WO2015085687A1 - Procédé de fixation de terre rare lourde pour aimant au néodyme ndfeb fritté - Google Patents

Procédé de fixation de terre rare lourde pour aimant au néodyme ndfeb fritté Download PDF

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Publication number
WO2015085687A1
WO2015085687A1 PCT/CN2014/074933 CN2014074933W WO2015085687A1 WO 2015085687 A1 WO2015085687 A1 WO 2015085687A1 CN 2014074933 W CN2014074933 W CN 2014074933W WO 2015085687 A1 WO2015085687 A1 WO 2015085687A1
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WO
WIPO (PCT)
Prior art keywords
rare earth
heavy rare
sintered ndfeb
magnet
ndfeb magnet
Prior art date
Application number
PCT/CN2014/074933
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English (en)
Chinese (zh)
Inventor
孙爱芝
杨俊�
高学绪
吴深
包小倩
李成明
邹超
程川
路振文
杨金锡
Original Assignee
北京科技大学
北京盛磁科技有限公司
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Application filed by 北京科技大学, 北京盛磁科技有限公司 filed Critical 北京科技大学
Publication of WO2015085687A1 publication Critical patent/WO2015085687A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/001—Magnets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H01F41/0293—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets diffusion of rare earth elements, e.g. Tb, Dy or Ho, into permanent magnets

