CN1186154C - Process for producing rare-earth-iron-boron permanent magnet alloy powder by reduction diffusion - Google Patents
Process for producing rare-earth-iron-boron permanent magnet alloy powder by reduction diffusion Download PDFInfo
- Publication number
- CN1186154C CN1186154C CNB021596646A CN02159664A CN1186154C CN 1186154 C CN1186154 C CN 1186154C CN B021596646 A CNB021596646 A CN B021596646A CN 02159664 A CN02159664 A CN 02159664A CN 1186154 C CN1186154 C CN 1186154C
- Authority
- CN
- China
- Prior art keywords
- powder
- raw material
- reduction
- alloy powder
- diffusion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
The present invention provides a method for preparing rare earth permanent magnetic alloy powder using a reduction diffusion method. The method has the technological processes of selection and pre-treatment of raw materials, proportioning of reactants, mixture of the reactants, metallothermic reduction, diffusion alloying, reaction product chemical separation, dehydration of metal powder and fabrication of anisotropic R-Fe-B bonded permanent magnets. The method is characterized in that rare earth oxide, selected and controlled granularity of base alloy element iron powder, metal Ca, CaH2, auxiliary agent NdCl3 and CaCl2 are carried out reduction diffusion reaction within a lower temperature range of 820 to 960 DEG C; alloy powder, the needed granularity of which can be used for fabricating anisotropic bonded permanent magnets, can be directly obtained after products of the reduction diffusion reaction are separated in a chemical method. The method has the advantage of simple process, and the loss of alloy powder magnetic performance is avoided.
Description
Technical field
The invention belongs to technical field of magnetic materials, the manufacture method at a kind of rare earth permanent magnet alloy powder end particularly is provided.
Background technology:
Nd-Fe-B is that rare earth permanent magnet is the permanent-magnet material that a class has excellent properties, and this material has sintering and bonds two types.Bonding R-Fe-B magnet can be made slim, special-shaped and can be one-body molded with device, precision height, stock utilization height, fill demagnetization characteristics such as characteristic is good, the magnetic technology of preparing of R-Fe-B permanent magnetism of being used at present to bond have quick quenching technique (US4802931, US4851858) and the HDDR method.Quick quenching technique is with high-purity neodymium metal, high purity iron and boron or ferro-boron are raw material, become the R-Fe-B foundry alloy through vacuum metling, and then remelting, melt is ejected into by high-pressure inert gas stream on the water-cooled copper roller of at a high speed rotation and is frozen into the band bits rapidly, is broken into alloy powder subsequently and carries out crystallization and thermal treatment at 600-800 ℃.This magnetic can be used to make isotropism R-Fe-B bonded permanent magnet.HDDR (hydrogenation-disproportionation--dehydrogenation-reorganization) method is with high-purity neodymium metal, pure iron or ferro-boron are raw material, vacuum melting becomes the R-Fe-B alloy, be broken into meal less than 1mm, place hydrogen to handle stove respectively under different temperatures, hydrogen pressure and condition of negative pressure, the R-Fe-B alloy passes through hydrogenation-disproportionation--dehydrogenation-regrouping process and fragmentation, again through grinding the requirement that reaches the refinement powder size.This magnetic can be used for making anisotropy R-Fe-B bonded permanent magnet, and anisotropic bonded magnet is than isotropic bonded magnet magnetic property height.
Quick quenching technique and HDDR method all are to adopt complex techniques process and the high pure rare earth metals and the high purity iron that make are raw material.Bonded permanent magnet has certain requirement to powder size in addition, and for reaching granularity requirements, these two kinds of methods all will be used the further refinement powder size of Mechanical Crushing method, tend to damage the magnetic property of powder particle like this.
If with the conventional method powder process of the R-Fe-B mother alloy ingot being carried out Mechanical Crushing, then magnetic does not have good hard magnetic property.
Summary of the invention
The present invention adopts metallothermic reduction and the controlled R-Fe-B alloy powder of diffusion-alloying method prepared sizes, when having solved with the further refinement powder size of Mechanical Crushing method, and the problem of damage powder particle magnetic property.
Technology of the present invention is: raw material select and the proportioning → reactant mixing → metallothermic reduction → diffusion-alloying → product Chemical Decomposition → metal dust of preliminary treatment → reactant dehydrate → make anisotropy R-Fe-B bonded permanent magnet.
