CN106158201B - Magnetic anisotropy rare-earth iron-boron permanent-magnet alloy submicron particles and preparation method thereof - Google Patents
Magnetic anisotropy rare-earth iron-boron permanent-magnet alloy submicron particles and preparation method thereof Download PDFInfo
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- 239000002245 particle Substances 0.000 title claims abstract description 55
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 51
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 45
- 239000000956 alloy Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 11
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 9
- ZDVYABSQRRRIOJ-UHFFFAOYSA-N boron;iron Chemical compound [Fe]#B ZDVYABSQRRRIOJ-UHFFFAOYSA-N 0.000 title abstract description 5
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 9
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 9
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 9
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 9
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 6
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 6
- 229910052796 boron Inorganic materials 0.000 claims description 44
- 238000000498 ball milling Methods 0.000 claims description 40
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 37
- 239000001257 hydrogen Substances 0.000 claims description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims description 37
- 238000010791 quenching Methods 0.000 claims description 37
- 230000000171 quenching effect Effects 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 22
- 239000004094 surface-active agent Substances 0.000 claims description 17
- FMGSKLZLMKYGDP-USOAJAOKSA-N dehydroepiandrosterone Chemical class C1[C@@H](O)CC[C@]2(C)[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CC=C21 FMGSKLZLMKYGDP-USOAJAOKSA-N 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 10
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 5
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 5
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 5
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000005642 Oleic acid Substances 0.000 claims description 5
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 5
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 5
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- OBETXYAYXDNJHR-UHFFFAOYSA-N alpha-ethylcaproic acid Natural products CCCCC(CC)C(O)=O OBETXYAYXDNJHR-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000011805 ball Substances 0.000 claims 10
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 229910001172 neodymium magnet Inorganic materials 0.000 description 30
- 238000002441 X-ray diffraction Methods 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 8
- 230000005389 magnetism Effects 0.000 description 7
- 238000000137 annealing Methods 0.000 description 5
- 235000013339 cereals Nutrition 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 229910000521 B alloy Inorganic materials 0.000 description 3
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000005298 paramagnetic effect Effects 0.000 description 3
- -1 rare earth hydride Chemical class 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
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- 238000001035 drying Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
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- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- GUBSQCSIIDQXLB-UHFFFAOYSA-N cobalt platinum Chemical compound [Co].[Pt].[Pt].[Pt] GUBSQCSIIDQXLB-UHFFFAOYSA-N 0.000 description 1
- 238000009770 conventional sintering Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 238000000713 high-energy ball milling Methods 0.000 description 1
- OBACEDMBGYVZMP-UHFFFAOYSA-N iron platinum Chemical compound [Fe].[Fe].[Pt] OBACEDMBGYVZMP-UHFFFAOYSA-N 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 125000005473 octanoic acid group Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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Abstract
The present invention relates to a kind of rare-earth iron-boron permanent-magnet alloy submicron particles and preparation method thereof with magnetic anisotropy, the molecular formula of rare-earth iron-boron permanent-magnet alloy of the present invention are：RExFey1My2Bz；Wherein RE is Ce, Pr, Nd, Dy, at least one of Tb；M is at least one of Co, Cu, Al, Ga, Zr；And 26≤x≤34,0≤y2≤10,0.95≤z≤1.10, y1=100 x y2 z.Compared with prior art, the Effective Regulation to particle mean size may be implemented in preparation method of the invention；And manufacturing cost is low, simple and practicable, is suitble to be prepared on a large scale the sub-micron rare-earth iron-boron permanent-magnet alloy particle with magnetic anisotropy, has good application value.
Description
Technical field
The invention belongs to field of magnetic material, and in particular to a kind of rare-earth-iron-boron permanent-magnet alloy with magnetic anisotropy
Submicron particles and preparation method thereof.
