CN115798850A - Magnetic steel containing high-abundance rare earth elements and preparation method and application thereof - Google Patents
Magnetic steel containing high-abundance rare earth elements and preparation method and application thereof Download PDFInfo
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- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 69
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- 238000005324 grain boundary diffusion Methods 0.000 claims abstract description 15
- 238000000465 moulding Methods 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 10
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- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 38
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- 230000000694 effects Effects 0.000 description 6
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- 238000004453 electron probe microanalysis Methods 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 229910001172 neodymium magnet Inorganic materials 0.000 description 4
- 229910001279 Dy alloy Inorganic materials 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
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- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000000462 isostatic pressing Methods 0.000 description 2
- 238000010902 jet-milling Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
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- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/06—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys in the form of particles, e.g. powder
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/06—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys in the form of particles, e.g. powder
- H01F1/08—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys in the form of particles, e.g. powder pressed, sintered, or bound together
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Hard Magnetic Materials (AREA)
Abstract
The invention discloses magnetic steel containing high-abundance rare earth elements and a preparation method and application thereof. The preparation method of the magnetic steel containing the high-abundance rare earth element comprises the following steps: (1) Mixing the powder of the main alloy and the powder of the auxiliary alloy, and crushing, molding and sintering the mixture to obtain the alloy; wherein the composition of the main alloy is (RE) a Pr b Nd c ) d Fe e Al f Cu g Ga h Zr i Ti j B k (ii) a RE is a high-abundance rare earth element and comprises one or more of La, ce, Y, er, yb, gd, tm and Sm; the composition of the secondary alloy is R m Fe n Cu o Al p (ii) a R is a rare earth element; (2) To pairAnd (3) carrying out grain boundary diffusion on the sintered body obtained in the step (1) and the diffusion source raw material composition. The invention improves the magnetic property of the magnet containing abundant rare earth by constructing the composite magnetic hardening shell.
Description
Technical Field
The invention relates to magnetic steel containing high-abundance rare earth elements and a preparation method and application thereof.
Background
The neodymium iron boron permanent magnet material is widely applied to the fields of electronic products, automobiles, wind power, household appliances, elevators, industrial robots and the like due to excellent magnetic performance, for example, a focusing motor, a driving motor, a wind driven generator, an elevator tractor, a positioning motor and other permanent magnet motors provide a magnetic field and the like, the demand of the neodymium iron boron permanent magnet material is gradually expanded, the demand of the neodymium iron boron permanent magnet material on Pr/Nd/Dy/Tb is greatly increased, and meanwhile, abundant rare earth and other rare earth are greatly placed, so that waste is caused;
however, the addition of high-abundance rare earth elements such as La, ce, Y, er, yb, gd, tm, or Sm to a neodymium iron boron permanent magnet material can reduce the magnetic performance of the permanent magnet material, and limit the application of high-abundance rare earth elements such as La, ce, Y, er, yb, gd, tm, or Sm to permanent magnet materials.
Disclosure of Invention
The invention mainly aims to overcome the defects that the coercivity cannot be effectively improved and the remanence cannot be maintained by adopting high-abundance rare earth in the prior art, and provides magnetic steel containing high-abundance rare earth elements, and a preparation method and application thereof. The invention fully utilizes HA of Y/Er/Yb/Gd/Tm/Sm, pr/Nd/Ho/Dy and Dy/Tb by constructing the composite magnetic hardening shell layer, and improves the magnetic property of the magnet containing the high-abundance rare earth.
The present invention mainly solves the above technical problems by the following technical solutions.
One of the technical schemes of the invention is as follows: a preparation method of magnetic steel containing high-abundance rare earth elements comprises the following steps:
(1) Mixing the powder of the main alloy and the powder of the auxiliary alloy, and crushing, molding and sintering the mixture to obtain the alloy;
wherein the composition of the main alloy is (RE) a Pr b Nd c ) d Fe e Al f Cu g Ga h Zr i Ti j B k ；
RE is a high-abundance rare earth element; RE comprises one or more of La, ce, Y, er, yb, gd, tm and Sm;
in atomic percent: a is 0.05 to 0.3; b is 0.1 to 1.2; c is 0.5 to 0.9; d is 13 to 15; e is 78 to 80; f is 0.2 to 0.4; g is 0.1 to 0.3; h is 0.2 to 0.5; i is 0.2 to 0.4; j is 0.2 to 0.4; k is 5to 6;
wherein the composition of the secondary alloy is R m Fe n Cu o Al p ；
R is a rare earth element;
in atomic percentage: m is 45 to 55; n is 35to 45; o is 4 to 8; p is 4 to 8;
(2) Performing grain boundary diffusion treatment on the sintered body obtained in the step (1) and the diffusion source raw material composition;
wherein, the content of the heavy rare earth element in the diffusion source raw material composition is more than m in atomic percentage.
In the present invention, in the composition of the main alloy, RE preferably includes Y.
In the present invention, it is preferable that the composition of the main alloy is, in atomic percent: a is 0.1.
In the present invention, it is preferable that, in the composition of the main alloy, in atomic percentage: b is 0.18 to 1, more preferably 0.22 to 0.9.
In the present invention, it is preferable that the composition of the main alloy is, in atomic percent: c is 0.55 to 0.8, more preferably 0.57 to 0.68.
In the present invention, it is preferable that, in the composition of the main alloy, in atomic percentage: d is 13 to 14, more preferably 13.64.
In the present invention, it is preferable that the composition of the main alloy is, in atomic percent: e is from 78.5 to 80, more preferably from 78.88 to 79.48, for example 79.26.
In the present invention, it is preferable that the composition of the main alloy is, in atomic percent: f is 0.2 to 0.3, more preferably 0.24.
In the present invention, it is preferable that the composition of the main alloy is, in atomic percent: g is 0.2.
In the present invention, it is preferable that the composition of the main alloy is, in atomic percent: h is 0.3 to 0.4, more preferably 0.36.
