CN110556243A - neodymium iron boron surface dysprosium penetration method - Google Patents
neodymium iron boron surface dysprosium penetration method Download PDFInfo
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- CN110556243A CN110556243A CN201910764772.5A CN201910764772A CN110556243A CN 110556243 A CN110556243 A CN 110556243A CN 201910764772 A CN201910764772 A CN 201910764772A CN 110556243 A CN110556243 A CN 110556243A
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- iron boron
- neodymium iron
- dysprosium
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- 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
Abstract
the invention belongs to the technical field of permanent magnet materials, in particular to a neodymium iron boron surface dysprosium penetration method, which comprises the following steps: (1) mixing dysprosium oxide powder with a sodium chloride solution to obtain a suspension, coating the suspension on the surface of neodymium iron boron, standing for 30min in an environment with the pressure of 5-10 MPa and the temperature of 170-300 ℃, taking out, washing away residues on the surface of the neodymium iron boron, and drying for later use; (2) mixing dysprosium oxide powder and an ethanol solution to form slurry, coating the slurry on the surface of the neodymium iron boron treated in the step (1), and quickly drying to obtain a semi-finished product; (3) carrying out laser shock treatment on the surface of the neodymium iron boron of the semi-finished product, then washing with deionized water, and drying; the method for dysprosium surface infiltration of neodymium iron boron provided by the invention realizes high-efficiency infiltration of dysprosium element on the surface of a neodymium iron boron magnet in a mode of matching high-temperature high-pressure induction and laser shock treatment, and the method for dysprosium surface infiltration is simple and convenient and has important application prospect.
Description
Technical Field
The invention belongs to the technical field of permanent magnet materials, and particularly relates to a neodymium iron boron surface dysprosium penetration method.
background
neodymium iron boron as one of rare earth permanent magnetic materials has extremely high magnetic energy and coercive force, can realize the mutual conversion between magnetic energy and electric energy, and is widely applied to the technical fields of information communication, medical equipment, aerospace, modern industry and electronics. Meanwhile, due to the advantage of high energy density, the neodymium iron boron permanent magnet material is applied to more in modern industry and electronic technology, so that the miniaturization, light weight and thinning of instruments, electro-acoustic motors, magnetic separation and magnetization and other equipment become possible.
the neodymium iron boron is divided into sintered neodymium iron boron and bonded neodymium iron boron, researchers mostly concentrate on adding a proper amount of elements or improving a magnet preparation process to improve the intrinsic coercivity of the sintered neodymium iron boron magnet, and the high coercivity of the magnet is utilized to resist the reduction of the performance of the magnet caused by the change of the external environment. The method for improving the coercive force of the sintered neodymium-iron-boron magnet comprises two methods: one is to improve the microstructure of the sintered Nd-Fe-B magnet, improve the grain boundary and the internal microstructure of the crystal of the sintered Nd-Fe-B magnet, reduce the existence of a stray magnetic field and improve the intrinsic coercive force of the sintered Nd-Fe-B magnet; the other method is to add a proper amount of trace elements such as heavy rare earth (dysprosium, terbium, yttrium and the like), copper, aluminum and the like in the preparation process of the sintered neodymium-iron-boron magnet, improve the anisotropy field HA of the sintered neodymium-iron-boron magnet by adding the trace elements, and drive the improvement of the intrinsic coercive force of the sintered neodymium-iron-boron magnet by utilizing the increase of the anisotropy field.
In the prior art, in order to ensure that the neodymium iron boron has higher coercive force, a certain amount of dysprosium or terbium needs to be added; moreover, based on the prior art, in order to ensure the content of dysprosium or terbium in neodymium iron boron, the amount of the added heavy rare earth is more, so that not only is the resource wasted, but also the production cost is increased. How to reduce the usage amount of dysprosium in the dysprosium infiltration process and ensure that enough dysprosium is contained in neodymium iron boron so as to ensure the coercive force of the neodymium iron boron magnet is the difficult point of continuous research of technicians in the field.
Disclosure of Invention
The invention aims to provide a method for dysprosium penetration on the surface of neodymium iron boron, which has the advantages that the consumption of dysprosium is low, and the processed neodymium iron boron has higher coercivity.