Background technology
Magnetic energy product is one of the key technical index for characterizing permanent-magnet material magnetic property.The raising of magnetic energy product is to related device
It minimizes most important.Anisotropic spin-exchange-coupled nanometer two-phase composite permanent magnet has due to its theoretically high magnetic energy product
It is likely to become next-generation high-performance permanent magnet.Nanometer two-phase composite permanent magnet has stringent limitation to soft magnetism phase size therein,
It cannot be more than at least in certain one-dimensional square twice of permanent magnetism phase domain wall thickness.The size of permanent magnetism phase size determines a nanometer two-phase
The number of soft magnetic phase can be added in composite permanent magnet, permanent magnetism is mutually more tiny, and the soft magnetic phase that can be added is more.Therefore nanoscale
Paramagnetic particles be to prepare a nanometer fundamental for two-phase composite permanent magnet from bottom to top.On the other hand, paramagnetic particles have one
A corresponding single domain size, i.e., the size that magnetic structure changes from multidomain to single domain, under this size, the coercivity of paramagnetic particles
Highest, magnetic property are best.It is the best permanent magnetism of current comprehensive performance by the rare-earth-iron-boron permanent-magnet alloy of representative of Nd-Fe-B
Material, and as one of the optimal selection of permanent magnetism phase in nanometer two-phase composite permanent magnet, single domain size is generally received 300
Rice or so.Therefore, size is prepared at 100 nanometers or more, and one micron of rare-earth-iron-boron permanent-magnet alloy magnetic anisotropy below is sub-
Micron particles are of great significance.
The method that tradition prepares nanometer-submicron particles mainly has chemical method and top-down physics from bottom to top
Method.Chemical method is preparing the relatively simple binary system permanent-magnet alloy of some structures, such as iron platinum, the nano particle side of cobalt platinum
Face has been achieved for prodigious success.However rare earth-transition race permanent-magnet alloy crystal structure is complicated, and the chemical reaction of rare earth is lived
Property it is very high, therefore using chemical method be difficult to prepare the little particle of rare earth-transition race permanent-magnet alloy.Physical method includes mainly height
Energy ball milling, low energy ball milling, airflow milling etc. is using Mechanical Crushing as the process for refining of main mechanism.Surfactant auxiliary high-energy ball milling
Technique is applied to the preparation of rare earth-transition race permanent-magnet alloy nanometer-submicron particles in recent years, successfully solves traditional height
In energy ball-milling technology the problem of nanoparticle agglomerates, cold welding.But ingot casting of the technique mostly with crystallite dimension in tens microns is
Raw material, nanometer-submicron particles by the Mechanical Crushing of main mechanism of transgranular fracture mainly by obtaining, particle size distribution
Very wide, the Particle production in specified size section is low, and pattern is difficult to preferably be controlled.In addition, conventional sintering neodymium iron boron is led
The widely used air-flow grinding process in domain can obtain the rare-earth-iron-boron particle that particle size uniformity is distributed near several microns,
But it is difficult further to be down to one micron or less.
Invention content
In view of this, the rare-earth-iron-boron permanent-magnet alloy submicron particles with magnetic anisotropy that are that it is necessary to provide a kind of
And preparation method thereof.
The technical purpose of the present invention is achieved through the following technical solutions：
A kind of rare-earth-iron-boron permanent-magnet alloy submicron particles with magnetic anisotropy, molecular formula are：
RExFey1My2Bz；Wherein RE is Ce, Pr, Nd, Dy, at least one of Tb；M is at least one of Co, Cu, Al, Ga, Zr；
X, y1, y2, z are the mass fraction of respective element, and 26≤x≤34,0≤y2≤10,0.95≤z≤1.10, y1=100-x-
y2-z。
Preferably, the rare-earth-iron-boron permanent-magnet alloy submicron particles are prepared by following steps：
1) isotropic rare-earth-iron-boron quick quenching band is heat-treated under 500 DEG C~900 DEG C of oxygen-free environment,
It is grown to average grain size to 0.1~1 μm；The heat treatment time is 0.5h~10h；
2) it under 250 DEG C~350 DEG C, the Hydrogen Vapor Pressure of 50kPa~500kPa, carries out inhaling hydrogen processing；Then 250 DEG C~
350 DEG C of progress Dehydroepiandrosterone derivatives；Main use vacuumizes carry out Dehydroepiandrosterone derivative, and Dehydroepiandrosterone derivative can slough the hydrogen in main phase, crystal boundary
Hydrogen in place's Nd-rich phase remains in wherein；
3) quick quenching band obtained in step 2) is placed in the ball grinder with abrading-ball, surfactant and organic is added
Solvent under inert gas protection seals ball grinder, and ball grinder, which is put into ball mill, carries out ball milling；Ball milling 0.5h~200h
Afterwards, organic solvent, surfactant are removed, rare-earth-iron-boron permanent-magnet alloy magnetic anisotropy submicron particles are made.