Definitions

  • the invention belongs to the technical field of rare earth magnetic functional materials, and relates to a method for attaching heavy rare earths of sintered NdFeB magnets. Background technique
  • NdFeB has a very high magnetic energy product, and its high energy density makes it widely used in modern industrial and electronic technology.
  • the insufficiency of NdFeB magnetic materials is that the Curie temperature point is low and the temperature characteristics are poor.
  • higher requirements are imposed on the permanent magnet materials used, which not only have a high magnetic energy product, but also have a high coercive force.
  • the most common way to improve the coercivity is to directly add a certain amount of heavy Dy and Tb in the sintered NdFeB master alloy, and replace the Nd in the Nd 2 Fe 14 B grains of the sintered NdFeB main phase with heavy rare earth elements such as Dy/Tb.
  • formation of (Nd, Dy) 2 Fe 14 B phase will increase the anisotropy field of the main phase magnetocrystalline, so that the coercive force of the magnet is greatly increased, but the rare earth resources are scarce and expensive, and the coking force is improved by the traditional alloying method. It will greatly increase the production cost.
  • the force NdFeB preparation method, and the grain boundary diffusion method is an effective method.
  • the grain boundary diffusion method is a metal, alloy or compound with a heavy rare earth element such as Dy/Tb attached to the surface of the NdFeB sintered magnet, and after suitable heat treatment, Dy/Tb on the surface of the magnet passes through the grain boundary of the sintered body to enter the sintering. Inside the body, it diffuses from the grain boundary to the inside of the main phase Nd 2 Fe 14 B. This treatment causes a significant increase in the coercive force of the magnet and a decrease in the residual magnetization.
  • the object of the present invention is to electroplate a layer of heavy rare earth metal film on the surface of the pretreated sintered NdFeB magnet, and then heat-treat, and the heavy rare earth element diffuses into the inside of the magnet through the grain boundary, thereby effectively increasing the coercive force of the magnet.
  • the heavy rare earth salt organic solution is used as a plating solution, and the surface of the surface-pretreated sintered NdFeB magnet is electroplated, and a thin layer of a heavy rare earth metal having a predetermined thickness and a flat shape is obtained by controlling the electroplating process; high temperature diffusion treatment or high temperature diffusion and low temperature
  • the tempering two-stage heat treatment causes the heavy rare earth elements in the heavy rare earth metal film to diffuse into the inside of the magnet through the grain boundary to increase the coercive force, and the specific steps are as follows:
  • A. Preparation of electroplating solution Dissolving a certain amount of heavy rare earth salt and organic acid in an organic solvent to prepare a heavy rare earth salt organic plating solution;
  • Electroplating using smooth graphite as the anode, the surface pretreated NdFeB magnet as the cathode, placed in the heavy rare earth salt organic solution prepared in step A, and subjected to direct current electroplating, wherein the direct current density is 0.01 A / cm 2 -50 A / cm 2 , electrodeposition temperature is room temperature ⁇ 100 ° C;
  • the organic acid is at least one selected from the group consisting of amino acid, glycolic acid, citric acid, and ethylenediaminetetraacetic acid, and the concentration of the organic acid in the solution is 0.001 mol/L to 10.0 mol/L.
  • the organic solvent is at least one of decanoic acid amide, dichloro decane, dimethyl hydrazine amide, and dimethyl sulfoxide.
  • the invention electroplating a heavy rare earth metal film on the surface of the sintered NdFeB magnet and high-temperature diffusion treatment, thereby improving the coercive force of the magnet; ⁇ depositing a dense elemental germanium layer on the surface of the magnet by a new plating method, and then performing grain boundary diffusion treatment, the magnet
  • the coercivity is obviously improved.
  • the interface between the plated element and the magnet is dense and the element has a large diffusion coefficient of the magnet, the process is simple and controllable, and the efficiency is high, which provides an efficient and low-cost way for industrial production. .
  • Figure 1 is a schematic view of the process of the present invention
  • Fig. 2 is a SEM topographical view of the Dy metal film on the surface of the magnet obtained in Example 1. detailed description
  • a graphite with a smooth surface as an anode and a cathode with a NdFeB magnet as a cathode are placed in the above-mentioned organic salt solution of cerium salt, and a direct current is applied thereto, and the current density is 0.05 A/cm 2 . Duration is 10 min. The temperature is 30 °C.
  • the NdFeB magnet coated with a base metal layer is taken out from the solution; the air-dried magnet is placed in a vacuum heat treatment furnace, and tempered at a temperature of 850 ° C for 10 h in an Ar atmosphere, and at a temperature of 500 ° C. Tempered for 2 h.
  • Tb Take a certain amount of Tb (N0 3 ). 63 ⁇ 40 and anhydrous citric acid dissolved in phthalamide organic solution, after dissolution The concentrations were 0.08 mol/L and 0.09 mol/L, respectively.
  • a graphite with a smooth surface as an anode and a cathode with a NdFeB magnet as a cathode are placed in the above-mentioned organic salt solution of cerium salt, and a direct current is applied thereto, and the current density is 20 A/cm 2 .
  • the duration is 5 min.
  • the temperature is 30 °C.
  • the NdFeB magnet coated with a ruthenium metal film on the surface is taken out from the solution; the air-dried magnet is placed in a vacuum heat treatment furnace, and tempered at a temperature of 900 ° C for 3 h in an Ar atmosphere at a temperature of 500 ° C for two times. Fire 1 h.
  • the invention electroplating a heavy rare earth metal film on the surface of the sintered NdFeB magnet and high-temperature diffusion treatment, thereby improving the coercive force of the magnet; ⁇ depositing a dense elemental germanium layer on the surface of the magnet by a new plating method, and then performing grain boundary diffusion treatment, the magnet
  • the coercivity is obviously improved.
  • the interface between the plated element and the magnet is dense and the element has a large diffusion coefficient of the magnet, the process is simple and controllable, and the efficiency is high, which provides an efficient and low-cost way for industrial production. .

