈菊芳, 强文江, 张锦标, 黎文安 2006 物理学报 55 3049 Google Scholar Pang L J, Sun G F, Chen J F, Qiang W J, Zhang J B, Li W A 2006 Acta Phys. Sin. 55 3049 Google Scholar
[5]	Hernando A, Gonzalez J M 2000 Hyperfine Interact. 130 221 Google Scholar
[6]	夏静, 张溪超, 赵国平 2013 物理学报 62 227502 Google Scholar Xia J, Zhang X C, Zhao G P 2013 Acta Phys. Sin. 62 227502 Google Scholar
[7]	Yang C J, Park E B 1997 J. Magn. Magn. Mater. 168 278 Google Scholar
[8]	Mohseni F, Pullar R C, Vieira J M, Amaral J S 2020 J. Phys. D:Appl. Phys. 53 494003 Google Scholar
[9]	Kuma J, Kitajima N, Kanai Y, Fukunaga H 1998 J. Appl. Phys. 83 6623
[10]	Attyabi S N, Radmanesh S M A, Seyyed Ebrahimi S A, Dehghan H 2022 J. Supercond. Novel Magn. 35 1229 Google Scholar
[11]	Skomski R, Coey J M D 1993 Phys. Rev. B 48 15812 Google Scholar
[12]	Bauer J, Seager M, Zerm A, Kronmüller H 1996 J. Appl. Phys. 80 1667 Google Scholar
[13]	Deng W K, Wei B N, Shan W K, Hua Y X, Li X, Guo D F 2021 Physica B 620 413263 Google Scholar
[14]	Ma Y, Yin X, Shao B, Yang Q, Shen Q, Zhou X, Sun J, Guo D, Li K 2019 J. Mater. Sci. 54 2658 Google Scholar
[15]	Yang S, Song X P, Li S, Liu X, Tian Z, Gu B, Du Y 2003 J. Magn. Magn. Mater. 263 134
[16]	Ngo H M, Lee G, Haider S K, Pal U, Hawari T, Kim K M, Kim J, Kwon H, Kang Y S 2021 RSC Adv. 11 32376 Google Scholar
[17]	Kim C, Ding S L, O Y J, Zha L, Yun C, Yang W Y, Han J Z, Liu S Q, Du H L, Wang C S, Yang J B 2021 J. Phys. D:Appl. Phys. 54 245003 Google Scholar
[18]	何学敏, 钟伟, 都有为 2018 物理学报 67 227501 Google Scholar He X M, Zhong W, Du Y W 2018 Acta Phys. Sin. 67 227501 Google Scholar
[19]	Semaida A M, Bordyuzhin I G, El-Dek S I, Kutzhanov M K, Menushenkov V P, Savchenko A G 2021 Mater. Res. Express 8 076101 Google Scholar
[20]	Wang Y, Song W, Huang G 2022 J. Supercond. Novel Magn. 35 1261 Google Scholar
[21]	Pan M, Li Z, Wu Q, Ge H, Xu H 2019 J. Magn. Magn. Mater. 471 457 Google Scholar
[22]	Zhang S Y, Xu H, Ni J S, Wang H L, Hou X L, Dong Y D 2007 Physica B 393 153 Google Scholar
[23]	Zhang W, Zhang S, Yan A, Zhang H, Shen B 2001 J. Magn. Magn. Mater. 225 389 Google Scholar
[24]	Yang S, Song X, Gu B, Du Y 2005 J. Alloys Compd. 394 1 Google Scholar
[25]	Hono K, Ping D H, Ohnuma M, Onodera H 1999 Acta Mater. 47 997 Google Scholar
[26]	Ping D H, Hono K, Kanekiyo H, Hirosawa S 1999 Acta Mater. 47 4641 Google Scholar
[27]	Yang S, Song X, Du Y 2003 Microelectron. Eng. 66 121 Google Scholar
[28]	Kelly P E, O’Grady K, Chantrell R W 1989 IEEE Trans. Magn. 25 3881 Google Scholar
[29]	Wohlfarth E P 1958 J. Appl. Phys. 29 595

施引文献

图 1 Nd₈Fe₈₆B₆ (a), (b) 和 Nd₈Fe₈₅Ti₁B₆ (c), (d)合金快淬带的DSC分析曲线以及结晶过程中–ln(R/T²)与1/T的关系曲线

Fig. 1. The DSC results and –ln(R/T²) as a function of 1/T in the crystallization of Nd₈Fe₈₆B₆ (a), (b) and Nd₈Fe₈₅Ti₁B₆ (c), (d) ribbons at different heating rates.