Preferably, the organic solvent is at least one of absolute ethyl alcohol, normal heptane, aviation gasoline；It lives on the surface
Property agent be oleyl amine, oleic acid, octanoic acid, at least one of octylame.
A kind of preparation method of the rare-earth-iron-boron permanent-magnet alloy submicron particles with magnetic anisotropy comprising following
Step：
1) isotropic rare-earth-iron-boron quick quenching band is heat-treated under anaerobic：
2) it carries out inhaling hydrogen processing under Hydrogen Vapor Pressure；Then Dehydroepiandrosterone derivative is carried out；
3) quick quenching band obtained in step 2) is placed in the ball grinder with abrading-ball, surfactant and organic is added
Solvent under inert gas protection seals ball grinder, and ball grinder, which is put into ball mill, carries out ball milling；After ball milling, remove organic
Rare-earth-iron-boron permanent-magnet alloy magnetic anisotropy submicron particles are made in solvent, surfactant.
Preferably, the preparation method of the rare-earth-iron-boron permanent-magnet alloy submicron particles with magnetic anisotropy,
Include the following steps：
1) isotropic rare-earth-iron-boron quick quenching band is heat-treated under 500 DEG C~900 DEG C of oxygen-free environment,
It is grown to average grain size to 0.1~1 μm；The heat treatment time is 0.5h~10h；
2) it under 250 DEG C~350 DEG C, the Hydrogen Vapor Pressure of 50kPa~500kPa, carries out inhaling hydrogen processing；Then 250 DEG C~
350 DEG C of progress Dehydroepiandrosterone derivatives；Main use vacuumizes carry out Dehydroepiandrosterone derivative, and Dehydroepiandrosterone derivative can slough the hydrogen in main phase, crystal boundary
Hydrogen in place's Nd-rich phase remains in wherein；
3) quick quenching band obtained in step 2) is placed in the ball grinder with abrading-ball, surfactant and organic is added
Solvent under inert gas protection seals ball grinder, and ball grinder, which is put into ball mill, carries out ball milling；Ball milling 0.5h~200h
Afterwards, organic solvent, surfactant are removed, rare-earth-iron-boron permanent-magnet alloy magnetic anisotropy submicron particles are made.
The rare-earth-iron-boron permanent-magnet alloy middle rare earth is Nd, Ce, Pr, Dy, Tb.
Preferably, the molecular formula of the rare-earth-iron-boron permanent-magnet alloy with magnetic anisotropy obtained is：
RExFey1My2Bz；Wherein RE is Ce, Pr, Nd, Dy, at least one of Tb；M is at least one of Co, Cu, Al, Ga, Zr；
X, y1, y2, z are the mass fraction of respective element, and 26≤x≤34,0≤y2≤10,0.95≤z≤1.10, y1=100-x-
y2-z。
Preferably, the organic solvent is at least one of absolute ethyl alcohol, normal heptane, aviation gasoline.
Preferably, the surfactant is at least one of oleyl amine, oleic acid, octanoic acid, octylame.
Preferably, the ball mill is low energy ball mill.
Compared with prior art, preparation method of the invention has the advantages that：
(1) rare-earth-iron-boron quick quenching band is heat-treated, heat treatment appropriate can make the crystal grain of quick quenching band long
Greatly to suitable dimension；
(2) simultaneously, hydrogen processing appropriate can be such that the Nd-rich phase of grain boundaries in the rare-earth-iron-boron quick quenching band inhales
Hydrogen generates the stronger rare earth hydride of brittleness, when carrying out low energy ball milling, it is possible to reduce ball milling intra-die structural damage makes
Its more generation intercrystalline fracture, to which crystallite dimension be made evenly, and the Asia with magnetic anisotropy of size tunable
Micron rare-earth-iron-boron permanent-magnet alloy.
(3) average grain diameter of the rare-earth-iron-boron permanent-magnet alloy of magnetic anisotropy produced by the present invention is 100nm~1 μm,
The preparation method of the present invention realizes the Effective Regulation to particle mean size.
