CN103849809B - A kind of method adding holmium in neodymium iron boron - Google Patents
A kind of method adding holmium in neodymium iron boron Download PDFInfo
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- CN103849809B CN103849809B CN201210516584.9A CN201210516584A CN103849809B CN 103849809 B CN103849809 B CN 103849809B CN 201210516584 A CN201210516584 A CN 201210516584A CN 103849809 B CN103849809 B CN 103849809B
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- holmium
- neodymium iron
- iron boron
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Abstract
The invention provides a kind of method adding holmium in neodymium iron boron, the method adopts Holmium trioxide, calcium metal and alkali metal chloride or alkaline earth metal chloride to make reductive agent, mixes and obtain mixture in mixing machine; Under the protection higher than barometric point 20-50kpa nitrogen or rare gas element, block neodymium iron boron is arranged in graphite-made or quartz lidded container processed, then mixture is poured into cover on neodymium iron boron in container and compress, cover tightly sealing of lid; Then lidded container is put into sintering box, again sintering box is placed in sintering oven, be filled with rare gas element with exhausted air or first vacuumize and be filled with rare gas element again, make in stove Control for Oxygen Content at below 5000ppm, then be filled with rare gas element and make furnace pressure reach 0.101-0.125Mpa; Then in sintering oven, sinter 1-10 hour at 1000-1150 DEG C, at 450-700 DEG C of temperature, tempering 2-4 hour obtains the Nd-Fe-B permanent magnet adding holmium.This sintering method reaction product fusing point is low, sintering process is that malleation, technique are comparatively simple, can be widely used in the deep processing of Nd-Fe-Bo permanent magnet material.
Description
Technical field
The present invention relates to new material technology field, specifically a kind of method adding holmium in neodymium iron boron.
Background technology
Rare earth permanent-magnetic material (Nd
2fe
14b), be mainly prepared from by powder metallurgical technique by iron, rare earth metal and boron, the industries such as widespread use electronics, machinery, especially high-performance, high-coercive force rare earth permanent magnetic material, is widely applied in national defense industry, and its market outlook are very wide.
In order to improve rare earth permanent-magnetic material (Nd
2fe
14b) magnetic property, especially improves HCJ and thermostability, often at rare earth permanent-magnetic material (Nd
2fe
14b) all add other a small amount of metals during powder metallurgy melting, as added rare earth metal holmium etc., they can play makes homogeneous grain size, grain refining, improve the composition of Grain-Boundary Phase, Grain-Boundary Phase is distributed and more evenly waits effect.
State Intellectual Property Office of the People's Republic of China website discloses a kind of preparation method of Dy-Fe alloy powder, and the matrix that the method adopts is iron powder, and utilizing pure calcium reduction diffusion process, is the compound between a kind of pure rare earth and iron.Simple employing calcium is product as the shortcoming that reductive agent exists is calcium oxide, its fusing point is 2580 DEG C, be still solid-state under reduction temperature, inhibition is had to the diffusion of reduction of rare earth metal, even oxidized for as-reduced rare earth metal calcium can be comprised, not only purify to alloy and bring difficulty, and make it cannot form rare earth ferroalloy with metallic iron.
Also have a kind of method being prepared rare-earth permanent magnet by osmose process in prior art, what the method adopted is the fluorochemical of heavy rare earths metalloid, and the equipment of employing is vacuum sintering furnace, and furnace pressure is lower than 10
-3pa, need to use the special graphite with bracket with holes, mother metal is placed on bracket with holes, has particular requirement to equipment.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, provides a kind of method that reduzate fusing point is low, sintering process is malleation, technique simply adds holmium in neodymium iron boron.
The present invention is achieved by the following scheme:
(1) by Holmium trioxide (Ho
2o
3), calcium metal and alkali metal chloride mixing machine mix and obtain compound, or, by Holmium trioxide (Ho
2o
3), calcium metal and alkaline earth metal chloride mix and obtain compound.
(2) in the operation box higher than barometric point 20-50kpa nitrogen or protection of inert gas; common block neodymium iron boron for adding holmium is arranged in the lidded container of graphite-made or quartz system; the compound that step (1) obtains is poured in container and covers neodymium iron boron compression, cover tightly sealing of lid.
(3) lidded container of cover lid in step (2) is put into sintering box, again sintering box is put into sintering oven, be filled with rare gas element with exhausted air or first vacuumize and be filled with rare gas element again, to make in stove Control for Oxygen Content at below 5000ppm, then be filled with rare gas element and make furnace pressure reach 0.101-0.125Mpa.
(4) sinter, sintering oven temperature is raised to 1000-1150 DEG C with 1-15 DEG C/min speed, insulation 1-10 hour;
(5) tempering, by the neodymium iron boron after sintering under the protection of vacuum or rare gas element, tempering heat treatment 1-4 hour at the temperature of 450-700 DEG C, obtain the neodymium iron boron adding holmium;
The relative neodymium iron boron quality of each constituent mass of mixture in described step (1) is respectively: Holmium trioxide 5-20%, calcium metal 5-10%, alkali metal chloride or alkaline earth metal chloride 0.5-1%.
In described step (1), alkali metal chloride is sodium-chlor or Repone K.
In described step (2), step (3), rare gas element is argon gas.
In described step (1), the mixing time used is 1.0 hours.
Advantage of the present invention is:
(1) be filled with argon gas before sintering, sintering process is malleation, instead of the vacuum sintering higher to vacuum level requirements, and graphite required during sintering or quartz container conventional do not need special, and technique is simpler.
(2) product during sintered NdFeB is calcium oxide and alkali metal chloride or alkaline earth metal chloride, and its fusing point is lower than calcium oxide, and (such as CaONaCl fusing point is 801 DEG C, 2CaOCaCl
2fusing point is 782 DEG C), be conducive to holmium spread in neodymium iron boron Grain-Boundary Phase make the HCJ of Nd-Fe-B permanent magnet improve more obvious.
Accompanying drawing explanation
Fig. 1 is the Nd-Fe-B permanent magnet metallograph that usual way adds holmium;
Fig. 2 is the Nd-Fe-B permanent magnet metallograph that the present invention adds holmium;
Embodiment
Embodiment is described further the present invention by reference to the accompanying drawings.
Embodiment 1:
By Ho
2o
3100 grams, Ca grain 50 grams, NaCl7 gram mixes 1 hour with mixing machine and obtains compound.In the operation box higher than barometric point 20-50kpa argon shield, 1000 grams are arranged in for the block neodymium iron boron adding holmium in the lidded container of graphite-made or quartz system, above-mentioned compound are poured in container and compresses, cover tightly lid and lidded container is sealed; These containers are put into sintering box, then sintering box is put into sintering oven, first vacuumize and be filled with argon gas again, to make in sintering oven Control for Oxygen Content at below 5000ppm, then be filled with argon gas and make pressure reach 0.101Mpa; Then sinter, sintering in-furnace temperature is incubated 4 hours when rising to 1000 DEG C with the speed of 8 DEG C/min, finally under the protection of vacuum or rare gas element, tempering heat treatment 2 hours at 560 DEG C of temperature, come out of the stove and obtain adding the neodymium iron boron of holmium.
The neodymium iron boron that described in embodiment, block neodymium iron boron is pressed into for ordinary method in industry, for conventionally known to one of skill in the art, can obtain by the following method: (1) melting-casting: make starting material form the aluminium alloy of melting by vacuum melting method or emergency cooling roll method, then the casting of the aluminium alloy of melting being cooled to book shape thickness is the alloy pig of 0.2-40mm; (2) pulverize: by coarse reduction with fine powder is broken that bulk alloy ingot is broken into the powder that mean particle size is 3-6 μm; (3) shaping: to add isostatic cool pressing by compression molding, mold pressing or powder compression is become pressed compact by rubber mold platen press.What mainly introduce due to the present invention is the method adding holmium in neodymium iron boron, to the block neodymium iron boron suppressed without particular requirement, not at scope, does not therefore describe in detail the melting-casting of neodymium iron boron, pulverizing, moulding process.Embodiment 2, embodiment 3, embodiment 4 are this method and obtain.
Embodiment 2:
By Ho
2o
3100 grams, Ca grain 50 grams, CaCl
27 grams mix 1 hour with mixing machine and obtain compound.In the operation box higher than barometric point 20-50kpa argon shield, 1000 grams are arranged in for the block neodymium iron boron adding holmium in the lidded container of graphite-made or quartz system, above-mentioned compound are poured in container and compresses, cover tightly lid and lidded container is sealed; These containers are put into sintering box, then sintering box is put into sintering oven, first vacuumize and be filled with argon gas again, to make in sintering oven Control for Oxygen Content at below 5000ppm, then be filled with argon gas and make pressure reach 0.105Mpa; Then sinter, sintering in-furnace temperature is incubated 2 hours when rising to 1050 DEG C with the speed of 5 DEG C/min, finally under the protection of vacuum or rare gas element, tempering heat treatment 4 hours at 540 DEG C of temperature, come out of the stove and obtain adding the neodymium iron boron of holmium.
Embodiment 3:
By Ho
2o
3100 grams, Ca grain 50 grams, KCl7 gram mixes 1 hour with mixing machine and obtains compound.In the operation box higher than barometric point 20-50kpa argon shield, 1000 grams are arranged in for the block neodymium iron boron adding holmium in the lidded container of graphite-made or quartz system, above-mentioned compound are poured in container and compresses, cover tightly lid and lidded container is sealed; These containers are put into sintering box, then sintering box is put into sintering oven, first vacuumize and be filled with argon gas again, to make in sintering oven Control for Oxygen Content at below 5000ppm, then be filled with argon gas and make pressure reach 0.115Mpa; Then sinter, sintering in-furnace temperature is incubated 5 hours when rising to 1080 DEG C with the speed of 3 DEG C/min, finally under the protection of vacuum or rare gas element, tempering heat treatment 2 hours at 520 DEG C of temperature, come out of the stove and obtain adding the neodymium iron boron of holmium.
Embodiment 4:
By Ho
2o
3200 grams, Ca grain 100 grams, MgCl
210 grams mix 1 hour with mixing machine and obtain compound.In the operation box of the argon shield higher than barometric point 20-50kpa, 1000 grams are arranged in for the block neodymium iron boron adding holmium in the lidded container of graphite-made or quartz system, above-mentioned compound are poured in container and compresses, cover tightly lid and lidded container is sealed; These containers are put into sintering box, then sintering box is put into sintering oven, first vacuumize and be filled with argon gas again, to make in sintering oven Control for Oxygen Content at below 5000ppm, then be filled with argon gas and make pressure reach 0.12Mpa; Then sinter, sintering in-furnace temperature is incubated 8 hours when rising to 1100 DEG C with the speed of 2 DEG C/min, finally under the protection of vacuum or rare gas element, tempering heat treatment 2 hours at 500 DEG C of temperature, come out of the stove and obtain adding the neodymium iron boron of holmium.
The holmium Nd-Fe-B permanent magnet that adds adopting the inventive method to obtain contrasts with the holmium neodymium iron boron performance that adds adopting usual way to obtain, and comparing result is as follows:
| Specimen coding | Remanent magnetism (KGs) | HCJ (KOe) |
| Sample 1(the present invention adds holmium) | 13.29 | 13.02 |
| Sample 1(is common adds holmium) | 13.31 | 12.79 |
| Sample 2(the present invention adds holmium) | 13.30 | 13.85 |
| Sample 2(is common adds holmium) | 13.32 | 13.68 |
| Sample 3(the present invention adds holmium) | 13.27 | 14.98 |
| Sample 3(is common adds holmium) | 13.28 | 14.81 |
| Sample 4(the present invention adds holmium) | 13.26 | 17.15 |
| Sample 4(is common adds holmium) | 13.29 | 17.06 |
Holmium Nd-Fe-B permanent magnet Performance comparision is added according in 4 groups of embodiments, under different technique, adopting present method to sinter the permanent magnet obtained, to sinter than usual way its HCJ of permanent magnet obtained higher, performance is better, sintering process is malleation simultaneously, instead of the vacuum sintering higher to vacuum level requirements, required graphite or quartz container do not need special, and technique is simpler.
We carry out metallurgical analysis to the Nd-Fe-B permanent magnet of the interpolation holmium that the Nd-Fe-B permanent magnet of the interpolation holmium adopting the inventive method to obtain and usual way obtain, can see according to Fig. 1 and Fig. 2 contrast, it is thinner that what the present invention obtained add holmium Nd-Fe-B permanent magnet metallographic, grain size evenly, Grain-Boundary Phase distribution is more reasonable, proving that the present invention is a kind of process innovation in the production technique adding holmium toward Nd-Fe-B permanent magnet, is a kind of invention newly.
Claims (3)
1. in neodymium iron boron, add a method for holmium, it is characterized in that: the method comprises the following steps:
(1) Holmium trioxide, calcium metal and alkali metal chloride mixing machine are mixed obtain compound, or, Holmium trioxide, calcium metal and alkaline earth metal chloride mixing machine are mixed and obtains compound;
(2) in the operation box higher than barometric point 20-50kpa nitrogen or protection of inert gas, block neodymium iron boron for adding holmium is arranged in the lidded container of graphite-made or quartz system, the compound that step (1) obtains is poured in container and covers and compress neodymium iron boron, cover tightly lid and lidded container is sealed;
(3) lidded container covering tightly lid in step (2) is put into sintering box, again sintering box is put into sintering oven, be filled with rare gas element with exhausted air or first vacuumize and be filled with rare gas element again, to make in stove Control for Oxygen Content at below 5000ppm, then be filled with rare gas element and make furnace pressure reach 0.101-0.125Mpa;
(4) sinter, sintering oven temperature is raised to 1000-1150 DEG C with 1-15 DEG C/min speed, insulation 1-10 hour;
(5) tempering, by the tempering heat treatment 1-4 hour at the temperature of 450-700 DEG C in sintering oven of the neodymium iron boron after sintering, obtains the neodymium iron boron adding holmium; Alkali metal chloride is sodium-chlor, and each constituent mass of mixture relatively sinters front neodymium iron boron quality and is respectively: Holmium trioxide 5-20%, calcium metal 5-10%, sodium-chlor 0.5-1%.
2. according to the described method adding holmium in neodymium iron boron according to claim 1, it is characterized in that: step (2), step (3) described rare gas element are argon gas.
3. according to the described method adding holmium in neodymium iron boron according to claim 1, it is characterized in that: in step (1), the mixing time used is 1 hour.
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| CN103849809B true CN103849809B (en) | 2016-03-16 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102092327B1 (en) | 2017-11-28 | 2020-03-23 | 주식회사 엘지화학 | Manufacturing method of magnetic powder and magnetic powder |
| CN108933010B (en) * | 2018-06-28 | 2020-06-30 | 宁波招宝磁业有限公司 | Preparation method of high-coercivity neodymium-iron-boron magnet |
| CN110211797A (en) * | 2019-06-17 | 2019-09-06 | 江西理工大学 | A method of promoting Sintered NdFeB magnet magnetic property |
| CN111136268B (en) * | 2020-01-13 | 2022-04-19 | 桂林电子科技大学 | High-throughput alloy preparation and Ho-Fe-B phase diagram test method |
| CN111933441B (en) * | 2020-08-10 | 2022-12-02 | 有研稀土(荣成)有限公司 | Micro-size high-performance sintered neodymium-iron-boron magnet and preparation method thereof |
| CN114496541B (en) * | 2022-01-17 | 2023-04-07 | 中南大学 | High-performance R-T-B permanent magnet material, and diffusion method and diffusion source thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1743104A (en) * | 2004-08-31 | 2006-03-08 | 任英良 | Terbium-iron (Fe2Tb) alloy powder preparing method |
| CN1743105A (en) * | 2004-08-30 | 2006-03-08 | 段莉萍 | Dysprosium-iron alloy powder preparation by reduction diffusion method |
| CN101877266A (en) * | 2009-04-30 | 2010-11-03 | 比亚迪股份有限公司 | Sintered neodymium iron boron permanent magnetic material and preparation method thereof |
| CN102361372A (en) * | 2011-11-04 | 2012-02-22 | 无锡天宝电机有限公司 | Method for preparing corrosion-resistant neodymium iron boron permanent magnet for motor |
-
2012
- 2012-12-04 CN CN201210516584.9A patent/CN103849809B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1743105A (en) * | 2004-08-30 | 2006-03-08 | 段莉萍 | Dysprosium-iron alloy powder preparation by reduction diffusion method |
| CN1743104A (en) * | 2004-08-31 | 2006-03-08 | 任英良 | Terbium-iron (Fe2Tb) alloy powder preparing method |
| CN101877266A (en) * | 2009-04-30 | 2010-11-03 | 比亚迪股份有限公司 | Sintered neodymium iron boron permanent magnetic material and preparation method thereof |
| CN102361372A (en) * | 2011-11-04 | 2012-02-22 | 无锡天宝电机有限公司 | Method for preparing corrosion-resistant neodymium iron boron permanent magnet for motor |
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