In the present invention, it is preferable that the composition of the main alloy is, in atomic percent: i is 0.2 to 0.3, more preferably 0.26.
In the present invention, it is preferable that the composition of the main alloy is, in atomic percent: j is 0.2 to 0.3, more preferably 0.27.
In the present invention, it is preferable that, in the composition of the main alloy, in atomic percentage: k is 5.5 to 6, more preferably 5.75.
In the present invention, preferably, the composition of the main alloy is (Y) 0.1 PrNd 0.9 ) 13.64 Fe 79.26 Al 0.24 Cu 0.2 Ga 0.36 Zr 0.26 Ti 0.27 B 5.75 (ii) a Or (Y) 0.05 Pr 0.18 Nd 0.57 ) 13.64 Fe 78.88 Al 0.24 Cu 0.2 Ga 0.36 Zr 0.26 Ti 0.27 B 5.75 (ii) a Or (La) 0.1 Pr 0.22 Nd 0.68 ) 13.64 Fe 79.48 Al 0.24 Cu 0.2 Ga 0.36 Zr 0.26 Ti 0.27 B 5.75 (ii) a Or, (Ce) 0.1 Pr 0.22 Nd 0.68 ) 13.64 Fe 79.48 Al 0.24 Cu 0.2 Ga 0.36 Zr 0.26 Ti 0.27 B 5.75 (ii) a Or, (Yb) 0.1 Pr 0.22 Nd 0.68 ) 13.64 Fe 79.48 Al 0.24 Cu 0.2 Ga 0.36 Zr 0.26 Ti 0.27 B 5.75 (ii) a Or, (Tm) 0.1 Pr 0.22 Nd 0.68 ) 13.64 Fe 79.48 Al 0.24 Cu 0.2 Ga 0.36 Zr 0.26 Ti 0.27 B 5.75 (ii) a Or (Gd) 0.1 Pr 0.22 Nd 0.68 ) 13.64 Fe 79.48 Al 0.24 Cu 0.2 Ga 0.36 Zr 0.26 Ti 0.27 B 5.75 (ii) a Or (Sm) 0.1 Pr 0.22 Nd 0.68 ) 13.64 Fe 79.48 Al 0.24 Cu 0.2 Ga 0.36 Zr 0.26 Ti 0.27 B 5.75 。
In the present invention, the main alloy may be used to form a main phase center and a main phase outer layer.
In the present invention, it is preferable that in the composition of the secondary alloy, R is Dy or Pr.
In the present invention, it is preferable that, in the composition of the secondary alloy, in atomic percentage: m is 50; n is 40; o is 5; p is 5.
In the present invention, it is preferable that the composition of the auxiliary alloy is Dy 50 Fe 40 Cu 5 Al 5 Or Pr 50 Fe 40 Cu 5 Al 5 。
In the present invention, in the step (1), the mass ratio of the powder of the main alloy to the powder of the secondary alloy is preferably (90 to 99): (10-1), more preferably 98:2;
in the present invention, in the step (1), preferably, the pulverization process includes hydrogen pulverization and micro pulverization.
Wherein, the hydrogen crushing is preferably carried out by hydrogen absorption, dehydrogenation and cooling treatment.
Wherein the micro-crushing is preferably jet mill crushing.
The jet mill pulverization is preferably carried out in a nitrogen atmosphere having an oxidizing gas content of 150ppm or less.
The pressure of a crushing chamber for crushing by the jet mill is preferably 0.38MPa.
The jet mill pulverizing time is preferably 3 hours.
In the present invention, in the step (1), preferably, the molding process is a magnetic field molding method or a hot-press thermal deformation method.
The magnetic field intensity of the magnetic field forming method is preferably 1.5T or more, for example, 1.6T;
in the present invention, in step (1), preferably, the sintering process is performed by preheating, sintering, and cooling under a vacuum condition.
Wherein the preheating temperature is preferably 300-600 ℃. The preheating time is preferably 1 to 2 hours. More preferably, the preheating is preheating at temperatures of 300 ℃ and 600 ℃ for 1h, respectively.
Wherein the sintering temperature is preferably 1080-1090 ℃.
Wherein, the sintering time is preferably 4h.
In the present invention, in the step (2), preferably, the diffusion source raw material composition is an alloy powder containing a heavy rare earth element; can be used to form a main phase epitaxial layer.
Wherein the heavy rare earth element preferably includes Dy and/or Tb.
The atomic percentage of the heavy rare earth element is preferably 50 to 80at%; more preferably 60 to 70at%.
In the present invention, in the step (2), preferably, the diffusion source raw material composition further includes M; the M preferably comprises one or more of Al, cu and Ga; more preferably Al and Cu.
Wherein, the atomic percentage of M is preferably 20 to 50at%; more preferably 30 to 40at%;
when said M comprises Cu, the atomic percentage of said Cu is preferably from 10 to 25at%; more preferably 15 to 20at%.
When said M comprises Al, the atomic percent of said Al is preferably 10 to 25at%; more preferably 15 to 20at%.
In the present invention, in the step (2), it is preferable that the diffusion source material composition is Dy 70 Cu 15 Al 15 。
In the present invention, the mass ratio of the sintered body obtained in step (1) to the diffusion source raw material composition is (98 to 99.5): (0.5 to 2), preferably 99.2:0.8.
in the present invention, in the step (2), preferably, the grain boundary diffusion is performed in a high-purity Ar gas atmosphere. The pressure of the high-purity Ar gas atmosphere is preferably 8X 10 -3 Pa～2×10 5 Pa。
In the present invention, in the step (2), the temperature of the grain boundary diffusion is preferably 800 to 980 ℃, for example, 900 ℃.
In the present invention, in the step (2), preferably, in the grain boundary diffusion, the time of the grain boundary diffusion is 12 to 30 hours, preferably 15 to 28 hours; for example 24h.
In the present invention, in the step (2), preferably, after the grain boundary diffusion, a diffusion heat treatment and/or an aging heat treatment is further included.