(4) at low cost, simple and practicable, it is suitble to be prepared on a large scale the sub-micron rare-earth-iron-boron permanent magnetism with magnetic anisotropy
Alloying pellet has good application value.
Description of the drawings
Fig. 1 be in embodiment 1 Ball-milling Time be 4h, 16h, for 24 hours and hydrogen processing after quick quenching band scanning electron microscope
Image.
Fig. 2 is that Ball-milling Time is 4h, 16h in embodiment 1, for 24 hours and after quick quenching band is orientated in magnetic field after hydrogen processing
XRD spectrum.
Specific implementation mode
The present invention is more specifically described in detail with reference to specific embodiment, but embodiments of the present invention are unlimited
Routine techniques progress can refer to for not specifically specified technological parameter in this.
A kind of preparation method of the rare-earth-iron-boron permanent-magnet alloy submicron particles with magnetic anisotropy comprising following
Step：
1) isotropic rare-earth-iron-boron quick quenching band is heat-treated under 500 DEG C~900 DEG C of oxygen-free environment,
It is grown to average grain size to 0.1~1 μm；The heat treatment time is 0.5h~10h；
2) it under 250 DEG C~350 DEG C, the Hydrogen Vapor Pressure of 50kPa~500kPa, carries out inhaling hydrogen processing；Then 250 DEG C~
350 DEG C of progress Dehydroepiandrosterone derivatives；Main use vacuumizes carry out Dehydroepiandrosterone derivative, and Dehydroepiandrosterone derivative can slough the hydrogen in main phase, crystal boundary
Hydrogen in place's Nd-rich phase remains in wherein；
3) quick quenching band obtained in step 2) is placed in the ball grinder with abrading-ball, surfactant and organic is added
Solvent under inert gas protection seals ball grinder, and ball grinder, which is put into ball mill, carries out ball milling；Ball milling 0.5h~200h
Afterwards, organic solvent, surfactant are removed, rare-earth-iron-boron permanent-magnet alloy magnetic anisotropy submicron particles are made.
In the preferred embodiment, in the rare-earth-iron-boron of the isotropic, the preferred neodymium Nd of the rare earth, cerium
At least one of Ce, praseodymium Pr, dysprosium Dy, terbium Tb.
The molecular formula of the rare-earth-iron-boron permanent-magnet alloy with magnetic anisotropy obtained is：RExFey1My2Bz；Its
Middle RE is Ce, Pr, Nd, Dy, at least one of Tb；M is at least one of Co, Cu, Al, Ga, Zr；X, y1, y2, z are phase
Answer the mass fraction of element, and 26≤x≤34,0≤y2≤10,0.95≤z≤1.10, y1=100-x-y2-z.
In the preferred embodiment, the organic solvent includes, but are not limited to absolute ethyl alcohol, normal heptane, aviation
Gasoline.The dosage of the organic solvent is 1 times~10 times of the isotropic rare-earth-iron-boron alloy mass.
In the preferred embodiment, the surfactant includes, but are not limited to oleyl amine, oleic acid, sad, pungent
Amine.The dosage of the surfactant is the 10%~300% of the isotropic rare-earth-iron-boron alloy mass.
In the preferred embodiment, the ball mill is low energy ball mill, including but not limited to planetary ball mill,
Rotary mill, agitating ball mill.
In the preferred embodiment, the ball grinder and Material quality of grinding balls are unlimited.The abrading-ball and the items
The mass ratio of same sex rare-earth-iron-boron alloy is preferably 5:1~30:1.
The preparation method of the present invention is heat-treated rare-earth-iron-boron quick quenching band, and heat treatment appropriate can make fast quenching
The crystal grain of band is grown up to suitable dimension；Meanwhile hydrogen processing appropriate can make crystal boundary in the rare-earth-iron-boron quick quenching band
The Nd-rich phase at place inhales hydrogen and generates the stronger rare earth hydride of brittleness, when carrying out low energy ball milling, it is possible to reduce in ball milling crystal grain
Portion's structural damage, makes it that intercrystalline fracture more occur, and to which crystallite dimension be made evenly, and size tunable has
The sub-micron rare-earth-iron-boron permanent-magnet alloy of magnetic anisotropy.The sub-micron rare-earth-iron-boron of magnetic anisotropy produced by the present invention
Permanent-magnet alloy average grain diameter is 100nm~1 μm.