In order to achieve the purpose, the invention adopts the following technical scheme:
A dysprosium penetration method for a neodymium iron boron surface comprises the following steps:
(1) mixing dysprosium oxide powder with a sodium chloride solution to obtain a suspension, coating the suspension on the surface of neodymium iron boron, standing for 30min in an environment with the pressure of 5-10 MPa and the temperature of 170-300 ℃, taking out, washing away residues on the surface of the neodymium iron boron, and drying for later use;
(2) Mixing dysprosium oxide powder and an ethanol solution to form slurry, coating the slurry on the surface of the neodymium iron boron treated in the step (1), and quickly drying to obtain a semi-finished product;
(3) And carrying out laser shock treatment on the surface of the semi-finished neodymium iron boron, then washing with deionized water, and drying.
the inventor of the application finds that when the dysprosium penetration treatment is directly carried out on the non-pretreated neodymium iron boron surface, the rate of the dysprosium penetration is slow, and the purpose of high-efficiency dysprosium penetration cannot be further achieved. For this reason, the inventor of the present application contemplates that a sodium chloride solution having a corrosion effect on the surface of the ndfeb is used, and dysprosium oxide powder is supplemented to form a suspension, and a path through which dysprosium element invades into the interior of the ndfeb is opened in advance by coating the suspension on the surface of the ndfeb and inducing the suspension at a high temperature and a high pressure. When the sodium chloride rusts the surface of the neodymium iron boron magnet, dysprosium oxide doped in the suspension can preliminarily permeate along atom vacancies and gaps at the surface grain boundary; furthermore, dysprosium oxide powder and ethanol solution are mixed to form slurry, the slurry is coated on the surface of the pretreated neodymium iron boron, and dysprosium element is permeated into the neodymium iron boron in a laser shock treatment mode, so that the aim of improving the coercive force of the neodymium iron boron magnet is fulfilled. In addition, the inventor of the application also finds that the grain boundary phase composition and structure of the surface of the neodymium iron boron magnet are changed through the laser impact mode, the physicochemical property of the grain boundary phase is improved, and the compactness of the surface of the neodymium iron boron magnet is improved, so that the surface hardness, the fatigue life, the wear resistance and the corrosion resistance of the neodymium iron boron magnet are improved.
according to the invention, in the step (1), the mass fraction of the sodium chloride is 0.5-1%, and the particle size of the dysprosium oxide powder is 10-30 nm; the proportion of the dysprosium oxide powder to the sodium chloride solution is as follows: (1-5 g): (50-100 mL); the coating amount of the turbid liquid is 10-15 g per square centimeter of neodymium iron boron surface.
Further, according to the invention, in the step (2), the volume fraction of the ethanol solution is 95 vt%, and the particle size of the dysprosium oxide powder is 10-30 nm; the proportion of the dysprosium oxide powder to the ethanol solution is 1 g: 10 mL.
According to the present invention, the laser parameters used in the laser shock treatment in the present invention can be selected from a wide range, and preferably, in step (3), the laser shock treatment conditions include: the pulse width of the laser is 10-15 ns, the spot radius of the laser beam is 2-3 mm, and the single pulse energy is 5-20J.
further, the laser shock treatment conditions further comprise that the lap joint rate is 30% -50%, and shock is carried out for 2-3 times. In a specific implementation process, the center of a laser beam spot is overlapped with the upper left corner of the surface of the neodymium iron boron magnet to be processed to serve as an initial position of laser beam impact, so that the surface of the neodymium iron boron magnet is impacted line by line, and in order to obtain a better impact effect, the overlapped impact among lines is carried out, namely, when the next line is impacted, the impacted area of the previous line is impacted again, the overlapping rate is 30% -50%, and a good impact effect is ensured.
In the step (2), dysprosium oxide powder and ethanol solution form slurry and are coated on the surface of neodymium iron boron, multiple coatings can be carried out according to the requirement of dysprosium penetration, however, the amount of single coating is not too much or too little, if too little, energy is wasted by single laser impact, and if too much coating is carried out, dysprosium element contained in the slurry cannot be fully utilized to cause waste; preferably, according to the proportion of dysprosium oxide powder and ethanol solution in the slurry provided by the invention, the thickness of the slurry coated on the surface of neodymium iron boron is 1-5 μm.
Compared with the prior art, the invention has the following technical effects:
The method for dysprosium surface infiltration of neodymium iron boron provided by the invention realizes high-efficiency infiltration of dysprosium element on the surface of a neodymium iron boron magnet in a mode of matching high-temperature high-pressure induction and laser shock treatment, and the method for dysprosium surface infiltration is simple and convenient and has important application prospect.