下载: 全尺寸图片幻灯片

图 2 (a) Nd₈Fe₈₆B₆和(b) Nd₈Fe₈₅Ti₁B₆快淬合金带的TMA曲线; (c) Nd₈Fe₈₆B₆和(d) Nd₈Fe₈₅Ti₁B₆快淬合金带在不同温度3 min晶化处理后的XRD曲线

Fig. 2. TMA results of the ribbons of (a) Nd₈Fe₈₆B₆, (b) Nd₈Fe₈₅Ti₁B₆; XRD patterns of (c) Nd₈Fe₈₆B₆ (d) Nd₈Fe₈₅Ti₁B₆ ribbons annealed at different temperature for 3 min.

下载: 全尺寸图片幻灯片

图 3 (a) Nd₈Fe₈₆B₆合金快淬带650 ℃晶化10 min后局部TEM图谱; Nd₈Fe₈₅Ti₁B₆合金快淬带在不同温度下晶化3 min后的TEM图谱 (b) 快淬; (c) 600 ℃; (d) 650 ℃; (e) 700 ℃. 插图为对应的高分辨电子衍射谱

Fig. 3. TEM micrographs of (a) Nd₈Fe₈₆B₆ ribbons annealed at 650 ℃ for 10 min, and Nd₈Fe₈₅Ti₁B₆ ribbons annealed at different temperature for 3 min: (b) as-spun; (c) 600 ℃; (d) 650 ℃; (e) 700 ℃. The insets are the corresponding electron diffraction patterns.

下载: 全尺寸图片幻灯片

图 4 Nd₈Fe₈₅Ti₁B₆快淬合金带650 ℃晶化60 min后的形貌像(a)和晶格像(b)

Fig. 4. TEM micrographs (a) and electron diffraction patterns (b) of Nd₈Fe₈₅Ti₁B₆ ribbons annealed at 650 ℃ for 60 min.

下载: 全尺寸图片幻灯片

图 5 650 ℃下退火10 min的Nd₈Fe₈₆B₆和Nd₈Fe₈₅Ti₁B₆快淬合金带的磁滞回线 (a)和 ΔM曲线 (b)

Fig. 5. Hysteresis loops (a) and ΔM (b) as a function of applied field of Nd₈Fe₈₆B₆ and Nd₈Fe₈₅Ti₁B₆ ribbons annealed at 650 ℃ for 10 min.

