WO2015085687A1 - Heavy rare earth attachment method for sintered ndfeb magnet - Google Patents

Heavy rare earth attachment method for sintered ndfeb magnet Download PDF

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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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rare earth
heavy rare
sintered ndfeb
magnet
ndfeb magnet
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PCT/CN2014/074933
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French (fr)
Chinese (zh)
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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
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北京科技大学
北京盛磁科技有限公司
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Publication of WO2015085687A1 publication Critical patent/WO2015085687A1/en

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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/54Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00Electroplating characterised by the article coated
    • C25D7/001Magnets
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00Apparatus 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
    • H01F41/02Apparatus 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
    • H01F41/0253Apparatus 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
    • H01F41/0293Apparatus 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

A heavy rare earth attachment method for a sintered NdFeB magnet, which relates to the field of rare earth magnetic functional materials and preparation technologies. The preparation process particularly comprises the steps: placing a sintered NdFeB magnet after surface pretreatment in a heavy rare earth salt organic solution, a heavy rare earth element being deposited on a surface of the sintered NdFeB magnet under the action of a current, so as to form a dense heavy rare earth metal thin layer, and in the process of high-temperature diffusion treatment or two-stage thermal treatment comprising high-temperature diffusion and low temperature tempering, the heavy rare earth element in a heavy rare earth metal film diffusing into the magnet through a grain boundary. Coercivity of a sintered NdFeB rare earth permanent magnetic material is remarkably improved, remanence is not obviously reduced, heavy rare earth consumption is small, the process is simple and controllable, the efficiency is high, and the method is suitable for industrial production.

