CN1059230A - Novel rare-earth-iron-nitrogen permanent magnetic material - Google Patents

Novel rare-earth-iron-nitrogen permanent magnetic material Download PDF

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CN1059230A
CN1059230A CN 90109166 CN90109166A CN1059230A CN 1059230 A CN1059230 A CN 1059230A CN 90109166 CN90109166 CN 90109166 CN 90109166 A CN90109166 A CN 90109166A CN 1059230 A CN1059230 A CN 1059230A
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nitrogen
permanent magnetic
alloy
earth
iron
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CN1022520C (en
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杨应昌
张晓东
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Peking University
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Peking University
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Abstract

The present invention makes with R by the nitrogen Technology for Heating Processing 2Fe 17Nx, R (TiFe) 12Nz, R (VFe) 12Alloys such as Nz are high-curie temperature, the high saturation and magnetic intensity of base, the rare-earth-iron of high monadic magnetocrystalline anisotropy-nitrogen novel permanent magnetic alloy.Other is the magnetic of the alloy of base with the rare-earth-iron for also available this kind process improving.The new material of being invented can be widely used in electrical equipment, motor and the electronic instrument.Wide because of its temperature applicable range, cost is low, and competitiveness will be arranged very much.

Description

Novel rare-earth-iron-nitrogen permanent magnetic material
This invention belongs to field of magnetic material.
Existing rare earth permanent-magnetic material has developed the three generations.First, second generation is with SmCo 5And Sm 2Co 17Rare earth-Co permanent magnetic alloy for base.Its Main Ingredients and Appearance is a cobalt, but cobalt resource is in short supply, cost is expensive, and since at the bottom of nineteen eighty-three, having developed with iron is the third generation Nd of Main Ingredients and Appearance 2Fe 14Type B magnet, but Nd 2Fe 14The B Curie temperature is not high, and temperature stability is poor, need improve its performance or development novel rare-earth-iron permanent-magnet material.This invention is a kind of novel rare-earth-iron-nitrogen (R-Fe-N) permanent magnetic material series.
Technical essential of the present invention is as follows:
1. with the rare-earth-iron alloy of base, as R 2Fe 17, R 2Fe 14B and R(Fe, M) 12, wherein M=Ti, V, Mo, W, Si, Al, Mn etc., pulverize, granularity is heat-treated in nitrogen between 10-100 μ.Treatment temperature is between 350 ℃-600 ℃, and temperature retention time 0.5-4 hour, air pressure was about 1 atmospheric pressure.After this handled, nitrogen-atoms can enter into the structure of R-Fe alloy, forms corresponding R-Fe-N alloy.As R 2Fe 17Nx, R 2Fe 14BNy and R(Fe, M) 12Nz etc., wherein R is a rare earth element, M is for stablizing ThMn 12The element of structure, x ≈ 2-3.Y, z ≈ 1(x, y, the numerical value of z be according to different structures and different).Neutron-diffraction study shows that nitrogen-atoms enters the interstitial site of above-mentioned all crystal, and table 1 is listed the crystal structure and the lattice constant of above-mentioned typical R-Fe-N alloy for example.
Table 1 Sm 2Fe 17N 2, Nd 2Fe 14BN and NdTiFe 11The crystal structure of N and lattice constant
Alloy Crystal structure a(nm) C(nm)
Sm 2Fe 17N 2 Water chestnut side R3m 0.8728 1.2657
Nd 2Fe 14BN Four directions P4 2／mnm 0.8851 1.2253
NdTiFe 11N Four directions I4/mmm 0.8701 0.4844
Above-mentioned R(Fe, M) 12The Nz alloy is characterized in as R=Nd, Tb, Ho etc., M=Ti, and V, Mo, Nb, W, Si, Ga, Al during Mn, is novel permanent-magnet alloy, as NdTiFe 11Nz, NdV 2Fe 10Nz etc., in order further to improve coercive force, saturation magnetization and Curie temperature Nd can partly use the heavy rare earth element replacement of the contour magnetocrystalline anisotropy of Tb, but Ti, V mixing match, the Mo of the trace that perhaps mixes, Nb, W, Ga, Si, Al etc., Fe can be with proper C o replacement, as (NdTb) (Ti, Nb, Al, Fe) 12Nz, and (Nd, Tb) (Ti, V, Co, Fe) 12Nz etc.
Above-mentioned alloy R 2Fe 17Nx wherein during R=Sm, is novel permanent-magnet alloy.For the further coercive force that improves, saturation magnetization and Curie temperature, Fe can partly be replaced by Ga, Al, Zr, Mn, Co, Cu, as Sm 2(Fe, Ga, Zr, Co) 17Nx.