The temperature of the diffusion heat treatment is preferably 850 to 950 ℃, for example, 900 ℃. The time for the aging heat treatment is preferably 20 to 40 hours, for example 24 hours.
The temperature of the aging heat treatment is preferably 440 to 580 ℃, for example, 500 ℃. The time for the ageing heat treatment is preferably 2 to 4 hours, for example 4 hours.
In the present invention, the powder of the main alloy is preferably prepared by the following method: mixing the RE, the Pr, the Nd, the Fe, the Al, the Cu, the Ga, the Zr, the Ti and the B according to a ratio, and smelting and casting the mixture.
Wherein, the smelting is preferably a high-frequency vacuum induction smelting furnace. The degree of vacuum of the melting is preferably 5X 10 - 2 Pa. The melting temperature is preferably 1500 ℃ or lower.
Wherein the casting is preferably performed in an Ar gas atmosphere at 10 deg.C 2 DEG C/sec-10 4 Cooling at a rate of DEG C/sec.
In the present invention, the powder of the secondary alloy is preferably prepared by the following method: mixing the R, the Fe, the Cu and the Al according to a ratio, heating and melting by a vacuum induction melting furnace under the protection of argon gas, and melting by 10 DEG 2 DEG C/sec-10 4 The speed is measured at a temperature/second.
The second technical scheme of the invention is as follows: the magnetic steel containing the high-abundance rare earth element is prepared by the preparation method of the magnetic steel containing the high-abundance rare earth element.
The third technical scheme of the invention is as follows: a magnetic steel containing high-abundance rare earth elements comprises a main phase center, a main phase outer layer and a main phase epitaxial layer; the main phase outer layer is positioned outside the main phase center and completely covers the main phase center; the main phase epitaxial layer is positioned on the outer side of the main phase outer layer and completely covers the main phase outer layer;
wherein the main phase center is high-abundanceRare earth element RE 1 Is A in an amount of 1 at%, at% refers to the atomic percentage of the high-abundance rare earth element in the center of the main phase in the magnetic steel containing the high-abundance rare earth element;
high abundance rare earth element RE in the outer layer of the main phase 2 Is A in an amount of 2 at percent, at percent refers to the atomic percentage of the high-abundance rare earth element in the outer layer of the main phase in the magnetic steel containing the high-abundance rare earth element;
A 1 at％＞A 2 at％；
wherein the average diameter of the center of the main phase is r 1 The average thickness of the main phase outer layer is r 2 ，1<r 1 /r 2 <5；
Wherein the main phase epitaxial layer comprises a heavy rare earth element RH; the average thickness of the main phase epitaxial layer is r 3 ，2nm<r 3 <500nm。
In the present invention, the main phase center may include a light rare earth element RL 1 Said light rare earth element RL 1 Including a high abundance of rare earth element RE 1 。
In the center of the main phase, the light rare earth element RL 1 Preferably comprising Pr and/or Nd. The light rare earth element RL 1 The atomic percentage of (B) is preferably 9.0at% to 10.0at%, for example 9.63at%.
In the core of the main phase, the abundant rare earth element RE 1 The atomic percentage of (B) is preferably 0.5at% to 3.0at%, more preferably 2.0at% to 3.0at%, for example 2.69at%.
In the present invention, the main phase outer layer may include a light rare earth element RL 2 Said light rare earth element RL 2 Including a high abundance of rare earth element RE 2 。
In the outer layer of the main phase, the light rare earth element RL 2 Preferably comprising Pr and/or Nd. The light rare earth element RL 2 The atomic percentage of (B) is preferably 9.0at% to 10.0at%, for example 9.91at%.
In the present invention, the highly abundant rare earth element RE in the center of the main phase 1 And a high abundance rare earth element RE in the outer layer of the main phase 2 May independently comprise one or more of La, ce, Y, er, yb, gd, tm, and Sm; preferably Y, yb, gd, tm or Sm.
In the invention, in the outer layer of the main phase, the abundant rare earth element RE 2 The atomic percentage of (b) is preferably 0.5at% to 3.0at%, more preferably 2.0at% to 3.0at%, for example 2.28at%.
In the present invention, the average diameter of the main phase is R, preferably 2 μm < R <15 μm.
In the present invention, the average diameter of the center of the main phase is r 1 The average thickness of the main phase outer layer is r 2 ，r 1 /r 2 Preferably 2 to 4, for example 3.
In the invention, the average thickness of the main phase epitaxial layer is r 3 ，r 3 Preferably from 100 to 400nm, for example from 200 to 300nm.
In the main phase epitaxial layer, the heavy rare earth element RH preferably includes Dy and/or Tb.
In the main phase epitaxial layer, the content of the heavy rare earth element RH is preferably 2.5wt%; the percentage is the mass percentage of the heavy rare earth element RH in the magnetic steel containing the high-abundance rare earth element.
In the invention, the magnetic steel containing the high-abundance rare earth element generally also comprises a grain boundary phase. The grain boundary phase may be conventional in the art. Preferably, the grain boundary phase comprises elements such as Fe, al, cu, ga, zr, ti, B and the like.
In the invention, the anisotropic fields of the main phase epitaxial layer, the main phase center and the main phase outer layer are reduced in sequence.
The fourth technical scheme of the invention is as follows: the magnetic steel containing the high-abundance rare earth element is applied to an electronic component in a motor.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
in the magnetic steel containing the high-abundance rare earth element, the content of the high-abundance rare earth element in the center of the main phase can be higher than that of the high-abundance rare earth element in the outer layer of the main phase, and the magnetic performance of the magnetic steel is better; meanwhile, the main phase outer layer and the main phase epitaxial layer in the main phase of the magnetic steel containing the high-abundance rare earth elements can form a composite magnetic hardening shell layer, so that the magnetic performance of the magnetic steel is improved, and the utilization rate of the heavy rare earth elements is improved.