Description

一种烧结 NdFeB磁体的重稀土附着方法 本专利申请要求申请号 201310676521.4、 申请日 20131211、 发明名称为 一种烧结 NdFeB磁体的重稀土附着方法的中国专利申请的优先权。 技术领域  A method for adhering a heavy rare earth of a sintered NdFeB magnet. The present application claims priority to Chinese Patent Application No. 201310676521.4, the filing date of the Japanese Patent No. 20131211. Technical field
本发明属于稀土磁性功能材料技术领域, 涉及一种烧结 NdFeB磁体的重 稀土附着方法。 背景技术  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
钕铁硼具有极高的磁能积,高能量密度的优点使其在现代工业和电子技术 中获得了广泛应用。钕铁硼磁性材料不足之处在于居里温度点低,温度特性差。 而新能源等节能环保领域对所使用的永磁材料提出了更高的要求,不仅具有高 的磁能积, 而且具有高的矫顽力。  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. In the field of energy conservation and environmental protection such as new energy, 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.
提高矫顽力最常用的途径是在烧结 NdFeB母合金中直接添加一定量的重 稀 Dy和 Tb, Dy/Tb等重稀土元素取代烧结钕铁硼主相 Nd2Fe14B晶粒内的 Nd, 形成 (Nd,Dy)2Fe14B相, 将提高主相磁晶各向异性场, 使磁体矫顽力大幅增加, 但是重稀土资源稀缺价格昂贵,釆用传统合金化法提高矫顽力会大幅增加生产 成本, 更严重的是, 由于重稀土离子与铁离子之间的反铁磁耦合, 造成重稀土 元素添加后剩磁及磁能积大幅下降, 因此, 需要开发更经济的高矫顽力的 NdFeB制备方法, 而晶界扩散法是一种有效的方法。 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. More seriously, due to the antiferromagnetic coupling between heavy rare earth ions and iron ions, the remanence and magnetic energy product after the addition of heavy rare earth elements are greatly reduced. Therefore, it is necessary to develop a more economical high coercivity. The force NdFeB preparation method, and the grain boundary diffusion method is an effective method.
晶界扩散方法是在 NdFeB烧结磁体的表面附有 Dy/Tb等重稀土元素的金 属、 合金或化合物, 并经适宜的热处理后, 磁体表面的 Dy/Tb会穿过烧结体 的晶界进入烧结体内部, 从晶界向主相 Nd2Fe14B 内部扩散。 这样处理会使磁 体的矫顽力明显提高而剩磁下降不明显。 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.
近些年研究晶界扩散处理方法有多种, 如中国专利 CN102280240A提出 的 "磁控溅射法"、 中国专利 CN10296911 OA提出的 "气相沉积法"、 中国专利 CN101845637A提出的 "涂覆法"、 中国专利 CN102776547A提出的 "电脉沉 积法" 等。 磁控溅射、 气相沉积等方法提高磁体矫顽力的效果好, 但存在生产 效率低、 成本高、 批量生产难度大以及设备投入大等问题。 涂覆法的涂层厚度 不易控制且不平整, 易脱落、 残留而造成浪费, 并且提高矫顽力的效果欠佳。 电脉沉积表面所沉积的 (Dy)2(OH)5N03 n¾0等化合物在随后高温处理阶段分 解成高熔点的氧化物,扩散系数低,扩散保温时间长,提高矫顽力的效果欠佳。 发明内容 In recent years, there have been many research methods for grain boundary diffusion treatment, such as the "magnetron sputtering method" proposed by Chinese patent CN102280240A, the "vapor deposition method" proposed by Chinese patent CN10296911 OA, and the Chinese patent. CN101845637A proposed "coating method", "electric pulse deposition method" proposed by Chinese patent CN102776547A, and the like. Magnetron sputtering, vapor deposition and other methods improve the coercivity of the magnet, but there are problems such as low production efficiency, high cost, difficulty in mass production, and large equipment investment. The coating thickness of the coating method is not easy to control and is uneven, easy to fall off, residual and waste, and the effect of improving the coercive force is not good. Compounds such as (Dy) 2 (OH) 5 N0 3 n3⁄40 deposited on the surface of the electrodeposited surface are decomposed into high melting point oxides at the subsequent high temperature treatment stage, with low diffusion coefficient, long diffusion holding time, and poor coercivity. . Summary of the invention
本发明的目的是在经过预处理的烧结 NdFeB磁体表面电镀一层重稀土金 属膜, 然后经热处理, 重稀土元素通过晶界扩散进入磁体内部, 从而有效提高 磁体的矫顽力。  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.
本发明实施例提供的一种高矫顽力 NdFeB 重稀土扩散层的电镀制备方 法,  A method for preparing a high coercivity NdFeB heavy rare earth diffusion layer provided by an embodiment of the present invention,
以重稀土盐有机溶液为电镀溶液, 在经过表面预处理的烧结 NdFeB磁体 表面进行电镀, 通过控制电镀工艺得到预定厚度且形貌平整的重稀土金属薄 层;通过高温扩散处理或高温扩散及低温回火两级热处理使重稀土金属膜中的 重稀土元素通过晶界扩散到磁体内部, 提高其矫顽力, 其具体步聚如下:  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. 电镀溶液的配制: 将一定量的重稀土盐与有机酸溶于有机溶剂中, 配 制重稀土盐有机电镀溶液;  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;
B. 电镀:以光滑的石墨为阳极,以经过表面预处理的 NdFeB磁体为阴极, 置放于步骤 A中配制的重稀土盐有机溶液中, 通入直流电, 进行电镀, 其中 直流电流密度为 0.01 A/cm2 -50 A/cm2, 电沉积温度为室温〜 100°C; B. 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;