Above-mentioned alloy R 2Fe 14BNy wherein when R=Nd, is the Nd-Fe-B type permanent magnetic material of high-curie temperature, is further to improve coercive force and Curie temperature, can use Nb with Tb, the Dy Nd that partly replaces, Al, and Cu, Ga, Co partly replace Fe as (NdDy) 2(FeNbAl) 14BNy and (NdDy) 2(FeCoNbGa) 14BNy.
2. at novel rare-earth-iron described in 1-nitrogen permanent magnetic material, promptly adopted the Technology for Heating Processing under nitrogen atmosphere, made it to inhale that Curie temperature raises behind the nitrogen, saturation magnetization increases, magnetocrystalline anisotropy generation great change simultaneously.Therefore the nitrogen Technology for Heating Processing both can be used as a kind of method of improving magnet magnetic, as Nd 2Fe 14B inhales after the nitrogen, and Curie temperature rises to 640K from 585K; Be again a kind of means of making high-curie temperature novel rare-earth-iron permanent-magnet material, as Sm 2Fe 17With R(Fe, M) 12, wherein R is Nd, Tb, Ho etc., not only Curie temperature raises later on, Curie temperature T to inhale nitrogen CAll more than 700K, and the C axle becomes direction of easy axis, has strong anisotropy field, particularly Sm under the room temperature 2Fe 17Nx and Nd(TiFe) 12Nz has high saturation and magnetic intensity, can be made into high-coercive force, the high energy product magnet, and the theoretical value of maximum magnetic energy product is respectively 55MGOe and 60MGOe, table 2 is listed Sm 2Fe 17N 2And NdTiFe 11The basic magnetic of N.
Table 2 Sm 2Fe 17N 2And NdTiFe 11The saturation magnetization σ of N S, Curie temperature Tc, anisotropy field H AAnd direction of easy axis
Alloy σS(emu/g) Tc(K) H A(tesla) Direction of easy axis
1.5K 293K 1.5K 293K
Sm 2Fe 17N 2 148.72 137.56 747 17.0 12.0 The C-axle
NdTiFe 11N 158.80 145.35 740 11.5 8.0 The C-axle
The condition of nitrogen Technology for Heating Processing recited above is: the purity of nitrogen is more than 99.9%; Heat treatment temperature is 350-600 ℃; Heat treatment period is 0.5-4 hour; Nitrogen pressure is 1 atmospheric pressure; The granularity of sample is between 10-100 μ, and promptly technical process is under these conditions made the R-Fe-N permanent magnetic material.
If further permanent magnetic material R-Fe-N alloy powder is made permanent-magnet, built-up magnet technology has been adopted in this invention, its method is to be that zinc powder, glass putty or the aluminium powder of 10Wt%-50Wt% evenly mixes with permanent magnetic alloy powder with weight ratio, moulding in magnetic field under the pressure of 100-300MPa then, anisotropic built-up magnet is promptly made in heat treatment under 400 ℃ of-500 ℃ of temperature again.
Also can adopt mechanical alloying method and quick-quenching method earlier, make R-Fe nano microcrystalline powder, heat treatment in nitrogen then forms R-Fe-N nano microcrystalline powder, and this powder can directly adopt rubber or resin bonding or direct die mould to make isotropic permanent magnet.
In addition, above-mentioned rare-earth-iron-nitrogen permanent magnetic material also can adopt the technology of alloy melting to prepare, be characterized in utilizing in the alloy constituent element corresponding nitrogen alloy or the compound that forms with nitrogen as raw material preparation then carrying out melting.
The invention has the advantages that the R-Fe-N alloy has very high Curie temperature (more than the 700K), therefore the permanent magnet of making can use under higher temperature, has overcome Nd 2Fe 14The shortcoming of B magnet.In addition, Nd(TiFe) 12The permanent magnet that the Nz alloy is made cost an arm and a leg and rare samarium (Sm) metal because can not use, thereby cost is low, helps market competition.
Embodiment
Arc furnace or induction furnace melting Nd(TiFe) 12Alloy.
The alloy abrasive dust, about 30 μ of granularity put into the molybdenum ware.Put the molybdenum ware in quartz ampoule, heat-treat.Heat treatment temperature is 480 ℃.Inject the high pure nitrogen of circulation in the quartz ampoule, pressure is an atmospheric pressure.Be incubated 2 hours, from stove, take out quartz ampoule then, use the water cooling quartz ampoule.Make Nd(TiFe) 12The Nz alloy, Z ≈ 1.This alloy Curie temperature is 740K.The C axle is a direction of easy axis, room temperature anisotropy field 8 teslas, and saturation magnetization 4 π Ms are respectively 14759 gaussian sums, 13509 Gausses when temperature is 1.5K and 300K.
The Nd(TiFe that makes above) 12The Nz alloy powder, further being ground to granularity is 3 μ, evenly mix with the zinc powder of 15Wt% then, the high pressure die mould, built-up magnet is promptly made in heat treatment under 400 ℃ temperature again.