According to the micro-magnetic theory, impurities or defects on the surface of the crystal grains make the surface of the crystal grains more susceptible to demagnetization, thereby causing the entire crystal grains to be demagnetized, and the areas closer to the surface of the crystal grains are more susceptible to demagnetization. In order to enhance the demagnetization resistance and improve the coercive force of the magnet, the surface area of the crystal grain needs to be magnetically strengthened. The magnetic steel containing the high-abundance rare earth elements has the advantages that the demagnetization resistance from the center to the surface of the main phase crystal grains is gradually weakened, but the composite magnetic hardening shell layer with the gradually improved magnetic hardening strength of the center, the outer layer and the epitaxial layer of the main phase crystal grains can improve the demagnetization resistance of the crystal grains and simultaneously keep the cost optimization.
Drawings
Fig. 1 is a schematic diagram of the main phase structure of the magnetic steel containing the high-abundance rare earth element in embodiments 1 to 10.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
The preparation method of the Y-containing magnetic steel in the embodiment 1 is as follows:
the general formula of the main phase raw material of the Y-containing permanent magnet is as follows according to atom percentage: (Y) 0.1 PrNd 0.9 ) 13.64 Fe 79.26 Al 0.24 Cu 0.2 Ga 0.36 Zr 0.26 Ti 0.27 B 5.75 . Placing the prepared raw materials into a crucible made of alumina, and smelting in a high-frequency vacuum induction smelting furnace at a temperature of 5 x 10 -2 Vacuum melting is carried out at a temperature of 1500 ℃ or lower in a vacuum of Pa. After vacuum meltingAfter Ar gas was introduced into the melting furnace to make the gas pressure reach 5.5 ten thousand Pa, the casting was carried out at 10 degrees 2 DEG C/sec-10 4 The cooling speed of DEG C/second obtains the quenched main phase alloy.
Dy is the composition of the grain boundary auxiliary alloy 50 Fe 40 Cu 5 Al 5 (at.%) preparing raw materials according to the composition of said crystal boundary alloy, heating and melting by vacuum medium-frequency induction smelting furnace under the protection of argon gas, and heating to 10 deg.C 2 DEG C/sec-10 4 The cooling speed of DEG C/second obtains the quenched grain boundary auxiliary phase alloy.
Mixing the main phase alloy and the grain boundary auxiliary phase alloy according to the weight ratio of 98:2, and mixing uniformly.
Hydrogen crushing and crushing: putting the alloy into a hydrogen breaking furnace, introducing hydrogen with the purity of 99.9% into the hydrogen breaking furnace, maintaining the hydrogen pressure at 0.15MPa, fully absorbing the hydrogen, vacuumizing while heating, fully dehydrogenating, cooling, and taking out the powder after hydrogen breaking and crushing.
A micro-grinding process: the powder after hydrogen crushing was pulverized by jet milling for 3 hours under a nitrogen atmosphere having an oxidizing gas content of 150ppm or less at a pressure in the pulverization chamber of 0.38MPa to obtain a fine powder. The oxidizing gas refers to oxygen or moisture.
Adding zinc stearate into the powder crushed by the jet mill, wherein the addition amount of the zinc stearate is 0.12 percent of the weight of the mixed powder, and fully mixing the zinc stearate and the mixed powder by using a V-shaped mixer.
Magnetic field forming process: using a magnetic field forming machine of a perpendicular orientation type, in an orientation magnetic field of 1.6T, at 0.35ton/cm 2 The zinc stearate-added powder was once formed into a cube with a side length of 25mm under the molding pressure of (1), and was demagnetized in a magnetic field of 0.2T after the primary molding. The molded article obtained after the primary molding was sealed so as not to contact air, and then subjected to secondary molding (isostatic pressing) at 1.3ton/cm 2 Is subjected to secondary forming under pressure.
And (3) sintering: the molded bodies were transferred to a sintering furnace and sintered at 5X 10 -3 Pa at 300 deg.C and 600 deg.C for 1 hr, and sintering at 1080 deg.C for 4 hrThen, ar gas was introduced so that the pressure became 0.1MPa, and then the mixture was cooled to room temperature.
After preparing the sintered body, performing grain boundary diffusion to process the sintered body into a magnet with a diameter of 20mm and a sheet thickness of less than 7mm, wherein the thickness direction is a magnetic field orientation direction, cleaning the surface, and then using Dy alloy to prepare alloy powder (Dy) 70 Cu 15 Al 15 ) The magnet was spray coated on the entire surface, the coated magnet was dried, alloy powder of Dy element was attached to the surface of the magnet in an Ar gas atmosphere of high purity, and diffusion heat treatment was carried out at 900 ℃ for 24 hours. And cooling to room temperature. Aging heat treatment is carried out on the diffused magnet, the heat treatment temperature is 500 ℃, and the heat treatment time is 4 hours
Example 2
The preparation method of the Y-containing magnetic steel in the embodiment 1 is as follows:
the general formula of the main phase raw material of the Y-containing permanent magnet is as follows by atomic percentage: (Y) 0.1 PrNd 0.9 ) 13.64 Fe 79.26 Al 0.24 Cu 0.2 Ga 0.36 Zr 0.26 Ti 0.27 B 5.75 . Placing the prepared raw materials into a crucible made of alumina, and smelting in a high-frequency vacuum induction smelting furnace at a temperature of 5 x 10 -2 Vacuum melting is carried out at a temperature of 1500 ℃ or lower in vacuum of Pa. Ar gas is introduced into a melting furnace after vacuum melting to make the gas pressure reach 5.5 ten thousand Pa, and then casting is carried out at 10 degrees 2 DEG C/sec-10 4 The cooling speed of DEG C/second obtains the quenched main phase alloy.
The composition of the grain boundary auxiliary alloy is Pr 50 Fe 40 Cu 5 Al 5 (at.%) preparing raw materials according to the composition of said crystal boundary alloy, heating and melting by vacuum medium-frequency induction smelting furnace under the protection of argon gas, and heating to 10 deg.C 2 DEG C/sec-10 4 The cooling speed of DEG C/second obtains the quenched grain boundary auxiliary phase alloy.