Embodiment 1
A kind of preparation method of the Nd-Fe-B permanent-magnet alloy submicron particles with magnetic anisotropy comprising following step
Suddenly：
1) isotropic Nd-Fe-B quick quenching band is subjected to annealing 1h under 750 DEG C of oxygen-free environment；
2) it under 320 DEG C, the Hydrogen Vapor Pressure of 300kPa, carries out inhaling hydrogen processing；Then it at 320 DEG C, vacuumizes and is taken off
Hydrogen processing；
3) the Nd-Fe-B quick quenching band of 10 grams of above-mentioned processing of process is taken to be put into the ball grinder with abrading-ball, the abrading-ball
A diameter of 4 millimeters, the mass ratio of the abrading-ball and Nd-Fe-B quick quenching band is 10:1；10 grams of oleyl amines are added, normal heptane is added
To ball grinder is filled it up with, it is put into planetary ball mill after ball grinder is sealed and carries out ball milling.The planetary ball mill autorotation speed is 300
Rev/min.
4) ball milling 4h, 16h, and for 24 hours after, respectively take out portion of product be cleaned by ultrasonic 20min in n-hexane, in vacuum ring
It is tested and is characterized after drying under border.Nd-Fe-B particle size obtained is between 200 nanometers to 600 nanometers.
By hydrogen treated quick quenching band, by 4h, 16h, and the product after ball milling for 24 hours uses scanning electron microscopy respectively
Mirror (scanning electron microscope, SEM, abbreviation scanning electron microscope) is tested to obtain Fig. 1, as shown in Figure 1, respectively
The Nd-Fe-B quick quenching band particle size of the item same sex is about 40 microns in thickness direction, and direction is about hundreds of microns in face.With
After the method for the present invention ball milling 4 hours, particle size has been decreased to 3 microns or less.After ball milling 16 hours, particle size base
Originally it is reduced to sub-micrometer scale, but still there are many little particles to reunite together.After ball milling 24 hours, particle size is further uniform
Refinement, dispersibility is more preferably.
XRD (X-ray diffraction, X-ray diffraction) is carried out to test：As shown in Fig. 2, ball made from the present embodiment
Grind 4h, 16h, and for 24 hours after, anisotropy is gradually increased with the increase of Ball-milling Time.Non- milled sample XRD spectrum diffraction peak intensity
Degree and position coincide with standard neodymium iron boron PDF cards fine.After ball milling 4h, each diffraction maximum relative intensity changes, but
Still without apparent texture.After ball milling 16h, (004) of sample XRD spectrum, (006), (008) diffraction maximum relative intensity is remarkably reinforced.
Ball milling for 24 hours after, (004), (006), (008) diffraction maximum relative intensity further enhances, and (006) becomes highest peak, illustrates sample
Very strong c-axis texture is provided with after magnetic field orientating, ball milling product is with anisotropic neodymium iron boron particles.
Embodiment 2
A kind of preparation method of the Nd-Fe-B permanent-magnet alloy submicron particles with magnetic anisotropy comprising following step
Suddenly：
1) isotropic Nd-Fe-B quick quenching band is subjected to annealing 0.5h under 900 DEG C of oxygen-free environment；
2) it under 300 DEG C, the Hydrogen Vapor Pressure of 200kPa, carries out inhaling hydrogen processing；Then it at 300 DEG C, vacuumizes and is taken off
Hydrogen processing；
3) the Nd-Fe-B quick quenching band of 10 grams of above-mentioned processing of process is taken to be put into the ball grinder with abrading-ball, the abrading-ball
A diameter of 4 millimeters, the mass ratio of the abrading-ball and Nd-Fe-B quick quenching band is 5:1；20 grams of oleic acid are added, absolute ethyl alcohol is added
To ball grinder is filled it up with, it is put into planetary ball mill after ball grinder is sealed and carries out ball milling.The rotary mill autorotation speed is 300
Rev/min.
4) after ball milling 8h, portion of product is taken out respectively and is cleaned by ultrasonic 20min in n-hexane, after drying under vacuum conditions
It is tested and is characterized.
Product obtained is tested through SEM and XRD：Nd-Fe-B particle size is 100 nanometers to 1 micron, and obtained
Product has magnetic anisotropy.