C.热处理: 将表面沉积有重稀土金属膜的 NdFeB磁体从溶液中取出; 将 风干后的磁体置于真空热处理炉中, 然后在保护气氛下进行热处理, 高温扩散 处理是在 700 1000 °C条件下保温 1~50 h, 低温回火处理是在 400 700 °C条件 下保温 l~10h, 得到带有重稀土扩散层的烧结 NdFeB稀土永磁材料。  C. Heat treatment: The NdFeB magnet with a heavy rare earth metal film deposited on the surface is taken out from the solution; the air-dried magnet is placed in a vacuum heat treatment furnace, and then heat treated under a protective atmosphere, and the high temperature diffusion treatment is at 700 1000 °C. The lower temperature is tempered for 1~50 h, and the low temperature tempering treatment is kept at 400 700 °C for l~10h to obtain sintered NdFeB rare earth permanent magnet material with heavy rare earth diffusion layer.
其中, 所述的重稀土盐选自 R( N03 )· n¾0( n=0~9 )、RCl3、R2(S04)3*n¾0, 其中 R代表包含礼、 铽、 镝、 钬、 铒、 铥、 镱、 镥、 钇在内的重稀土元素中 的至少一种, 重稀土盐溶后在溶液中浓度为 0.001 mol/L~10.0 mol/L。 其中, 所述的有机酸选自氨基横酸、 羟基乙酸、 柠檬酸、 乙二胺四乙酸中 的至少一种, 有机酸溶后其在溶液中浓度为 0.001mol/L~10.0 mol/L。 Wherein, the heavy rare earth salt is selected from the group consisting of R(N0 3 )· n3⁄40 (n=0~9), RCl 3 , R 2 (S0 4 ) 3 *n3⁄40, wherein R represents ritual, 铽, 镝, 钬, At least one of heavy rare earth elements such as lanthanum, cerium, lanthanum, cerium and lanthanum is dissolved in a solution of 0.001 mol/L to 10.0 mol/L. Wherein, 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.
其中, 所述有机溶剂为曱酰胺、 二氯曱烷、 二曱基曱酰胺、 二曱基亚砜中 的至少一种。  The organic solvent is at least one of decanoic acid amide, dichloro decane, dimethyl hydrazine amide, and dimethyl sulfoxide.
本发明是在烧结 NdFeB磁体表面电镀重稀土金属膜并高温扩散处理, 从 而提高磁体矫顽力; 釆用电镀新途径在磁体表面沉积一层致密的单质镝层,再 经晶界扩散处理, 磁体的矫顽力得到明显提高, 相对于其他方法, 电镀单质镝 与磁体界面结合致密且单质镝在磁体扩散系数大, 工艺简单可控, 效率高, 为 工业化生产提供了一条高效、 低成本的途径。 附图说明  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; 釆 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. Compared with other methods, 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. . DRAWINGS
图 1为本发明工艺示意图;  Figure 1 is a schematic view of the process of the present invention;
图 2为实施例 1获得的磁体表面 Dy金属膜 SEM形貌图。 具体实施方式  Fig. 2 is a SEM topographical view of the Dy metal film on the surface of the magnet obtained in Example 1. detailed description
为使本发明要解决的技术问题、技术方案和优点更加清楚, 下面将结合附 图及具体实施例进行详细描述。  In order to make the technical problems, technical solutions, and advantages of the present invention more clear, the following detailed description will be made in conjunction with the accompanying drawings and specific embodiments.
实施例 1  Example 1
( 1 ) 配制成镝盐有机溶剂  (1) Formulated into a cerium salt organic solvent
取一定量的 Dy(N03) 6H20和无水柠檬酸溶于二氯曱烷有机溶液, 溶后 浓度分别为 2.5 mol/L和 2.6 mol/L。 A certain amount of Dy(N0 3 ) 6H 2 0 and anhydrous citric acid were dissolved in the organic solution of dichloromethane at a concentration of 2.5 mol/L and 2.6 mol/L, respectively.
( 2 )以表面光滑的石墨为阳极, 以 NdFeB磁体为阴极, 置放于上述配制 的镝盐有机溶液中, 通入直流电流, 电流密度为 0.05A/cm2。持续时间 10 min。 温度为 30°C。 将表面镀有镝金属层的 NdFeB磁体从溶液中取出; 将风干后的 磁体置于真空热处理炉中, 在 Ar气氛中 850°C条件下一级回火 10 h, 500°C条 件下二级回火 2 h。 (2) 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.
实施例 2  Example 2
( 1 ) 配制铽盐有机溶剂  (1) Preparation of bismuth salt organic solvent
取一定量的 Tb ( N03 ). 6¾0和无水柠檬酸溶于曱酰胺有机溶液, 溶后 浓度分别为 0.08 mol/L和 0.09 mol/L。 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.
( 2 )以表面光滑的石墨为阳极, 以 NdFeB磁体为阴极, 置放于上述配制 的镝盐有机溶液中, 通入直流电流, 电流密度为 20A/cm2。 持续时间 5 min。 温度为 30°C。 将表面镀有镝金属膜的 NdFeB磁体从溶液中取出; 将风干后的 磁体置于真空热处理炉中,在 Ar气氛中 900°C条件下一级回火 3h, 500°C条件 下二级回火 1 h。 (2) 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.
本发明是在烧结 NdFeB磁体表面电镀重稀土金属膜并高温扩散处理, 从 而提高磁体矫顽力; 釆用电镀新途径在磁体表面沉积一层致密的单质镝层,再 经晶界扩散处理, 磁体的矫顽力得到明显提高, 相对于其他方法, 电镀单质镝 与磁体界面结合致密且单质镝在磁体扩散系数大, 工艺简单可控, 效率高, 为 工业化生产提供了一条高效、 低成本的途径。  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; 釆 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. Compared with other methods, 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. .
以上所述是本发明的优选实施方式,应当指出,对于本技术领域的普通技 术人员来说,在不脱离本发明所述原理的前提下,还可以做出若干改进和润饰, 这些改进和润饰也应视为本发明的保护范围。  The above is a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make several improvements and retouchings without departing from the principles of the present invention. It should also be considered as the scope of protection of the present invention.