1, raw material are selected: the employing rare earth oxide is a raw material, comprises neodymia, praseodymium oxide, dysprosia, holimium oxide, also can select the didymium mixed oxide for use.Base alloying element raw material is straight iron powder and ferro-boron powder, needs its granularity of control at the 300-800 order; Also can select the ferro-boron powder of certain ingredients proportion requirement, will control its granularity equally at the 300-800 order; Can also select the oxide of iron or the oxide of boron is raw material.
At preparation polynary system alloy R-Fe-M-B; R
1,R
2-Fe-M-B; R-Fe-M
1,M
2-B; R
1,R
2-Fe-M
1,M
2During-B, wherein R, R
1, R
2Be rare earth, M, M
1, M
2Be magnesium-yttrium-transition metal, comprise: Co, Al, Cu, Cr, Zr, Nb.
Reducing agent is selected Ca and CaH
2, its granularity requirements 2-5mm.Auxiliary agent is selected NdCl
3With CaCl
2
2, pretreatment of raw material: rare earth oxide is calcination process under 860～900 ℃ of conditions, NdCl
3With CaCl
2Through the negative pressure processed.
3, raw-material allocating into: according to fundamental reaction formula (1) and R
xFe
yB
zTarget component carries out the adjustment of raw-material calculating and proportioning coefficient in conjunction with different reduction diffusion reaction conditions.
The span of parameter x is at 10-16, and the span of y is at 76-90, and the span of z is at 6-16, parameter matching relationship x+y+z=100.
Polynary system alloying element R
1Mainly be metal Nd, R
2Mainly be metal Pr, Dy, Tb.Dy wherein, Tb at 0-10%, exceeds the remanent magnetism Br that this scope can influence the R-Fe-B alloy, M, M to the replacement weight range of Nd
1, M
2Be magnesium-yttrium-transition metal, wherein the scope of Co replacement Fe amount is at 0-35%, and other transition element replaces the scope of Fe amount at 0-5%, exceeds the remanent magnetism Br that this scope can influence the R-Fe-B alloy.
Reducing agent is by the required chemical dose excess 10-30% of basic chemical equation
The addition of auxiliary agent is the 0-5% of target R-Fe-B gained amount.
4, reduction diffusion reaction: behind the reactant ratio, carry out metallothermic reduction reaction and diffusion-alloying, this reaction temperature is controlled at 820-960 ℃, and R-Fe-B alloy powder and accessory substance CaO washed Chemical Decomposition after reaction was finished.Obtain required R-Fe-B alloy powder through dehydrating again.
The method of manufacturing R-Fe-B alloy powder of the present invention is a raw material owing to adopted rare earth oxide, has saved the extraction process of high pure rare earth metals complexity, can obtain the anisotropic R-Fe-B magnetic of high-performance.Granularity by basic alloy raw material iron powder is selected and the adding of auxiliary agent, reduction diffusion reaction in lower temperature range by solid-liquid, Gu Gu-carry out under the state, can directly obtain the R-Fe-B alloy powder of required composition and granularity requirements like this.Needn't for reaching the powder size requirement, finally have to adopt mechanical crushing method refinement powder as quick quenching technique and HDDR method, cause the loss of alloy powder magnetic.
Example 1
Raw material adopts Nd
2O
3,Fe powder (400 order) B-Fe powder (400 order) is composition Nd according to target
15Fe
77B
8Allocate into, metal Ca particle diameter 3mm, addition metachemistry dosage 20% adds NdCl
3Amount to make its Nd be Nd in the gained target alloy chemical dose 3%, vacuum dehydration, Nd
2O
3Through calcination process.Reduction diffusion reaction: under the argon shield, 850 ℃ are incubated 3 hours, and reaction block is put in the water and stirred, and block efflorescence precipitation is isolated the CaO floccule, the vacuum drying again of alloyed powder drainage.The alloyed powder magnetic property that makes is: Br=10kGs,
MHc=9kOe, (BH) m=20MGOe.