Detailed Description
In order to make the technical means, the creation features, the achievement purposes and the effects of the invention easy to understand, the invention is further clarified with the specific embodiments.
example 1
a method for dysprosium surface infiltration of neodymium iron boron specifically comprises the following steps:
S1: dysprosium oxide powder (particle diameter of 20nm) was weighed, and 70mL of a sodium chloride solution (mass fraction of 0.5%) was mixed with 1g of dysprosium oxide powder to obtain a suspension,
the suspension was coated on neodymium iron boron (obtained from magnet under trade designation N48, gauge size)) Coating 12g of turbid liquid on each square centimeter of neodymium iron boron surface;
standing the neodymium iron boron coated with the suspension in an environment of 8MPa and 200 ℃ for 30min, taking out, washing away residues on the surface of the neodymium iron boron, and drying for later use;
S2: mixing dysprosium oxide powder (with the particle size of 20nm) and an ethanol solution (with the volume fraction of 95 vt%) into slurry, wherein the mixing ratio is that 10mL of ethanol solution is added to each 1g of dysprosium oxide powder; then coating the slurry on the surface of the neodymium iron boron treated in the step S1, wherein the thickness of the slurry coated on the surface of the neodymium iron boron is 3 microns, and quickly drying to obtain a semi-finished product;
S3: performing laser shock treatment on the surface of the semi-finished neodymium iron boron, wherein the laser pulse width of the laser is 12ns, the spot radius of a laser beam is 2mm, and the single pulse energy is 10J; the lapping rate during laser impact is 40%, and the laser impact is carried out for 2 times, and then the laser impact is washed by deionized water and dried.
Example 2
the method for dysprosium surface infiltration on neodymium iron boron as provided in example 1, except that in the step of preparing the suspension in step S1, 1g of dysprosium oxide powder is mixed with 10mL of sodium chloride solution (with a mass fraction of 0.5%) to obtain a suspension;
Keeping the rest unchanged to obtain the treated neodymium iron boron.
Example 3
the method for dysprosium surface infiltration on neodymium iron boron as provided in example 1, except that in the step of preparing the suspension in step S1, 1g of dysprosium oxide powder is mixed with 100mL of sodium chloride solution (with a mass fraction of 0.5%) to obtain a suspension;
Keeping the rest unchanged to obtain the treated neodymium iron boron.
comparative example 1
The method for dysprosium surface doping of neodymium iron boron as provided in example 1, except that the suspension does not contain dysprosium oxide powder, namely, the surface of neodymium iron boron is directly coated with sodium chloride solution, and the coating amount is consistent with that of example 1;
keeping the rest unchanged to obtain the treated neodymium iron boron.
Comparative example 2
The method for dysprosium surface infiltration on neodymium iron boron as provided in example 1, except that in the step of preparing the suspension in step S1, 1g of dysprosium oxide powder is mixed with 5mL of sodium chloride solution (with a mass fraction of 0.5%) to obtain a suspension;
Keeping the rest unchanged to obtain the treated neodymium iron boron.
example 4
The method for dysprosium penetration on a neodymium iron boron surface as provided in example 1, except that the coating amount of the suspension is 10g per square centimeter of the neodymium iron boron surface;
Keeping the rest unchanged to obtain the treated neodymium iron boron.
Example 5
The method for dysprosium penetration into a neodymium iron boron surface as provided in example 1, except that the suspension is applied in an amount of 15g per square centimeter of neodymium iron boron surface;
Keeping the rest unchanged to obtain the treated neodymium iron boron.
example 6
The method for dysprosium surface doping of neodymium iron boron as provided in example 1, except that the thickness of the slurry coated on the neodymium iron boron surface in the step S2 is 1 μm;
Keeping the rest unchanged to obtain the treated neodymium iron boron.
Example 7
The method for dysprosium surface doping of neodymium iron boron as provided in example 1, except that the thickness of the slurry coated on the neodymium iron boron surface in the step S2 is 5 μm;
Keeping the rest unchanged to obtain the treated neodymium iron boron.
Example 8
The method for dysprosium surface doping of neodymium iron boron as provided in example 1, except that in step S3, laser shock treatment is performed 3 times; keeping the rest unchanged to obtain the treated neodymium iron boron.
The performance of the treated ndfeb magnets of the above examples 1-8 and comparative examples 1-2 was tested according to GB/T3217-.
Table 1:
| Sample (7mm) | Coercive force (Hcj) Koe |
| Commercial brand N48 | 14.37 |
| Example 1 | 17.52 |
| Example 2 | 15.94 |
| Example 3 | 18.26 |
| example 4 | 17.48 |
| Example 5 | 17.57 |
| example 6 | 17.18 |
| example 7 | 17.83 |
| Example 8 | 18.06 |
| comparative example 1 | 15.23 |
| Comparative example 2 | 15.54 |
The data in table 1 show that the neodymium iron boron surface dysprosium penetration method provided by the invention can obviously improve the coercive force of neodymium iron boron.