Claims

权 利 要 求 书 Claim
1. 一种烧结 NdFeB磁体的重稀土附着方法, 其特征在于, A method for attaching a heavy rare earth of a sintered NdFeB magnet, characterized in that
以重稀土盐有机溶液为电镀溶液, 在经过表面预处理的烧结 NdFeB磁体 表面进行电镀, 通过控制电镀工艺得到预定厚度且形貌平整的重稀土金属薄 层;通过高温扩散处理或高温扩散及低温回火两级热处理使重稀土金属膜中的 重稀土元素通过晶界扩散到磁体内部, 提高其矫顽力, 其具体步聚如下:  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. 电镀溶液的配制: 将一定量的重稀土盐与有机酸溶于有机溶剂中, 配 制重稀土盐有机电镀溶液;  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;
B. 电镀: 以光滑的石墨为阳极, 以经过表面预处理的烧结 NdFeB磁体为 阴极, 置放于步骤 A中配制的重稀土盐有机溶液中, 通入直流电, 进行电镀, 其中电流密度为 0.01 A/cm2 -50 A/cm2, 电沉积温度为室温〜 100°C; B. Electroplating: using smooth graphite as the anode, a surface-pretreated sintered 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 current density is 0.01. A / cm 2 -50 A / cm 2 , electrodeposition temperature is room temperature ~ 100 ° C;
C. 热处理: 将表面沉积有重稀土金属膜的 NdFeB磁体从溶液中取出, 釆 用保护气体风干的方式使表面残留的有机溶剂挥发;将风干后的磁体置于真空 热处理炉中, 然后在保护气氛下进行热处理, 高温扩散处理是在 700-1000 °C 条件下保温 l~50 h, 低温回火处理是在 400~700°C条件下保温 l~10h, 得到带 有重稀土扩散层的烧结 NdFeB稀土永磁材料。  C. Heat treatment: The NdFeB magnet with a heavy rare earth metal film deposited on the surface is taken out from the solution, and the residual organic solvent on the surface is volatilized by air drying with a protective gas; the air-dried magnet is placed in a vacuum heat treatment furnace, and then protected. The heat treatment is carried out under the atmosphere. The high temperature diffusion treatment is maintained at 700-1000 °C for 1~50 h, and the low temperature tempering treatment is maintained at 400~700 °C for 1~10 h to obtain the sintering with the heavy rare earth diffusion layer. NdFeB rare earth permanent magnet material.
2. 如权利要求 1所述的一种烧结 NdFeB磁体的重稀土附着方法, 其特征 在于, 所述的重稀土盐选自 R ( N03 ). n¾O ( n=0~9 )、 RC13、 R2(S04)3'n¾0, 其中 R代表包含礼、 铽、 镝、 钬、 铒、 铥、 镱、 镥、 钇在内的重稀土元素中 的至少一种, 重稀土盐溶后在溶液中浓度为 0.001 mol/L~10.0 mol/L。 The method for attaching a heavy rare earth of a sintered NdFeB magnet according to claim 1, wherein the heavy rare earth salt is selected from the group consisting of R (N0 3 ). n3⁄4O (n=0~9), RC1 3 , R 2 (S0 4 ) 3 'n3⁄40, wherein R represents at least one of heavy rare earth elements including ritual, cerium, lanthanum, cerium, lanthanum, cerium, lanthanum, cerium, lanthanum, and the solution of the heavy rare earth salt in solution The medium concentration is 0.001 mol/L to 10.0 mol/L.
3. 如权利要求 1所述的一种烧结 NdFeB磁体的重稀土附着方法, 其特征 在于, 所述的有机酸选自氨基横酸、 羟基乙酸、 柠檬酸、 乙二胺四乙酸中的至 少一种, 有机酸溶后其在溶液中浓度为 0.001mol/L~10.0 mol/L。  The method of attaching a heavy rare earth of a sintered NdFeB magnet according to claim 1, wherein the organic acid is at least one selected from the group consisting of amino acid, glycolic acid, citric acid, and ethylenediaminetetraacetic acid. The concentration of the organic acid in the solution is 0.001 mol/L to 10.0 mol/L.
4. 如权利要求 1-3任一项所述的一种烧结 NdFeB磁体的重稀土附着方法, 其特征在于, 所述有机溶剂为曱酰胺、 二氯曱烷、 二曱基曱酰胺、 二曱基亚砜 中的至少一种。  The method for attaching a heavy rare earth of a sintered NdFeB magnet according to any one of claims 1 to 3, wherein the organic solvent is hydrazine amide, dichloro decane, dimercapto amide, and bismuth. At least one of the sulfoxides.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112908667A (en) * 2020-06-29 2021-06-04 京磁材料科技股份有限公司 Grain boundary diffusion method of rare earth permanent magnet