Claims (9)

1, a kind of novel permanent magnetic material is characterized in that containing the permanent-magnet alloy R of rare-earth-iron-nitrogen element 2Fe 17Nx, R 2Fe 14BNy and R (Fe, M) 12Nz, wherein:
(1) R is a rare earth element;
(2) M is for stablizing ThMn 12The element of structure;
(3)x≈2-3，y、z≈1。
2, according to the described rare-earth-iron of claim 1-nitrogen permanent magnetic material, wherein R(Fe, M) 12The feature of Nz alloy is:
(1) as R=Nd, Tb, Ho; When M=Ti, V, Mo, Nb, W, Si, Ga, Al, Mn novel permanent magnetic alloy NdTiFe 11N or NdV 2Fe 10N;
(2) partly replace as Nd with Tb; Mo, Nb, W, Ga, Si, the Al of Ti, V mixing match or the trace that mixes; Fe is with The addition of C o replacement, be novel permanent magnetic alloy (NdTb) (Ti, NbAl, Fe) 12N or (NdTb) (Ti, V, Co, Fe) 12N.
3, according to the described rare-earth-iron of claim 1-nitrogen permanent magnetic material, wherein R 2Fe 17The feature of Nx alloy is:
(1) during R=Sm, is the novel permanent magnetic alloy;
(2) Fe is partly replaced by Ga, Al, Zr, Mn, Co, Cu, is novel permanent magnetic alloy Sm 2(Fe, Ga, Zr, Co) 17Nx.
4, according to the described rare-earth-iron of claim 1-nitrogen permanent magnetic material, wherein R 2Fe 14BN yThe feature of alloy is:
(1) R=Nd is the Nd-Fe-B type permanent magnetic material of high-curie temperature;
(2) Tb, the Dy Nd that partly replaces, partly replacing Fe with Nb, Al, Cu, Ga, Co is novel permanent magnetic material (NdDy) 2(FeNbAl) 14BNy or (Nd, Dy) 2(FeCoNbGa) 14BNy.
5, the method for manufacturing technology of a kind of novel rare-earth-iron-nitrogen permanent magnetic material and magnet is characterized in that having adopted nitrogen Technology for Heating Processing and built-up magnet technology.
6, according to the manufacturing process of the described rare-earth-iron of claim 5-nitrogen permanent magnetic material, its nitrogen Technology for Heating Processing feature is:
(1) purity 99.9% of nitrogen;
(2) heat treatment temperature is 350 ℃-600 ℃;
(3) heat treatment time 0.5-4 hour;
(4) nitrogen pressure is 1 atmospheric pressure;
(5) granularity of sample is between 10-100 μ.
7, according to the manufacturing process of the described rare-earth-iron of claim 5-nitrogen permanent-magnet, the feature of its built-up magnet technology is:
(1) be that zinc powder, glass putty or the aluminium powder of 10Wt%-50Wt% evenly mixes with permanent magnetic alloy powder with weight ratio;
(2) at the 100-300MPa forming under the pressure;
(3) heat treatment under 400 ℃ of-500 ℃ of temperature;
(4) in magnetic field, be orientated, make anisotropic built-up magnet.
8, according to the manufacturing process of the described rare-earth-iron of claim 5 to 7-nitrogen permanent magnetic material and magnet, it is characterized in that to adopt mechanical alloying or quick-quenching method earlier, make R-Fe nano microcrystalline powder, R-Fe-N nano microcrystalline powder is made in heat treatment in nitrogen then, again with rubber or resin bonding or directly die mould make anisotropic permanent magnet.
9, according to the described rare-earth-iron of claim 1-nitrogen permanent magnetic material, also can adopt the technology of alloy melting to prepare, it is characterized in that utilizing in the alloy constituent element corresponding nitrogen alloy or prepare as raw material and then carry out melting with the compound that nitrogen forms.
CN 90109166 1990-11-16 1990-11-16 Rareearth -Fe-N permanent magnet Expired - Lifetime CN1022520C (en)