The foregoing shows and describes the general principles, essential features, and inventive features of this invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. The dysprosium penetration method for the neodymium iron boron surface is characterized by comprising the following steps of:
(1) mixing dysprosium oxide powder with a sodium chloride solution to obtain a suspension, coating the suspension on the surface of neodymium iron boron, standing for 30min in an environment with the pressure of 5-10 MPa and the temperature of 170-300 ℃, taking out, washing away residues on the surface of the neodymium iron boron, and drying for later use;
(2) Mixing dysprosium oxide powder and an ethanol solution to form slurry, coating the slurry on the surface of the neodymium iron boron treated in the step (1), and quickly drying to obtain a semi-finished product;
(3) and carrying out laser shock treatment on the surface of the semi-finished neodymium iron boron, then washing with deionized water, and drying.
2. The method for dysprosium surface infiltration of neodymium iron boron according to claim 1, characterized in that in step (1), the mass fraction of sodium chloride is 0.5-1%, and the particle size of dysprosium oxide powder is 10-30 nm;
The proportion of the dysprosium oxide powder to the sodium chloride solution is as follows: (1-5 g): (50-100 mL);
The coating amount of the turbid liquid is 10-15 g per square centimeter of neodymium iron boron surface.
3. the method for dysprosium surface infiltration of neodymium iron boron according to claim 1, characterized in that in step (2), the volume fraction of the ethanol solution is 95 vt%, and the particle size of the dysprosium oxide powder is 10-30 nm;
The proportion of the dysprosium oxide powder to the ethanol solution is 1 g: 10 mL.
4. The method for dysprosium surface infiltration of neodymium iron boron according to claim 1, wherein in step (3), the laser shock treatment conditions comprise: the pulse width of the laser is 10-15 ns, the spot radius of the laser beam is 2-3 mm, and the single pulse energy is 5-20J.
5. The method for dysprosium surface infiltration of neodymium iron boron according to claim 4, wherein in step (3), the laser shock treatment conditions further comprise that the lapping rate is 30% -50% and the shock is 2-3 times.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112712954A (en) * | 2020-12-23 | 2021-04-27 | 安徽大地熊新材料股份有限公司 | Preparation method of sintered neodymium-iron-boron magnet |
| CN112837921A (en) * | 2021-01-06 | 2021-05-25 | 陈凯华 | Method for dysprosium penetration of neodymium iron boron magnet |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6703915B1 (en) * | 2000-09-01 | 2004-03-09 | Kaneka Corporation | Magnet roller |
| 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 |
| CN103556208A (en) * | 2013-11-04 | 2014-02-05 | 北京工业大学 | Treating agent and electro-deposition method for forming rare earth hydride particle coating |
| US20140041761A1 (en) * | 2011-03-02 | 2014-02-13 | Adaptive Materials Technology - Adaptamat Oy | Method of producing magnetic shape memory alloy elements and the use thereof |
| CN105957706A (en) * | 2016-04-28 | 2016-09-21 | 北京科技大学 | Method for preparing high-performance neodymium iron boron magnet by pressure impregnation of Dy<3+>/Tb<3+> |
| CN106158205A (en) * | 2016-08-29 | 2016-11-23 | 京磁材料科技股份有限公司 | A kind of preparation method of neodymium iron boron magnetic body |
| CN108962525A (en) * | 2018-06-25 | 2018-12-07 | 山西师范大学 | A kind of preparation method of Sintered NdFeB magnet surface layer magnetic gradient nanostructure |
-
2019
- 2019-08-19 CN CN201910764772.5A patent/CN110556243B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6703915B1 (en) * | 2000-09-01 | 2004-03-09 | Kaneka Corporation | Magnet roller |
| 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 |
| US20140041761A1 (en) * | 2011-03-02 | 2014-02-13 | Adaptive Materials Technology - Adaptamat Oy | Method of producing magnetic shape memory alloy elements and the use thereof |
| CN103556208A (en) * | 2013-11-04 | 2014-02-05 | 北京工业大学 | Treating agent and electro-deposition method for forming rare earth hydride particle coating |
| CN105957706A (en) * | 2016-04-28 | 2016-09-21 | 北京科技大学 | Method for preparing high-performance neodymium iron boron magnet by pressure impregnation of Dy<3+>/Tb<3+> |
| CN106158205A (en) * | 2016-08-29 | 2016-11-23 | 京磁材料科技股份有限公司 | A kind of preparation method of neodymium iron boron magnetic body |
| CN108962525A (en) * | 2018-06-25 | 2018-12-07 | 山西师范大学 | A kind of preparation method of Sintered NdFeB magnet surface layer magnetic gradient nanostructure |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112712954A (en) * | 2020-12-23 | 2021-04-27 | 安徽大地熊新材料股份有限公司 | Preparation method of sintered neodymium-iron-boron magnet |
| CN112837921A (en) * | 2021-01-06 | 2021-05-25 | 陈凯华 | Method for dysprosium penetration of neodymium iron boron magnet |
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