Mixing the main phase alloy and the grain boundary auxiliary phase alloy according to the weight ratio of 98:2, the mixture is uniformly mixed.
Hydrogen crushing and crushing: putting the alloy into a hydrogen breaking furnace, introducing hydrogen with the purity of 99.9% into the hydrogen breaking furnace, maintaining the hydrogen pressure at 0.15MPa, fully absorbing the hydrogen, vacuumizing while heating, fully dehydrogenating, cooling, and taking out the powder after hydrogen breaking and crushing.
A micro-grinding process: the powder after hydrogen crushing was pulverized by jet milling for 3 hours under a nitrogen atmosphere having an oxidizing gas content of 150ppm or less at a pressure in the pulverization chamber of 0.38MPa to obtain a fine powder. The oxidizing gas refers to oxygen or moisture.
Adding zinc stearate into the powder crushed by the jet mill, wherein the adding amount of the zinc stearate is 0.12 percent of the weight of the mixed powder, and then fully mixing the zinc stearate and the mixed powder by using a V-shaped mixer.
Magnetic field forming process: using a magnetic field forming machine of a perpendicular orientation type, in an orientation magnetic field of 1.6T, at 0.35ton/cm 2 The powder added with zinc stearate was once formed into a cube with a side length of 25mm under the molding pressure of (1), and was once formed and then demagnetized in a magnetic field of 0.2T. The molded article after the primary molding was sealed so as not to contact air, and then subjected to secondary molding (isostatic pressing) at 1.3ton/cm 2 Secondary forming is performed under pressure of (1).
And (3) sintering: the molded bodies were transferred to a sintering furnace and sintered at 5X 10 -3 Pa at 300 deg.C and 600 deg.C for 1 hr, sintering at 1080 deg.C for 4 hr, introducing Ar gas to make the pressure reach 0.1MPa, and cooling to room temperature.
After preparing the sintered body, performing grain boundary diffusion to process the sintered body into a magnet with a diameter of 20mm and a sheet thickness of less than 7mm, wherein the thickness direction is a magnetic field orientation direction, cleaning the surface, and then using Dy alloy to prepare alloy powder (Dy) 70 Cu 15 Al 15 ) The magnet was spray coated on the entire surface, the coated magnet was dried, alloy powder of Dy element was attached to the surface of the magnet in an Ar gas atmosphere of high purity, and diffusion heat treatment was carried out at 900 ℃ for 24 hours. And cooling to room temperature. Aging heat treatment is carried out on the diffused magnet, the heat treatment temperature is 500 ℃, and the heat treatment time is 4 hours
Example 3
Example 3 sintered body raw material composition containing Y magnetic steelThe percentage is as follows: (Y) 0.05 Pr 0.18 Nd 0.57 ) 13.64 Fe 78.88 Al 0.24 Cu 0.2 Ga 0.36 Zr 0.26 Ti 0.27 B 5.75 ；
The rest of the procedure was the same as in example 1.
Example 4
In example 4, the raw material composition of the sintered body containing La magnetic steel is, in atomic percent: (La) 0.1 Pr 0.22 Nd 0.68 ) 13.6 4 Fe 79.48 Al 0.24 Cu 0.2 Ga 0.36 Zr 0.26 Ti 0.27 B 5.75 ；
The rest of the procedure was the same as in example 1.
Example 5
In example 5, the Ce magnetic steel-containing sintered body raw material composition comprises, in atomic percent: (Ce) 0.1 Pr 0.22 Nd 0.68 ) 13.6 4 Fe 79.48 Al 0.24 Cu 0.2 Ga 0.36 Zr 0.26 Ti 0.27 B 5.75 ；
The rest was the same as in example 1.
Example 6
In example 6, the raw material composition of the sintered body containing Yb magnetic steel is, in atomic percent: (Yb) 0.1 Pr 0.22 Nd 0.68 ) 13.6 4 Fe 79.48 Al 0.24 Cu 0.2 Ga 0.36 Zr 0.26 Ti 0.27 B 5.75 ；
The rest was the same as in example 1.
Example 7
In example 7, the raw material composition of the sintered body containing Tm magnetic steel is, in atomic percent: (Tm) 0.1 Pr 0.22 Nd 0.68 ) 13.6 4 Fe 79.48 Al 0.24 Cu 0.2 Ga 0.36 Zr 0.26 Ti 0.27 B 5.75 ；
The rest was the same as in example 1.
Example 8
In example 8, the raw material composition of the sintered body containing Gd magnetic steel is, in atomic percent: (Gd) 0.1 Pr 0.22 Nd 0.68 ) 13.6 4 Fe 79.48 Al 0.24 Cu 0.2 Ga 0.36 Zr 0.26 Ti 0.27 B 5.75 ；
The rest of the procedure was the same as in example 1.
Example 9
In example 9, the composition of the raw material of the sintered body containing Sm magnetic steel is, in atomic percent: (Sm) 0.1 Pr 0.22 Nd 0.68 ) 13.6 4 Fe 79.48 Al 0.24 Cu 0.2 Ga 0.36 Zr 0.26 Ti 0.27 B 5.75 ；
The rest was the same as in example 1.
Example 10
In example 10, the raw material composition of the sintered body containing Er magnetic steel is, in atomic percent: (Er) 0.1 Pr 0.22 Nd 0.68 ) 13.64 Fe 79.48 Al 0.24 Cu 0.2 Ga 0.36 Zr 0.26 Ti 0.27 B 5.75 ；
The rest of the procedure was the same as in example 1.