下载: 全尺寸图片幻灯片

[1]	Zeng H, Li J, Liu J P, Wang Z L, Sun S 2002 Nature 420 395 Google Scholar
[2]	Liu Z, He J, Ramanujan R V 2021 Mater. Des. 209 110004 Google Scholar
[3]	Quesada A, Granados-Miralles C, López-Ortega A, Erokhin S, Lottini E, Pedrosa J, Bollero A, Aragón A M, Rubio-Marcos F, Stingaciu M, Bertoni G, Fernández C de J, Sangregorio C, Fernández J F, Berkov D, Christensen M 2016 Adv. Electron. Mater. 2 1500365 Google Scholar
[4]	庞利佳, 孙光飞, 陈菊芳, 强文江, 张锦标, 黎文安 2006 物理学报 55 3049 Google Scholar Pang L J, Sun G F, Chen J F, Qiang W J, Zhang J B, Li W A 2006 Acta Phys. Sin. 55 3049 Google Scholar
[5]	Hernando A, Gonzalez J M 2000 Hyperfine Interact. 130 221 Google Scholar
[6]	夏静, 张溪超, 赵国平 2013 物理学报 62 227502 Google Scholar Xia J, Zhang X C, Zhao G P 2013 Acta Phys. Sin. 62 227502 Google Scholar
[7]	Yang C J, Park E B 1997 J. Magn. Magn. Mater. 168 278 Google Scholar
[8]	Mohseni F, Pullar R C, Vieira J M, Amaral J S 2020 J. Phys. D:Appl. Phys. 53 494003 Google Scholar
[9]	Kuma J, Kitajima N, Kanai Y, Fukunaga H 1998 J. Appl. Phys. 83 6623
[10]	Attyabi S N, Radmanesh S M A, Seyyed Ebrahimi S A, Dehghan H 2022 J. Supercond. Novel Magn. 35 1229 Google Scholar
[11]	Skomski R, Coey J M D 1993 Phys. Rev. B 48 15812 Google Scholar
[12]	Bauer J, Seager M, Zerm A, Kronmüller H 1996 J. Appl. Phys. 80 1667 Google Scholar
[13]	Deng W K, Wei B N, Shan W K, Hua Y X, Li X, Guo D F 2021 Physica B 620 413263 Google Scholar
[14]	Ma Y, Yin X, Shao B, Yang Q, Shen Q, Zhou X, Sun J, Guo D, Li K 2019 J. Mater. Sci. 54 2658 Google Scholar
[15]	Yang S, Song X P, Li S, Liu X, Tian Z, Gu B, Du Y 2003 J. Magn. Magn. Mater. 263 134
[16]	Ngo H M, Lee G, Haider S K, Pal U, Hawari T, Kim K M, Kim J, Kwon H, Kang Y S 2021 RSC Adv. 11 32376 Google Scholar
[17]	Kim C, Ding S L, O Y J, Zha L, Yun C, Yang W Y, Han J Z, Liu S Q, Du H L, Wang C S, Yang J B 2021 J. Phys. D:Appl. Phys. 54 245003 Google Scholar
[18]	何学敏, 钟伟, 都有为 2018 物理学报 67 227501 Google Scholar He X M, Zhong W, Du Y W 2018 Acta Phys. Sin. 67 227501 Google Scholar
[19]	Semaida A M, Bordyuzhin I G, El-Dek S I, Kutzhanov M K, Menushenkov V P, Savchenko A G 2021 Mater. Res. Express 8 076101 Google Scholar
[20]	Wang Y, Song W, Huang G 2022 J. Supercond. Novel Magn. 35 1261 Google Scholar
[21]	Pan M, Li Z, Wu Q, Ge H, Xu H 2019 J. Magn. Magn. Mater. 471 457 Google Scholar
[22]	Zhang S Y, Xu H, Ni J S, Wang H L, Hou X L, Dong Y D 2007 Physica B 393 153 Google Scholar
[23]	Zhang W, Zhang S, Yan A, Zhang H, Shen B 2001 J. Magn. Magn. Mater. 225 389 Google Scholar
[24]	Yang S, Song X, Gu B, Du Y 2005 J. Alloys Compd. 394 1 Google Scholar
[25]	Hono K, Ping D H, Ohnuma M, Onodera H 1999 Acta Mater. 47 997 Google Scholar
[26]	Ping D H, Hono K, Kanekiyo H, Hirosawa S 1999 Acta Mater. 47 4641 Google Scholar
[27]	Yang S, Song X, Du Y 2003 Microelectron. Eng. 66 121 Google Scholar
[28]	Kelly P E, O’Grady K, Chantrell R W 1989 IEEE Trans. Magn. 25 3881 Google Scholar
[29]	Wohlfarth E P 1958 J. Appl. Phys. 29 595