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103617884A (en) * 2013-12-11 2014-03-05 北京科技大学 Heavy rear earth adhering method of sintered NdFeB magnet
JP2015228431A (en) * 2014-06-02 2015-12-17 インターメタリックス株式会社 Rare-earth iron boron based magnet and manufacturing method thereof
DE102014215873A1 (en) * 2014-08-11 2016-02-11 Siemens Aktiengesellschaft Electrochemical deposition of a heavy rare earth material to increase the coercivity of rare earth permanent magnets
CN105648487A (en) * 2014-12-03 2016-06-08 北京中科三环高技术股份有限公司 Electro-deposition method, electro-deposition liquid and method for preparing rare earth permanent magnetic material in electro-deposition manner
CN105839152A (en) * 2015-10-21 2016-08-10 北京中科三环高技术股份有限公司 Electrodeposition method, electrodeposition solution and method for preparation of rare earth permanent magnetic material by electrodeposition
WO2017155711A1 (en) * 2016-03-11 2017-09-14 Applied Materials, Inc. Method for electrochemically grown yttria or yttrium oxide on semiconductor processing equipment
CN106169346B (en) * 2016-08-31 2018-08-03 浙江凯文磁业有限公司 A kind of neodymium iron boron plating Dy thin-film techniques
CN106601464B (en) * 2016-12-14 2017-12-26 安徽大地熊新材料股份有限公司 A kind of low heavy rare earth, high-coercive force permanent-magnet material preparation method
CN107068380B (en) * 2017-01-23 2020-02-18 包头天和磁材科技股份有限公司 Method for producing permanent magnetic material
CN107617737B (en) * 2017-11-10 2019-11-26 湖南稀土金属材料研究院 Sintered Nd-Fe-B permanent magnetic material powder and its preparation method and application
CN109003799B (en) * 2018-07-06 2021-02-12 杭州永磁集团振泽磁业有限公司 Preparation method of high-coercivity neodymium-iron-boron magnet
CN111430142B (en) * 2019-01-10 2021-12-07 中国科学院宁波材料技术与工程研究所 Method for preparing neodymium iron boron magnet by grain boundary diffusion
CN115798908B (en) * 2022-11-14 2023-11-10 中磁科技股份有限公司 Preparation method of ultrathin-layer rare earth coated neodymium-iron-boron alloy powder