Comparative example 1
In comparative example 1, the raw material composition of the sintered body containing the Y magnetic steel is as follows by atomic percent: (Y) 0.1 Pr 0.22 Nd 0.68 ) 13.64 Fe 79.48 Al 0.24 Cu 0.2 Ga 0.36 Zr 0.26 Ti 0.27 B 5.75 Dy is used as the diffusion source raw material composition in atomic percentage 30 Fe 40 Cu 15 Al 15 ；
The rest of the procedure was the same as in example 1.
Comparative example 2
In comparative example 2, the raw material composition of the sintered body containing the Y magnetic steel comprises the following components in atomic percentage: (Y) 0.4 Pr 0.18 Nd 0.57 ) 13.64 Fe 79.48 Al 0.24 Cu 0.2 Ga 0.36 Zr 0.26 Ti 0.27 B 5.75 ；
The rest are the same as those in example 1
Comparative example 3
In comparative example 3, the raw material composition of the sintered body containing the Y magnetic steel is as follows by atomic percent: (Y) 0.1 Pr 0.22 Nd 0.68 ) 13.64 Fe 79.48 Al 0.24 Cu 0.2 Ga 0.36 Zr 0.26 Ti 0.27 B 5.75 (ii) a The temperature of the diffusion heat treatment is 800 ℃;
the rest of the procedure was the same as in example 1.
Effect example 1
1. Characterization of the microstructure
(1) The schematic structural diagram of the main phase in the magnetic steel containing high-abundance rare earth elements of examples 1 to 10 is shown in fig. 1.
(2) The magnetic steel containing the high-abundance rare earth elements in examples 1-2 was tested using a field emission electron probe microanalyzer EPMA surface distribution.
Measuring the average diameter R and the central diameter R of the main phase according to the EPMA surface distribution test result 1 Average thickness r of the outer layer of the main phase 2 And a main phase epitaxial layer, the specific method is as follows:
combining a system scale in the EPMA surface distribution test result and software of 'version 1.2 of particle size distribution calculation', measuring the average diameter R of the main phase and the average diameter R of the center of the main phase 1 The number of the measured grains is respectively 20, the sizes of the larger direction and the smaller direction of each grain are respectively measured due to the irregular shape of the grains, and the average value is calculated to obtain the average diameter R of the main phase and the average diameter R of the center of the main phase 1 The results are shown in Table 1 below.
Average thickness r of the outer layer of the main phase 2 Can pass through the average diameter R of the main phase and the average diameter R of the center of the main phase 1 The calculation specifically comprises the following steps: average thickness r of the outer layer of the main phase 2 = (mean diameter of major phase R-mean diameter of major phase center R 1 )/2。r 2 The results are shown in Table 1 below.
According to the EPMA surface distribution test result, the thickness of the Dy shell layer in the Dy surface distribution can be obtained, and the average thickness r of the main phase epitaxial layer can be calculated according to the thickness of the Dy shell layer 3 The method specifically comprises the following steps: average thickness r of main phase epitaxial layer 3 = shell thickness/2 of Dy in Dy plane distribution. r is 3 The results are shown in Table 1 below.
TABLE 1
2. Characterization of magnetic Properties
The magnetic properties of the magnetic steels containing the high-abundance rare earth elements in examples 1-2 before and after diffusion were respectively tested by using a permanent magnet material test system NIM-62000, and the test results are shown in table 2 below.
TABLE 2
As can be seen from the above table, the magnetic steels containing high-abundance rare earth elements prepared in examples 1 to 10 have excellent remanence, coercive force, maximum magnetic energy product, and squareness effect.
Comparative example 1a sintered body raw material composition containing Y alnico in which the atomic percent of Pr (0.22 at%) and the atomic percent of Nd (0.68 at%) are out of the ranges claimed in the present application, r is r in the microstructure of the alnico produced 1 /r 2 The coercive force, the maximum magnetic energy and the squareness effect of the magnetic steel are obviously poorer than those of the magnetic steel in the embodiment 1.
Comparative example 2a sintered body raw material composition containing Y alnico in which the atomic percent of Y (0.4 at%), pr (0.18 at%) and Nd (0.57 at%) are out of the ranges claimed herein, produced an alnico microstructure in which r is in the range 1 /r 2 The coercive force, the maximum magnetic energy and the squareness effect of the magnetic steel are obviously poorer than those of the magnetic steel in the embodiment 1.
Comparative example 3 containing YIn the raw material composition of sintered body of magnetic steel, the atomic percent of Pr (0.22 at%) and Nd (0.68 at%) are out of the range claimed in the application, and the microstructure of the magnetic steel is obtained by that r 1 /r 2 The coercive force, the maximum magnetic energy product and the squareness effect of the magnetic steel are obviously poorer than those of the embodiment 1.
Claims (10)
1. A preparation method of magnetic steel containing high-abundance rare earth elements is characterized by comprising the following steps:
(1) Mixing the powder of the main alloy and the powder of the auxiliary alloy, and crushing, molding and sintering the mixture to obtain the alloy;
wherein the composition of the main alloy is (RE) a Pr b Nd c ) d Fe e Al f Cu g Ga h Zr i Ti j B k ；
RE is a high-abundance rare earth element; RE comprises one or more of La, ce, Y, er, yb, gd, tm and Sm;
in atomic percentage: a is 0.05 to 0.3; b is 0.1 to 1.2; c is 0.5 to 0.9; d is 13 to 15; e is 78 to 80; f is 0.2 to 0.4; g is 0.1 to 0.3; h is 0.2 to 0.5; i is 0.2 to 0.4; j is 0.2 to 0.4; k is 5to 6;
wherein the composition of the auxiliary alloy is R m Fe n Cu o Al p ；
R is a rare earth element;
in atomic percentage: m is 45 to 55; n is 35to 45; o is 4 to 8; p is 4 to 8;
(2) Performing grain boundary diffusion treatment on the sintered body obtained in the step (1) and the diffusion source raw material composition;
wherein, the content of the heavy rare earth element in the diffusion source raw material composition is more than m in atomic percentage.