Example 2
Raw material adopts Nd
2O
3, Dy
2O
3, Fe powder (500 orders) B-Fe powder (500 order) and Co powder (500 order), according to target composition (Nd
0.95Dy
0.05)
15(Fe
0.90Co
0.1)
77B
8Batching, the particle diameter of metal Ca is 3mm, addition metachemistry dosage 15% adds NdCl
3Amount to make its Nd be Nd in the gained target alloy chemical dose 5%.Reduction diffusion reaction: under the argon shield, 860 ℃ are incubated 3 hours, and reaction block is put in the water and stirred, and block efflorescence precipitation is isolated the CaO floccule, the vacuum drying again of alloyed powder drainage.The alloyed powder magnetic property that makes is: Br=11kGs,
MHc=11kOe, (BH) m=25MGOe.
Other embodiment see the following form
| Alloy | Magnetic Br/kGs MHc/kOe (BH)m/MGOe |
| (Nd 0.9Pr 0.1) 15(Fe 0.98Zr 0.02) 77B 8 | 10 9.6 21 |
| Nd 15(Fe 0.98Nb 0.02) 77B 8 | 10.5 10 25 |
| (Nd 0.95Tb 0.05) 15(Fe 0.98Cr 0.02) 77B 8 | 9.8 12 18 |
| Nd 15(Fe 0.88Co 0.1Nb 0.02) 77B 8 | 10.2 10 23 |
| Nd 15(Fe 0.88Co 0.1Cu 0.02) 77B 8 | 10.4 10.2 22 |
Claims (2)
1, a kind of method that adopts reduction-diffusion process to make the rare-earth iron-boron permanent magnetic alloy powder, technological process is: raw material select and the proportioning → reactant mixing → metallothermic reduction → diffusion-alloying → product Chemical Decomposition → metal dust of preliminary treatment → reactant dehydrate → make anisotropy R-Fe-B bonded permanent magnet; It is characterized in that:
A, raw material are selected: the employing rare earth oxide is a raw material, comprises neodymia, praseodymium oxide, dysprosia, and basic alloying element raw material is straight iron powder and ferro-boron powder, and its granularity is at 400～500 orders; At preparation polynary system alloy R-Fe-M-B, R
1, R
2-Fe-M-B, R-Fe-M
1, M
2-B, R
1, R
2-Fe-M
1, M
2During-B, R wherein, R
1, R
2, be rare earth, M, M
1, M
2, be magnesium-yttrium-transition metal, comprising: Co, Al, Cu, Cr, Zr, Nb; Reducing agent is selected Ca, and auxiliary agent is selected NdCl
3
B, pretreatment of raw material: rare earth oxide is calcination process under 860～900 ℃ of conditions, NdCl
3With CaCl
2Through the negative pressure processed;
C, raw-material allocating into: according to fundamental reaction formula (1) and R
xFe
yB
zTarget component, carry out the adjustment of raw-material calculating and proportioning coefficient in conjunction with different reduction diffusion reaction conditions:
The span of parameter x is 14～16, and the span of y is 76～78, and the span of z is 8～9, parameter matching relationship x+y+z=100;
Polynary system alloying element R
1Be metal Nd, R
2Be wherein a kind of of metal Pr, Dy, Tb; Wherein 0～5%, Co replaces the scope of Fe amount 0～10% to the replacement weight range of Nd for Dy, Tb, and other transition element replaces the scope of Fe amount 0～2%;
Reducing agent is by the required chemical dose excess 15～20% of basic chemical equation, and the addition of auxiliary agent is 3～5% of a target R-Fe-B gained amount;
D, reduction diffusion reaction: behind the reactant ratio; carry out metallothermic reduction reaction and diffusion-alloying; this is reflected under the argon shield and carries out; temperature is controlled at 850～860 ℃; temperature retention time was not less than 3 hours; R-Fe-B alloy powder and accessory substance CaO washed Chemical Decomposition after reaction was finished, and obtained required R-Fe-B alloy powder through dehydrating again.