Embodiment 3
A kind of preparation method of the Nd-Fe-B permanent-magnet alloy submicron particles with magnetic anisotropy comprising following step
Suddenly：
1) isotropic Nd-Fe-B quick quenching band is subjected to annealing 10h under 500 DEG C of oxygen-free environment；
2) it under 350 DEG C, the Hydrogen Vapor Pressure of 50kPa, carries out inhaling hydrogen processing；Then at 350 DEG C, carry out dehydrogenation is vacuumized
Processing；
3) the Nd-Fe-B quick quenching band of 10 grams of above-mentioned processing of process is taken to be put into the ball grinder with abrading-ball, the abrading-ball
A diameter of 4 millimeters, the mass ratio of the abrading-ball and Nd-Fe-B quick quenching band is 10:1；1 gram of oleyl amine is added, normal heptane is added extremely
Ball grinder is filled it up with, rotary mill is put into after ball grinder is sealed and carries out ball milling.The rotary mill autorotation speed is 300
Rev/min.
4) after ball milling 80h, portion of product is taken out respectively and is cleaned by ultrasonic 20min in n-hexane, is dried under vacuum conditions
After tested and characterized.
Product obtained is tested through SEM and XRD：Nd-Fe-B particle size is 100 nanometers to 550 nanometers, and is made
Product have magnetic anisotropy.
Embodiment 4
A kind of preparation method of the Nd-Fe-B permanent-magnet alloy submicron particles with magnetic anisotropy comprising following step
Suddenly：
1) isotropic Nd-Fe-B quick quenching band is subjected to annealing 8h under 600 DEG C of oxygen-free environment；
2) it under 250 DEG C, the Hydrogen Vapor Pressure of 500kPa, carries out inhaling hydrogen processing；Then it at 250 DEG C, vacuumizes and is taken off
Hydrogen processing；
3) the Nd-Fe-B quick quenching band of 10 grams of above-mentioned processing of process is taken to be put into the ball grinder with abrading-ball, the abrading-ball
A diameter of 4 millimeters, the mass ratio of the abrading-ball and Nd-Fe-B quick quenching band is 20:1；15 grams of octanoic acids are added, aviation vapour is added
Oil is put into rotary mill and carries out ball milling to ball grinder is filled it up with after sealing ball grinder.The rotary mill autorotation speed is
300 revs/min.
4) after ball milling 40h, portion of product is taken out respectively and is cleaned by ultrasonic 20min in n-hexane, is dried under vacuum conditions
After tested and characterized.
Product obtained is tested through SEM and XRD：Nd-Fe-B particle size is 100 nanometers to 550 nanometers, and is made
Product have magnetic anisotropy.
Embodiment 5
A kind of preparation method of the Nd-Fe-B permanent-magnet alloy submicron particles with magnetic anisotropy comprising following step
Suddenly：
1) isotropic Nd-Fe-B quick quenching band is subjected to annealing 5h under 700 DEG C of oxygen-free environment；
2) it under 320 DEG C, the Hydrogen Vapor Pressure of 350kPa, carries out inhaling hydrogen processing；Then it at 320 DEG C, vacuumizes and is taken off
Hydrogen processing；
3) the Nd-Fe-B quick quenching band of 10 grams of above-mentioned processing of process is taken to be put into the ball grinder with abrading-ball, the abrading-ball
A diameter of 4 millimeters, the mass ratio of the abrading-ball and Nd-Fe-B quick quenching band is 30:1；30 grams of octylames are added, normal heptane is added
To ball grinder is filled it up with, it is put into rotary mill after ball grinder is sealed and carries out ball milling.The rotary mill autorotation speed is 300
Rev/min.
4) after ball milling 200h, portion of product is taken out respectively and is cleaned by ultrasonic 20min in n-hexane, is dried under vacuum conditions
After tested and characterized.
Product obtained is tested through SEM and XRD：Nd-Fe-B particle size is 400 nanometers to 1 micron, and obtained
Product has magnetic anisotropy.
The invention is not limited in the above embodiments, if the various changes or deformation to the present invention do not depart from the present invention
Spirit and scope, if these changes and deformation belong within the scope of the claim or equivalent technologies of the present invention, then this hair
It is bright to be also intended to comprising these changes and deformation.