2. The method for preparing magnetic steel containing abundant rare earth elements according to claim 1, wherein the method for preparing magnetic steel containing abundant rare earth elements satisfies one or more of the following conditions (i) to (vi):
(i) In the composition of the main alloy, RE comprises Y;
(ii) The composition of the main alloy comprises the following components in atomic percentage: a is 0.1;
b is preferably 0.18 to 1, more preferably 0.22 to 0.9;
c is preferably 0.55 to 0.8, more preferably 0.57 to 0.68;
d is preferably 13 to 14, more preferably 13.64;
e is preferably from 78.5 to 80, more preferably from 78.88 to 79.48, and still more preferably 79.26;
f is preferably 0.2 to 0.3, more preferably 0.24;
g is preferably 0.2;
h is preferably 0.3 to 0.4, more preferably 0.36;
i is preferably 0.2 to 0.3, more preferably 0.26;
j is preferably 0.2 to 0.3, more preferably 0.27;
k is preferably 5.5 to 6, more preferably 5.75;
(iii) The composition of the main alloy is (Y) 0.1 PrNd 0.9 ) 13.64 Fe 79.26 Al 0.24 Cu 0.2 Ga 0.36 Zr 0.26 Ti 0.27 B 5.75 (ii) a Or (Y) 0.05 Pr 0.18 Nd 0.57 ) 13.64 Fe 78.88 Al 0.24 Cu 0.2 Ga 0.36 Zr 0.26 Ti 0.27 B 5.75 (ii) a Or (La) 0.1 Pr 0.22 Nd 0.68 ) 13.64 Fe 79.48 Al 0.24 Cu 0.2 Ga 0.36 Zr 0.26 Ti 0.27 B 5.75 (ii) a Or, (Ce) 0.1 Pr 0.22 Nd 0.68 ) 13.64 Fe 79.48 Al 0.24 Cu 0.2 Ga 0.36 Zr 0.26 Ti 0.27 B 5.75 (ii) a Or, (Yb) 0.1 Pr 0.22 Nd 0.68 ) 13.64 Fe 79.48 Al 0.24 Cu 0.2 Ga 0.36 Zr 0.26 Ti 0.27 B 5.75 (ii) a Or, (Tm) 0.1 Pr 0.22 Nd 0.68 ) 13.64 Fe 79.48 Al 0.24 Cu 0.2 Ga 0.36 Zr 0.26 Ti 0.27 B 5.75 (ii) a Or (Gd) 0.1 Pr 0.22 Nd 0.68 ) 13.64 Fe 79.48 Al 0.24 Cu 0.2 Ga 0.36 Zr 0.26 Ti 0.27 B 5.75 (ii) a Or (Sm) 0.1 Pr 0.22 Nd 0.68 ) 13.64 Fe 79.48 Al 0.24 Cu 0.2 Ga 0.36 Zr 0.26 Ti 0.27 B 5.75 ；
(iv) In the composition of the auxiliary alloy, R is Dy or Pr;
(v) The composition of the secondary alloy comprises the following components in atomic percentage: m is 50; n is 40; o is 5; p is 5;
(vi) The auxiliary alloy consists of Dy 50 Fe 40 Cu 5 Al 5 Or Pr 50 Fe 40 Cu 5 Al 5 ；
Preferably, the preparation method of the magnetic steel containing the high-abundance rare earth element simultaneously satisfies the conditions (i) to (vi).
3. The method for preparing magnetic steel containing abundant rare earth elements according to claim 1, wherein the method for preparing magnetic steel containing abundant rare earth elements satisfies one or more of the following conditions I to VIII:
I. in the step (1), the mass ratio of the powder of the main alloy to the powder of the auxiliary alloy is (90-99): (10-1), preferably 98:2;
II. In the step (1), the crushing process comprises hydrogen crushing and micro crushing;
wherein, the hydrogen crushing is preferably performed by hydrogen absorption, dehydrogenation and cooling treatment;
wherein, the micro-crushing is preferably jet mill crushing;
the jet mill pulverization is preferably carried out in a nitrogen atmosphere having an oxidizing gas content of 150ppm or less;
the pressure of a crushing chamber for crushing by the jet mill is preferably 0.38MPa;
the jet mill is used for crushing for 3 hours;
III, in the step (1), the molding process is a magnetic field molding method or a hot-pressing thermal deformation method;
the magnetic field intensity of the magnetic field forming method is preferably 1.5T or more, for example, 1.6T;
IV, in the step (1), the sintering process comprises preheating, sintering and cooling under a vacuum condition;
wherein the preheating temperature is preferably 300-600 ℃; the preheating time is preferably 1-2 h; more preferably, the preheating is preheating for 1h at the temperature of 300 ℃ and 600 ℃ respectively;
wherein the sintering temperature is preferably 1080-1090 ℃;
wherein the sintering time is preferably 4h;
v, in the step (2), the diffusion source raw material composition is alloy powder containing heavy rare earth elements;
wherein the heavy rare earth element preferably comprises Dy and/or Tb;
the atomic percentage of the heavy rare earth element is preferably 50 to 80at%; more preferably 60 to 70at%;
VI, in the step (2), the diffusion source raw material composition further comprises M; the M preferably comprises one or more of Al, cu and Ga; more preferably Al and Cu;
wherein, the atomic percentage of M is preferably 20 to 50at%; more preferably 30 to 40at%;
when said M comprises Cu, the atomic percentage of said Cu is preferably from 10 to 25at%; more preferably 15 to 20at%;
when said M comprises Al, the atomic percent of said Al is preferably 10 to 25at%; more preferably 15 to 20at%;
VII, in the step (2), dy is used as the diffusion source raw material composition 70 Cu 15 Al 15 ；
VIII, the mass ratio of the sintered body obtained in the step (1) to the diffusion source raw material composition is (98-99.5): (0.5 to 2), preferably 99.2:0.8;
preferably, the preparation method of the magnetic steel containing the high-abundance rare earth element simultaneously meets the conditions I to VIII.