[1]	卢一林, 董盛杰, 崔方超, 张开成, 刘春梅, 李杰森, 毛卓. 碳和氧掺杂紫磷烯作为双极磁性半导体材料的理论预测. 物理学报, 2024, 73(1): 016301. doi: 10.7498/aps.73.20231279
[2]	黄青松, 段波, 陈刚, 叶泽昌, 李江, 李国栋, 翟鹏程. Mn-In-Cu共掺杂优化SnTe基材料的热电性能. 物理学报, 2021, 70(15): 157401. doi: 10.7498/aps.70.20202020
[3]	沈忠慧, 江彦达, 李宝文, 张鑫. 高储能密度铁电聚合物纳米复合材料研究进展. 物理学报, 2020, 69(21): 217706. doi: 10.7498/aps.69.20201209
[4]	于鹏, 曹盛, 曾若生, 邹炳锁, 赵家龙. 金属离子掺杂提高全无机钙钛矿纳米晶发光性质的研究进展. 物理学报, 2020, 69(18): 187801. doi: 10.7498/aps.69.20200795
[5]	施伟, 周强, 刘斌. 基于旋转永磁体的超低频机械天线电磁特性分析. 物理学报, 2019, 68(18): 188401. doi: 10.7498/aps.68.20190339
[6]	李柱柏, 李赟, 秦渊, 张雪峰, 沈保根. 稀土永磁体及复合磁体反磁化过程和矫顽力. 物理学报, 2019, 68(17): 177501. doi: 10.7498/aps.68.20190364
[7]	马国亮, 李兴冀, 杨剑群, 刘超铭, 田丰, 侯春风. 电子辐照LDPE/MWCNTs复合材料的熔融与结晶行为. 物理学报, 2016, 65(20): 208101. doi: 10.7498/aps.65.208101
[8]	李丽丽, Xia Zhen-Hai, 杨延清, 韩明. SiC纳米纤维/C/SiC复合材料拉伸行为的分子动力学研究. 物理学报, 2015, 64(11): 117101. doi: 10.7498/aps.64.117101
[9]	刘奎立, 周思华, 陈松岭. 金属离子掺杂对CuO基纳米复合材料的交换偏置调控. 物理学报, 2015, 64(13): 137501. doi: 10.7498/aps.64.137501
[10]	张程宾, 程启坤, 陈永平. 分形结构纳米复合材料热导率的分子动力学模拟研究. 物理学报, 2014, 63(23): 236601. doi: 10.7498/aps.63.236601
[11]	马俊, 杨万民, 王妙, 陈森林, 冯忠岭. 辅助永磁体磁化方式对单畴GdBCO超导块材捕获磁场分布及其磁悬浮力的影响. 物理学报, 2013, 62(22): 227401. doi: 10.7498/aps.62.227401
[12]	何永周. 永磁体外部磁场的不均匀性研究. 物理学报, 2013, 62(8): 084105. doi: 10.7498/aps.62.084105
[13]	万步勇, 苑进社, 冯庆, 王奥. K,Na掺杂Cu-S纳米晶的水热合成及对结构、性能的影响. 物理学报, 2013, 62(17): 178102. doi: 10.7498/aps.62.178102
[14]	马俊, 杨万民, 李佳伟, 王妙, 陈森林. 辅助永磁体的引入方式对单畴GdBCO超导块材磁场分布及其磁悬浮力的影响. 物理学报, 2012, 61(13): 137401. doi: 10.7498/aps.61.137401
[15]	马俊, 杨万民, 李国政, 程晓芳, 郭晓丹. 永磁体辅助下单畴GdBCO超导体和永磁体之间的磁悬浮力研究. 物理学报, 2011, 60(2): 027401. doi: 10.7498/aps.60.027401
[16]	张云, 邵晓红, 王治强. 3C-SiC材料p型掺杂的第一性原理研究. 物理学报, 2010, 59(8): 5652-5660. doi: 10.7498/aps.59.5652
[17]	徐新发, 邵晓红. Y掺杂SrTiO3晶体材料的电子结构计算. 物理学报, 2009, 58(3): 1908-1916. doi: 10.7498/aps.58.1908
[18]	于宙, 李祥, 龙雪, 程兴旺, 王晶云, 刘颖, 曹茂盛, 王富耻. Mn掺杂ZnO稀磁半导体材料的制备和磁性研究. 物理学报, 2008, 57(7): 4539-4544. doi: 10.7498/aps.57.4539
[19]	徐国成, 潘玲, 关庆丰, 邹广田. 非晶钛酸铋的晶化过程. 物理学报, 2006, 55(6): 3080-3085. doi: 10.7498/aps.55.3080
[20]	计齐根, 都有为. 晶粒边界对Nd2Fe14B/α-Fe纳米复合材料性能的影响. 物理学报, 2000, 49(11): 2281-2286. doi: 10.7498/aps.49.2281

计量

文章访问数: 7130
PDF下载量: 107
被引次数: 0

姓名
邮箱
手机号码
标题
留言内容
验证码

搜索

留言板

Ti掺杂Nd₂Fe₁₄B/α-Fe纳米双相复合永磁体晶化动力学