Claims (7)
1. a kind of preparation method of the rare-earth-iron-boron permanent-magnet alloy submicron particles with magnetic anisotropy, which is characterized in that
Include the following steps：
1) isotropic rare-earth-iron-boron quick quenching band is heat-treated under 500 DEG C~900 DEG C of oxygen-free environment, until brilliant
Grain average-size is grown to 0.1 μm~1 μm；The heat treatment time is 0.5h~10h；
2) it under 250 DEG C~350 DEG C, the Hydrogen Vapor Pressure of 50kPa~500kPa, carries out inhaling hydrogen processing；Then 250 DEG C~350
DEG C carry out Dehydroepiandrosterone derivative；
3) quick quenching band obtained in step 2) is placed in the ball grinder with abrading-ball, surfactant and organic molten is added
Agent under inert gas protection seals ball grinder, and ball grinder, which is put into low energy ball mill, carries out ball milling；After ball milling, removing has
Rare-earth-iron-boron permanent-magnet alloy magnetic anisotropy submicron particles are made in solvent, surfactant.
2. the preparation side of the rare-earth-iron-boron permanent-magnet alloy submicron particles according to claim 1 with magnetic anisotropy
Method, which is characterized in that the detailed process of step 3) is：
The quick quenching band obtained in step 2) is placed in the ball grinder with abrading-ball, surfactant and organic solvent is added,
Ball grinder is sealed under inert gas protection, ball grinder, which is put into ball mill, carries out ball milling；After ball milling 0.5h~200h, remove
Rare-earth-iron-boron permanent-magnet alloy magnetic anisotropy submicron particles are made in organic solvent, surfactant.
3. the preparation side of the rare-earth-iron-boron permanent-magnet alloy submicron particles according to claim 2 with magnetic anisotropy
Method, which is characterized in that in the rare-earth-iron-boron quick quenching band, the rare earth is at least one of Nd, Ce, Pr, Dy, Tb.
4. the preparation side of the rare-earth-iron-boron permanent-magnet alloy submicron particles according to claim 3 with magnetic anisotropy
Method, which is characterized in that the molecular formula of the rare-earth-iron-boron permanent-magnet alloy with magnetic anisotropy obtained is：
RExFey1My2Bz；Wherein RE is Ce, Pr, Nd, Dy, at least one of Tb；M is at least one of Co, Cu, Al, Ga, Zr；
X, y1, y2, z are the mass fraction of respective element, and 26≤x≤34,0≤y2≤10,0.95≤z≤1.10, y1=100-x-
y2-z。
5. the preparation side of the rare-earth-iron-boron permanent-magnet alloy submicron particles according to claim 4 with magnetic anisotropy
Method, which is characterized in that the organic solvent is at least one of absolute ethyl alcohol, normal heptane, aviation gasoline.
6. the preparation side of the rare-earth-iron-boron permanent-magnet alloy submicron particles according to claim 5 with magnetic anisotropy
Method, which is characterized in that the surfactant is at least one of oleyl amine, oleic acid, octanoic acid, octylame.
7. a kind of preparation method according to any one of claim 1-6 is prepared dilute with magnetic anisotropy
Soil-iron-boron permanent-magnet alloy submicron particles, which is characterized in that the molecule of the rare-earth-iron-boron permanent-magnet alloy submicron particles
Formula is：RExFey1My2Bz；Wherein RE is Ce, Pr, Nd, Dy, at least one of Tb；M be Co, Cu, Al, Ga, Zr at least
It is a kind of；X, y1, y2, z are the mass fraction of respective element, and 26≤x≤34,0≤y2≤10,0.95≤z≤1.10, y1=
100-x-y2-z。
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| CN101982855A (en) * | 2010-09-16 | 2011-03-02 | 中国科学院宁波材料技术与工程研究所 | Sintered Nd-Fe-B permanent-magnet material and preparation method thereof |
| 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 |
| CN103928204A (en) * | 2014-04-10 | 2014-07-16 | 重庆科技学院 | Low-rare earth content anisotropy nanocrystalline NdFeB compact magnet and preparation method thereof |
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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 |
| CN103928204A (en) * | 2014-04-10 | 2014-07-16 | 重庆科技学院 | Low-rare earth content anisotropy nanocrystalline NdFeB compact magnet and preparation method thereof |
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