Abstract

L'invention concerne un procédé de fixation de terre rare lourde pour aimant au néodyme NdFeB fritté, qui relève du domaine des matériaux fonctionnels magnétiques en terre rare et de leurs technologies de préparation. Le procédé de préparation comprend en particulier les étapes suivantes : placement d'un aimant au néodyme NdFeB fritté après prétraitement de surface dans une solution organique de sel de terre rare; dépôt d'un élément de terre rare lourde sur une surface de l'aimant au néodyme NdFeB fritté sous l'action d'un courant, de façon à former une couche mince métallique de terre rare lourde dense; et, dans le processus de traitement de diffusion à haute température ou de traitement thermique à deux étapes comprenant la diffusion haute température et la trempe basse température, diffusion, dans l'aimant à travers une interface cristalline, de l'élément de terre rare lourde dans un film métallique de terre rare lourde. Le champ coercitif d'un matériau magnétique permanent en terre rare de NdFeB fritté est remarquablement amélioré, la rémanence n'est manifestement pas réduite, la consommation de terre rare lourde est faible, le traitement est simple et réglable, le rendement est élevé, et le procédé est approprié à une production industrielle.
PCT/CN2014/074933 2013-12-11 2014-04-08 Procédé de fixation de terre rare lourde pour aimant au néodyme ndfeb fritté WO2015085687A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201310676521.4 2013-12-11
CN201310676521.4A CN103617884A (zh) 2013-12-11 2013-12-11 一种烧结NdFeB磁体的重稀土附着方法

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WO2015085687A1 true WO2015085687A1 (fr) 2015-06-18

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CN (1) CN103617884A (fr)
WO (1) WO2015085687A1 (fr)

Cited By (1)

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CN112908667A (zh) * 2020-06-29 2021-06-04 京磁材料科技股份有限公司 稀土永磁体的晶界扩散方法

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CN103617884A (zh) * 2013-12-11 2014-03-05 北京科技大学 一种烧结NdFeB磁体的重稀土附着方法
JP2015228431A (ja) * 2014-06-02 2015-12-17 インターメタリックス株式会社 ＲＦｅＢ系磁石及びＲＦｅＢ系磁石の製造方法
DE102014215873A1 (de) * 2014-08-11 2016-02-11 Siemens Aktiengesellschaft Elektrochemische Abscheidung eines schweren Seltenerdmaterials zur Vergrößerung der Koerzitivfeldstärke von Seltenerddauermagneten
CN105648487A (zh) * 2014-12-03 2016-06-08 北京中科三环高技术股份有限公司 电沉积方法、电沉积液和电沉积制备稀土永磁材料的方法
CN105839152A (zh) 2015-10-21 2016-08-10 北京中科三环高技术股份有限公司 电沉积方法、电沉积液和电沉积制备稀土永磁材料的方法
KR102210971B1 (ko) * 2016-03-11 2021-02-01 어플라이드 머티어리얼스, 인코포레이티드 반도체 프로세싱 장비 상에 이트륨 산화물을 형성하기 위한 방법
CN106169346B (zh) * 2016-08-31 2018-08-03 浙江凯文磁业有限公司 一种钕铁硼电镀Dy薄膜工艺
CN106601464B (zh) * 2016-12-14 2017-12-26 安徽大地熊新材料股份有限公司 一种低重稀土、高矫顽力的永磁材料的制备方法
CN107068380B (zh) * 2017-01-23 2020-02-18 包头天和磁材科技股份有限公司 永磁材料的生产方法
CN107617737B (zh) * 2017-11-10 2019-11-26 湖南稀土金属材料研究院 烧结钕铁硼永磁材料用粉体及其制备方法和应用
CN109003799B (zh) * 2018-07-06 2021-02-12 杭州永磁集团振泽磁业有限公司 一种高矫顽力钕铁硼磁体的制备方法
CN111430142B (zh) * 2019-01-10 2021-12-07 中国科学院宁波材料技术与工程研究所 晶界扩散制备钕铁硼磁体的方法
CN115798908B (zh) * 2022-11-14 2023-11-10 中磁科技股份有限公司 一种超薄层稀土包覆钕铁硼合金粉末的制备方法

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CN112908667B (zh) * 2020-06-29 2022-07-15 京磁材料科技股份有限公司 稀土永磁体的晶界扩散方法

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