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CN 90109166 CN1022520C (en) 1990-11-16 1990-11-16 Rareearth -Fe-N permanent magnet

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CN1022520C CN1022520C (en) 1993-10-20

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Cited By (8)

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Publication number Priority date Publication date Assignee Title
CN100334656C (en) * 2003-01-28 2007-08-29 Tdk株式会社 Hard magnetic composition, permanent magnet powder, method for permanent magnet powder, and bonded magnet
CN100369165C (en) * 2004-11-09 2008-02-13 北矿磁材科技股份有限公司 Cohesive composite permanent magnetic material containing neodymium iron nitrogen and its preparation method
US7465363B2 (en) 2003-01-28 2008-12-16 Tdk Corporation Hard magnetic composition, permanent magnet powder, method for permanent magnet powder, and bonded magnet
CN102208234A (en) * 2010-03-29 2011-10-05 有研稀土新材料股份有限公司 Rare earth permanent magnetic powder and bonded magnet
CN106475555A (en) * 2015-08-25 2017-03-08 通用汽车环球科技运作有限责任公司 For preparing the quick consolidation method of block metastable state richness iron material
CN106548842A (en) * 2015-09-17 2017-03-29 丰田自动车株式会社 Magnetic compound and its manufacture method
CN107785139A (en) * 2016-08-24 2018-03-09 株式会社东芝 Ferromagnetic material, permanent magnet, electric rotating machine and vehicle
CN108831659A (en) * 2018-09-10 2018-11-16 重庆科技学院 It is a kind of to prepare a nanometer method and nanometer permanent magnetism powder for neodymium iron nitrogen permanent-magnet powder

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Cited By (15)

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CN100334656C (en) * 2003-01-28 2007-08-29 Tdk株式会社 Hard magnetic composition, permanent magnet powder, method for permanent magnet powder, and bonded magnet
US7465363B2 (en) 2003-01-28 2008-12-16 Tdk Corporation Hard magnetic composition, permanent magnet powder, method for permanent magnet powder, and bonded magnet
CN100369165C (en) * 2004-11-09 2008-02-13 北矿磁材科技股份有限公司 Cohesive composite permanent magnetic material containing neodymium iron nitrogen and its preparation method
CN102576588B (en) * 2010-03-29 2016-03-30 有研稀土新材料股份有限公司 Rare earth permanent magnet powder, bonded permanent magnet and comprise its device
CN102576588A (en) * 2010-03-29 2012-07-11 有研稀土新材料股份有限公司 Rare-earth permanent magnetic powder, bonded magnet, and device comprising the bonded magnet
US9245674B2 (en) 2010-03-29 2016-01-26 Grirem Advanced Materials Co., Ltd. Rare-earth permanent magnetic powder, bonded magnet, and device comprising the same
CN102208234A (en) * 2010-03-29 2011-10-05 有研稀土新材料股份有限公司 Rare earth permanent magnetic powder and bonded magnet
CN102208234B (en) * 2010-03-29 2016-11-09 有研稀土新材料股份有限公司 A kind of rare earth permanent magnet powder and bonded permanent magnet
CN106475555A (en) * 2015-08-25 2017-03-08 通用汽车环球科技运作有限责任公司 For preparing the quick consolidation method of block metastable state richness iron material
US10062482B2 (en) 2015-08-25 2018-08-28 GM Global Technology Operations LLC Rapid consolidation method for preparing bulk metastable iron-rich materials
CN106475555B (en) * 2015-08-25 2019-05-31 通用汽车环球科技运作有限责任公司 It is used to prepare the quick consolidation method of blocky metastable state richness iron material
US10930417B2 (en) 2015-08-25 2021-02-23 Gm Global Technology Operations Rapid consolidation method for preparing bulk metastable iron-rich materials
CN106548842A (en) * 2015-09-17 2017-03-29 丰田自动车株式会社 Magnetic compound and its manufacture method
CN107785139A (en) * 2016-08-24 2018-03-09 株式会社东芝 Ferromagnetic material, permanent magnet, electric rotating machine and vehicle
CN108831659A (en) * 2018-09-10 2018-11-16 重庆科技学院 It is a kind of to prepare a nanometer method and nanometer permanent magnetism powder for neodymium iron nitrogen permanent-magnet powder

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