2, make the method at rare earth permanent magnet alloy powder end according to the described employing reduction-diffusion process of claim 1, it is characterized in that: the oxide of raw material selection didymium mixed oxide or iron or the oxide of boron, base alloying element raw material is selected the ferro-boron powder of certain ingredients proportion requirement, and its granularity is at 400～500 orders.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021596646A CN1186154C (en) | 2002-12-30 | 2002-12-30 | Process for producing rare-earth-iron-boron permanent magnet alloy powder by reduction diffusion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021596646A CN1186154C (en) | 2002-12-30 | 2002-12-30 | Process for producing rare-earth-iron-boron permanent magnet alloy powder by reduction diffusion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1424164A CN1424164A (en) | 2003-06-18 |
| CN1186154C true CN1186154C (en) | 2005-01-26 |
Family
ID=4753330
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB021596646A Expired - Fee Related CN1186154C (en) | 2002-12-30 | 2002-12-30 | Process for producing rare-earth-iron-boron permanent magnet alloy powder by reduction diffusion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1186154C (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332053C (en) * | 2004-11-11 | 2007-08-15 | 宁波科宁达工业有限公司 | Multiplex rare-earth ferroalloy (RERAFe#-[2]) powder and method for preparing same |
| CN103030851A (en) * | 2012-12-20 | 2013-04-10 | 南通万宝磁石制造有限公司 | Magnetic ferrous powder |
| CN103785847A (en) * | 2014-02-26 | 2014-05-14 | 江门市新会区宇宏科技有限责任公司 | Method for preparing 1:12 type Nd-Fe(M)-N permanent magnet alloy powder through reduction diffusion method |
| KR102092327B1 (en) * | 2017-11-28 | 2020-03-23 | 주식회사 엘지화학 | Manufacturing method of magnetic powder and magnetic powder |
| KR102357085B1 (en) | 2018-08-10 | 2022-01-28 | 주식회사 엘지화학 | Magnetic powder and manufacturing method of magnetic powder |
| CN109440182B (en) * | 2018-11-28 | 2021-03-16 | 北京工业大学 | Method for manufacturing single crystal neodymium iron boron particles with adjustable size by reduction diffusion method and method for removing calcium by hydrogen |
-
2002
- 2002-12-30 CN CNB021596646A patent/CN1186154C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1424164A (en) | 2003-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102903472B (en) | A kind of Sintered NdFeB magnet and preparation method thereof | |
| CN101812606B (en) | Method for preparing low-cost neodymium iron boron (NdFeB) by adding heavy rare earth oxide into ingot recasting sheet | |
| CN103187133B (en) | A kind of RE permanent magnetic alloy and Magnetic Phase composite preparation process thereof | |
| CN107275027B (en) | Using the cerium-rich rare earth permanent magnet and preparation method thereof of yttrium | |
| CN103103442A (en) | Method for preparing neodymium-iron-boron material through main-auxiliary alloy method | |
| CN101996721A (en) | Method for improving coercive force of sintered neodymium ferrum boron (NdFeB) | |
| CN103056370A (en) | Method of improving coercivity of sintering Nd-Fe-B magnetic material | |
| JPWO2002103719A1 (en) | Rare earth permanent magnet material | |
| CN110911077B (en) | Preparation method of high-coercivity neodymium cerium iron boron magnet | |
| JP2022543487A (en) | High Cu high Al neodymium iron boron magnet and its manufacturing method | |
| CN103545079A (en) | Double-principal-phase yttrium-contained permanent magnet and preparing method of double-principal-phase yttrium-contained permanent magnet | |
| CN104821218A (en) | Sintered Nd-Fe-B magnet with zinc-aluminum-titanium-cobalt composite additive and preparation method thereof | |
| KR20210151946A (en) | R-T-B type rare earth permanent magnet material, manufacturing method and application thereof | |
| JP2023504931A (en) | RTB based sintered magnet and its manufacturing method | |
| CN1254338C (en) | Method for producing Sm-Fe-N permanent magnet alloy powder by reduction diffusion | |
| CN101599330A (en) | Nd-Fe-B magnetic material and production method | |
| CN1186154C (en) | Process for producing rare-earth-iron-boron permanent magnet alloy powder by reduction diffusion | |
| CN103153504A (en) | Alloy material for R-T-B system rare earth permanent magnet, method for producing R-T-B system rare earth permanent magnet, and motor | |
| CN103667920B (en) | Preparation method of Nd-Fe-B rare earth permanent magnetic alloy | |
| CN112712986B (en) | Low-temperature coefficient Sm2Co17Molded sintered magnet and method for producing same | |
| EP3754676B1 (en) | Method for manufacturing sintered magnet | |
| CN108597707B (en) | Ce-containing sintered magnet and preparation method thereof | |
| JPS6077960A (en) | Permanent magnet and its manufacture | |
| KR20240017949A (en) | Corrosion-resistant, high-performance NdFeB sintered magnet and manufacturing method and use thereof | |
| CN101552063A (en) | High-performance neodymium-iron-boron magnet with composite addition of titanium and zirconium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |