CN102784920A - Method for preparing rare earth permanent-magnet alloy nanosheet-shaped powder - Google Patents
Method for preparing rare earth permanent-magnet alloy nanosheet-shaped powder Download PDFInfo
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- CN102784920A CN102784920A CN2012102503627A CN201210250362A CN102784920A CN 102784920 A CN102784920 A CN 102784920A CN 2012102503627 A CN2012102503627 A CN 2012102503627A CN 201210250362 A CN201210250362 A CN 201210250362A CN 102784920 A CN102784920 A CN 102784920A
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Abstract
The invention discloses a method for preparing rare earth permanent-magnet alloy nanosheet-shaped powder. The method comprises the following steps: (1) crushing rare earth permanent-magnet alloy ingots into powder with smaller than 200 Mum sizes; (2) filling a ball milling tank with a proper ball milling medium, taking steel balls as milling balls, adding a surface active agent for assisting ball milling, and carrying out ball milling on the mixture in a high-energy ball grinder, so as to obtain nanosheet-shaped powder adopting a nanocrystalline microstructure; and (3), filtering to remove the ball milling medium, and drying the obtained powder. According to the method, the appearance and the performance of alloy powder can be changed, and the nanosheet-shaped powder with high coercive force and high anisotropy can be obtained. The nanosheet-shaped powder can be used in a servomotor, a pump coupling, a sensor and the like, and has a wide application prospect in the aspect of double-phase hard/soft nano composite magnets.
Description
Technical field
The present invention relates to a kind of method for preparing RE permanent magnetic alloy nano-sheet powder; The method that particularly prepares RE permanent magnetic alloy nano-sheet powder through surfactant auxiliary high-energy ball milling the invention still further relates to the RE permanent magnetic alloy nano-sheet powder of method preparation thus.
Background technology
Rare earth permanent magnet has been widely applied to fields such as the energy, traffic, machinery, medical treatment, IT, household electrical appliances as a kind of performance function material, becomes the basis of new high-tech industry.At present, most rare earth permanent-magnetic material products all are to adopt powder metallurgical technique to produce.Its main flouring technology step is: alloy preparation → prefabricated powder → powder correct grinding, that is: and the vacuum induction melting alloy raw material is cast into block ingot casting; In nitrogen atmosphere, carry out fragmentation then, till the particle diameter of raw material is less than 500 μ m with the high energy beater grinder.The Nd-Fe-B alloy also can adopt the quick-fried technology of hydrogen broken.For the powder after fragmentation correct grinding, traditional method is under inert gas shielding, to pack into organic liquid is housed for example carries out ball milling in the special ball mill of cyclohexane, perhaps adopts the airflow milling device to dry grind.What so prepare is particulate powder, is the powder particle of the isotropic that waits axle, and performance is difficult to further raising.
The invention provides and a kind ofly prepare the method for rare earth permanent magnet nano-sheet powder, can obtain to have the rare earth permanent magnet nano-sheet powder of high anisotropy, high-coercive force, excellent performance through surfactant auxiliary high-energy ball milling.
Summary of the invention
The invention provides a kind of method for preparing RE permanent magnetic alloy nano-sheet powder, is to carry out through surfactant auxiliary high-energy ball milling, comprises the steps:
(1) rare-earth permanent-magnet alloy ingot is broken, to its particle diameter less than 200 μ m;
(2) ball-milling medium that is fit to is filled it up with ball grinder, as abrading-ball, add the surfactant of auxiliary ball milling, in high energy ball mill, compound is carried out ball milling, obtain nano-sheet powder with nanocrystalline microstructure with steel ball; Wherein, said surfactant is selected from oleic acid, oleyl amine, trioctylamine, caproic acid or their mixture;
(3) filter away ball-milling medium, the gained powder is carried out dried.
In preparation method's of the present invention step (3) afterwards, the part surface activating agent is stayed in the ball-milling medium solvent, removes through filtration, and the part surface activating agent is stayed the flaky powder surface, plays protection to a certain degree, anti-oxidation effect.
Used motor speed for example can 1200-1500 rev/min (rpm) in the high-energy ball milling process, preferred 1425rpm, and the high-energy ball milling time is 1-10 hour.
Wherein, It is the steel ball of three kinds of different-grain diameters that said ball milling uses steel ball; GCr15 steel ball for example; Its particle diameter preferably is respectively the steel ball of
ball milling use and the weight ratio of RE permanent magnetic alloy raw material is 10: 1-30: 1, and the steel ball of three kinds of different-grain diameters uses together when carrying out ball milling.
Operable ball-milling medium is selected from the non-polar solven that can dissolve used surfactant, for example heptane or hexane.The purity of used heptane or hexane is preferably more than 99.8.
The addition of said surfactant is: 2～100 weight portions are the basis with alloy powder weight.
Preparation RE permanent magnetic alloy nano-sheet powder method of the present invention is applicable to for example SmCo
5, PrCo
5, RE permanent magnetic alloy, particularly SmCo such as Nd-Fe-B
5Permanent-magnet alloy.
The present invention has prepared a kind of RE permanent magnetic alloy nano-sheet alloy powder with orientation texture through surfactant auxiliary high-energy ball milling.Nanocrystalline microstructure sheet alloy powder of the present invention has high anisotropy and high-coercive force on the basis that keeps original superiority.For example, aspect anisotropy, the SmCo that obtains
5The easy magnetizing axis of flaky powder is perpendicular to the sheet surface, and the easy magnetizing axis parallel plate of Nd-Fe-B flaky powder is surperficial; Aspect coercivity, SmCo for example
5Ball milling reached 10.5kOe in 15 minutes, and ball milling reached 20.5kOe in 5 hours.
The invention still further relates to rare earth permanent magnet nano-sheet powder through said surfactant auxiliary high-energy ball grinding method preparation.
Be preferably SmCo according to the resulting rare earth permanent magnet nano-sheet of the inventive method powder
5Rare earth permanent magnet nano-sheet powder.
The flaky powder material that obtains according to the inventive method has nanocrystalline microstructures, the about 5-210nm of this flaky material thickness, and the about 0.2-13 μ of width m, crystallite dimension is 9-21nm.Said material has high anisotropy and high-coercive force.Said material has 001 orientation texture.For example, SmCo
5Coercivity be generally 10.5kOe-20.5kOe.
Method of the present invention not only can change the pattern and the performance of rare earth permanent-magnetic material, also can further improve its coercivity, obtains anisotropic nano-sheet powder.Gained nano-sheet powder for example can be processed the permanent magnet of synusia structure through pressure sintering and discharge plasma sintering technique; Be used for servomotor, pump coupling and sensor etc., the spin-exchange-coupled two-phase hard/also have broad application prospects aspect the soft Nanocomposite magnet.
The accompanying drawing summary
Fig. 1 be among the embodiment 4 10 weight % oleyl amines as the SmCo of 5 hours gained of high-energy ball milling under the situation of surfactant
5The nano-sheet powder is observed pattern photo under ESEM.
Fig. 2 is with the SmCo of 15 weight % caproic acids as 5 hours gained of high-energy ball milling under the situation of surfactant among the embodiment 1
5The high-resolution-ration transmission electric-lens photo.
Fig. 3 is with the SmCo of 15 weight % caproic acids as 5 hours gained of high-energy ball milling under the situation of surfactant among the embodiment 1
5The nano-sheet powder is observed pattern photo under ESEM.
The specific embodiment
Further exemplarily specify the present invention below in conjunction with instance.
Embodiment 1:
In the high-energy ball milling jar of SPEX8000M type ball mill, put into 5g SmCo
5RE permanent magnetic alloy is being that 10: 1 weight ratio is put into than the RE permanent magnetic alloy raw material
The ball milling steel ball of three kinds of different-grain diameters; Adding with the RE permanent magnetic alloy raw material weight be the caproic acid of benchmark 15 weight portions as surfactant, add heptane as ball-milling medium, install on the ball mill after the sealing; Motor speed with 1425rpm carried out high-energy ball milling 2 hours, obtained SmCo
5Rare earth permanent magnet nano-sheet powder uses vibrating specimen magnetometer to measure its coercivity H and is 17.2kOe, saturation magnetization M
sBe 75.1emu.g
-1This nano-sheet powder has [001] orientation texture perpendicular to the nanometer sheet surface.Its crystallite dimension is 21nm, the about 210nm of sheet thickness.
Embodiment 2:
In the high-energy ball milling jar of SPEX8000M type ball mill, put into 5g PrCo
5RE permanent magnetic alloy is being that 10: 1 weight ratio is put into than this RE permanent magnetic alloy raw material
The ball milling steel ball of three kinds of different-grain diameters; Adding with the RE permanent magnetic alloy raw material weight be the oleic acid of benchmark 15 weight portions as surfactant, add heptane as ball-milling medium, install on the ball mill after the sealing; Motor speed with 1425rpm carried out high-energy ball milling 4 hours, obtained PrCo
5Rare earth permanent magnet nano-sheet powder, measuring its coercivity H is 5.5kOe, saturation magnetization M
sBe 65.3emu.g
-1This nano-sheet powder has [001] orientation texture perpendicular to the nanometer sheet surface.Its crystallite dimension is 20nm, the about 160nm of sheet thickness.
Embodiment 3:
In the high-energy ball milling jar of SPEX8000M type ball mill, put into 5g SmCo
5RE permanent magnetic alloy is being that 10: 1 weight ratio is put into than this RE permanent magnetic alloy raw material
The ball milling steel ball of three kinds of different-grain diameters; Adding with the RE permanent magnetic alloy raw material weight be the trioctylamine of benchmark 100 weight portions as surfactant, add heptane as ball-milling medium, install on the ball mill after the sealing; Motor speed with 1425rpm carried out high-energy ball milling 1.5 hours, obtained SmCo
5Rare earth permanent magnet nano-sheet powder, measuring its coercivity H is 17.3kOe, saturation magnetization M
sBe 76.5emu.g
-1This nano-sheet powder has [001] orientation texture perpendicular to the nanometer sheet surface.Its crystallite dimension is 21nm, the about 210nm of sheet thickness.
Embodiment 4:
In the high-energy ball milling jar of SPEX8000M type ball mill, put into 5g Nd
2Fe
14The B permanent-magnet alloy is being that 30: 1 weight ratio is put into than this RE permanent magnetic alloy raw material
The ball milling steel ball of three kinds of different-grain diameters; Adding with the RE permanent magnetic alloy raw material weight be the oleyl amine of benchmark 15 weight portions as surfactant, add heptane as ball-milling medium, install on the ball mill after the sealing; Motor speed with 1425rpm carried out high-energy ball milling 4 hours, obtained Nd
2Fe
14B rare earth permanent magnet nano-sheet powder, measuring its coercivity H is 3.1kOe, saturation magnetization M
sBe 76.8emu.g
-1This nano-sheet powder has unilateral interior [001] orientation texture of nanometer.Its crystallite dimension is 14nm, the about 150nm of sheet thickness.
Embodiment 5:
In the high-energy ball milling jar of SPEX8000M type ball mill, put into 5g SmCo
5Permanent-magnet alloy is being that 10: 1 weight ratio is put into than this RE permanent magnetic alloy raw material
The ball milling steel ball of three kinds of different-grain diameters; Adding with the RE permanent magnetic alloy raw material weight be the oleic acid of benchmark 2 weight portions as surfactant, add hexane as ball-milling medium, install on the ball mill after the sealing; Motor speed with 1425rpm carried out high-energy ball milling 10 hours, obtained SmCo
5Rare earth permanent magnet nano-sheet powder, measuring its coercivity H is 20.1kOe, saturation magnetization M
sBe 56.2emu.g
-1This nano-sheet powder has [001] orientation texture perpendicular to the nanometer sheet surface.Its crystallite dimension is 10nm, the about 40nm of sheet thickness.
By above-mentioned visible,, on the basis that keeps original structure and superiority, has each to different and high coercivity through the rare earth permanent magnet nano-sheet powder of surfactant auxiliary high-energy ball grinding method preparation of the present invention.
Above embodiment only is used for exemplarily explaining the present invention, does not constitute any restriction of the present invention.Any variation and change in spirit of the present invention all falls into scope of the present invention.
Claims (10)
1. a method for preparing RE permanent magnetic alloy nano-sheet powder comprises the steps:
(1) rare-earth permanent-magnet alloy ingot is broken, to its particle diameter less than 200 μ m;
(2) ball-milling medium that is fit to is filled it up with ball grinder, as abrading-ball, add the surfactant of auxiliary ball milling, in high energy ball mill, compound is carried out ball milling, obtain nano-sheet powder with nanocrystalline microstructure with steel ball; Wherein, said surfactant is selected from oleic acid, oleyl amine, trioctylamine, caproic acid or their mixture;
(3) remove by filter ball-milling medium, the gained powder is carried out dried.
2. the method for claim 1, wherein: ball milling uses the weight ratio of steel ball and RE permanent magnetic alloy raw material to be 10:1-30:1.
3. according to claim 1 or claim 2 method; Wherein: it is the steel ball of three kinds of different-grain diameters that said ball milling uses steel ball, and its particle diameter is respectively
4. the method for claim 1, wherein: the used motor speed of high-energy ball milling process is 1200-1500rpm, is preferably 1425rpm; The high-energy ball milling time is 1-10 hour.
5. method as claimed in claim 4, wherein: said ball-milling medium is selected from the non-polar solven that can dissolve used surfactant, for example heptane or hexane.
6. the method for claim 1, wherein: the addition of surfactant is: 2 ~ 100 weight portions are the basis with alloy powder weight.。
7. require the RE permanent magnetic alloy nano-sheet powder of each described method preparation among the 1-6 according to aforesaid right.
8. RE permanent magnetic alloy nano-sheet powder according to claim 7, wherein said RE permanent magnetic alloy nano-sheet powder is SmCo
5Powder.
9. according to claim 7 or 8 described RE permanent magnetic alloy nano-sheet powders, wherein said flaky powder is anisotropic.
10. according to each described RE permanent magnetic alloy nano-sheet powder in claim 7 or 8, wherein said flaky powder thickness is 5-210nm, and width is 0.2-13 μ m, and crystallite dimension is 9-21nm.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103231066A (en) * | 2013-04-16 | 2013-08-07 | 中国科学院宁波材料技术与工程研究所 | Method for producing rare earth-transitional permanent magnet alloy micro/nanoparticles |
| CN104001928A (en) * | 2014-05-23 | 2014-08-27 | 中国科学院宁波材料技术与工程研究所 | Preparation method for rare earth and cobalt permanent magnetic particles with high remanence ratio |
| CN104174855A (en) * | 2014-08-13 | 2014-12-03 | 中国科学院物理研究所 | Method for preparing magnetic nanosheet |
| CN105414555A (en) * | 2015-11-17 | 2016-03-23 | 中国科学院宁波材料技术与工程研究所 | Method for preparing micron/nano particles of rare earth-transition group permanent magnetic alloy |
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| CN1545107A (en) * | 2003-11-12 | 2004-11-10 | 浙江大学 | Method for preparing high-performance biphase rare-earth permanent magnet material using hydrogenation heat treatment process |
| JP2008045214A (en) * | 2007-09-10 | 2008-02-28 | Dowa Holdings Co Ltd | Powder for producing sintered rare earth magnet alloy |
| CN102274974A (en) * | 2011-06-01 | 2011-12-14 | 横店集团东磁股份有限公司 | Method for preparing nanocrystalline rare-earth permanent magnet alloy powder |
| US20120019342A1 (en) * | 2010-07-21 | 2012-01-26 | Alexander Gabay | Magnets made from nanoflake precursors |
| CN102403118A (en) * | 2011-11-23 | 2012-04-04 | 北京航空航天大学 | Preparation method of anisotropic samarium cobalt-based nanocrystalline rare earth permanent magnet |
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| CN1545107A (en) * | 2003-11-12 | 2004-11-10 | 浙江大学 | Method for preparing high-performance biphase rare-earth permanent magnet material using hydrogenation heat treatment process |
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| US20120019342A1 (en) * | 2010-07-21 | 2012-01-26 | Alexander Gabay | Magnets made from nanoflake precursors |
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Cited By (6)
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| CN103231066A (en) * | 2013-04-16 | 2013-08-07 | 中国科学院宁波材料技术与工程研究所 | Method for producing rare earth-transitional permanent magnet alloy micro/nanoparticles |
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| CN104001928A (en) * | 2014-05-23 | 2014-08-27 | 中国科学院宁波材料技术与工程研究所 | Preparation method for rare earth and cobalt permanent magnetic particles with high remanence ratio |
| CN104174855A (en) * | 2014-08-13 | 2014-12-03 | 中国科学院物理研究所 | Method for preparing magnetic nanosheet |
| CN104174855B (en) * | 2014-08-13 | 2017-04-26 | 中国科学院物理研究所 | Method for preparing magnetic nanosheet |
| CN105414555A (en) * | 2015-11-17 | 2016-03-23 | 中国科学院宁波材料技术与工程研究所 | Method for preparing micron/nano particles of rare earth-transition group permanent magnetic alloy |
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Application publication date: 20121121 |