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0345092A1 (en) * 1988-06-02 1989-12-06 Shin-Etsu Chemical Co., Ltd. A method for producing a corrosion resistant rare earth- containing magnet
JP2004200387A (en) * 2002-12-18 2004-07-15 Sumitomo Special Metals Co Ltd Corrosion-resistant permanent magnet and its manufacturing method
CN101845637A (en) * 2009-03-25 2010-09-29 罗阳 Grain boundary diffusion process for neodymium iron boron magnet
CN102103916A (en) * 2009-12-17 2011-06-22 北京有色金属研究总院 Preparation method of neodymium iron boron magnet
CN102776547A (en) * 2012-08-23 2012-11-14 安泰科技股份有限公司 Method for preparing rare earth permanent magnetic material
CN102969110A (en) * 2012-11-21 2013-03-13 烟台正海磁性材料股份有限公司 Device and method for improving magnetic coercivity of NdFeB (neodymium iron boron)
CN103617884A (en) * 2013-12-11 2014-03-05 北京科技大学 Heavy rear earth adhering method of sintered NdFeB magnet

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0645913B2 (en) * 1989-05-25 1994-06-15 石原薬品株式会社 Rare earth metal plating solution
CN1217035C (en) * 2002-09-27 2005-08-31 长沙高新技术产业开发区英才科技有限公司 Process of electricity sedimentation in aqueous solution for producing rare earth magnetic film alloy material
CN1206391C (en) * 2003-07-18 2005-06-15 中山大学 Method for preparing rare earth alloy through sweeping electric potential sedimentation
JP4765747B2 (en) * 2006-04-19 2011-09-07 日立金属株式会社 Method for producing R-Fe-B rare earth sintered magnet
CN102400191B (en) * 2011-11-22 2014-04-09 沈阳理工大学 Method for preparing Sm-Fe (samarium-ferrum) alloy magnetic thin film under intense magnetic field

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0345092A1 (en) * 1988-06-02 1989-12-06 Shin-Etsu Chemical Co., Ltd. A method for producing a corrosion resistant rare earth- containing magnet
JP2004200387A (en) * 2002-12-18 2004-07-15 Sumitomo Special Metals Co Ltd Corrosion-resistant permanent magnet and its manufacturing method
CN101845637A (en) * 2009-03-25 2010-09-29 罗阳 Grain boundary diffusion process for neodymium iron boron magnet
CN102103916A (en) * 2009-12-17 2011-06-22 北京有色金属研究总院 Preparation method of neodymium iron boron magnet
CN102776547A (en) * 2012-08-23 2012-11-14 安泰科技股份有限公司 Method for preparing rare earth permanent magnetic material
CN102969110A (en) * 2012-11-21 2013-03-13 烟台正海磁性材料股份有限公司 Device and method for improving magnetic coercivity of NdFeB (neodymium iron boron)
CN103617884A (en) * 2013-12-11 2014-03-05 北京科技大学 Heavy rear earth adhering method of sintered NdFeB magnet

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112908667A (en) * 2020-06-29 2021-06-04 京磁材料科技股份有限公司 Grain boundary diffusion method of rare earth permanent magnet
CN112908667B (en) * 2020-06-29 2022-07-15 京磁材料科技股份有限公司 Grain boundary diffusion method of rare earth permanent magnet

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