4. The method for preparing magnetic steel containing abundant rare earth elements according to claim 1, wherein the method for preparing magnetic steel containing abundant rare earth elements satisfies one or more of the following conditions IX to XII:
IX, in the step (2), the grain boundary diffusion is carried out in a high-purity Ar gas atmosphere; the pressure of the high-purity Ar gas atmosphere is preferably 8X 10 -3 Pa～2×10 5 Pa；
X, in the step (2), the temperature of the grain boundary diffusion is 800-980 ℃, such as 900 ℃;
XI, in the grain boundary diffusion, the time of the grain boundary diffusion is 12-30 h, preferably 15-28 h; for example 24h;
XII, in the step (2), after the grain boundary diffusion, further comprising diffusion heat treatment and/or aging heat treatment;
wherein the temperature of the diffusion heat treatment is preferably 850-950 ℃, such as 900 ℃; the time of the aging heat treatment is preferably 20 to 40 hours, such as 24 hours;
wherein the temperature of the aging heat treatment is preferably 440-580 ℃, for example 500 ℃; the time of the aging heat treatment is preferably 2 to 4 hours, for example 4 hours;
preferably, the preparation method of the magnetic steel containing the high-abundance rare earth element simultaneously meets the conditions IX to XII.
5. The method for preparing magnetic steel containing abundant rare earth elements according to claim 1, wherein the powder of the main alloy is prepared by the following method: mixing the RE, the Pr, the Nd, the Fe, the Al, the Cu, the Ga, the Zr, the Ti and the B according to a ratio, and smelting and casting to obtain the alloy material;
wherein, the smelting is preferably a high-frequency vacuum induction smelting furnace; the degree of vacuum of the melting is preferably 5X 10 -2 Pa; the melting temperature is preferably 1500 ℃ or lower；
Wherein the casting is preferably performed in an Ar gas atmosphere at 10 deg.C 2 DEG C/sec-10 4 Cooling at a rate of DEG C/sec.
6. The method for preparing magnetic steel containing abundant rare earth elements according to claim 1, wherein the powder of the secondary alloy is prepared by the following method: mixing the R, the Fe, the Cu and the Al according to a ratio, heating and melting by a vacuum induction melting furnace under the protection of argon gas, and melting by a vacuum induction melting furnace at a temperature of 10 DEG C 2 DEG C/sec-10 4 The speed is measured at the temperature of DEG C/second.
7. Magnetic steel containing high-abundance rare earth elements is characterized by being prepared by the preparation method of the magnetic steel containing high-abundance rare earth elements according to any one of claims 1 to 6.
8. The magnetic steel containing the high-abundance rare earth element is characterized in that a main phase of the magnetic steel containing the high-abundance rare earth element comprises a main phase center, a main phase outer layer and a main phase epitaxial layer; the main phase outer layer is positioned outside the main phase center and completely covers the main phase center; the main phase epitaxial layer is positioned on the outer side of the main phase outer layer and completely covers the main phase outer layer;
wherein the rare earth element RE with high abundance in the center of the main phase 1 In an amount of A 1 at%, at% refers to the atomic percentage of the high-abundance rare earth element in the center of the main phase in the magnetic steel containing the high-abundance rare earth element;
high abundance rare earth element RE in the outer layer of the main phase 2 In an amount of A 2 at percent, at percent refers to the atomic percentage of the high-abundance rare earth element in the outer layer of the main phase in the magnetic steel containing the high-abundance rare earth element;
A 1 at％＞A 2 at％；
wherein the average diameter of the center of the main phase is r 1 The average thickness of the main phase outer layer is r 2 ，1<r 1 /r 2 <5；
Wherein the main phase is epitaxialThe layer comprises a heavy rare earth element RH; the average thickness of the main phase epitaxial layer is r 3 ，2nm<r 3 <500nm。
9. The magnetic steel containing a high abundance rare earth element according to claim 8, wherein said magnetic steel containing a high abundance rare earth element satisfies one or more of conditions (1) to (r):
(1) the main phase center comprises a light rare earth element RL 1 The light rare earth element RL 1 Including a high abundance of rare earth element RE 1 ；
In the center of the main phase, the light rare earth element RL 1 Preferably comprising Pr and/or Nd; the light rare earth element RL 1 Is preferably from 9.0at% to 10.0at%, for example 9.63at%;
(2) in the core of the main phase, the abundant rare earth element RE 1 The atomic percentage of (b) is 0.5at% to 3.0at%, preferably 2.0at% to 3.0at%, for example 2.69at%;
(3) the main phase outer layer comprises a light rare earth element RL 2 The light rare earth element RL 2 Including a high abundance of rare earth element RE 2 ；
In the outer layer of the main phase, the light rare earth element RL 2 Preferably comprising Pr and/or Nd; the light rare earth element RL 2 Is preferably 9.0at% to 10.0at%, for example 9.91at%;
(4) a high abundance rare earth element RE in the center of the main phase 1 And a high abundance rare earth element RE in the outer layer of the main phase 2 Independently comprise one or more of La, ce, Y, er, yb, gd, tm, and Sm; preferably Y, yb, gd, tm or Sm;
(5) in the outer layer of the main phase, the abundant rare earth element RE 2 Is 0.5at% to 3.0at%, preferably 2.0at% to 3.0at%, for example 2.28at%;
(6) the average diameter of the main phase is R,2 μm < R <15 μm;
preferably, the mean diameter of the center of the main phase is r 1 The outer layer of the main phaseHas an average thickness of r 2 ，r 1 /r 2 2 to 4, such as 3;
(7) the average thickness of the main phase epitaxial layer is r 3 ，r 3 From 100 to 400nm, for example from 200 to 300nm;
(8) in the main phase epitaxial layer, the heavy rare earth element RH comprises Dy and/or Tb;
in the main phase epitaxial layer, the content of the heavy rare earth element RH is preferably 2.5wt%; the percentage is the mass percentage of the heavy rare earth element RH to the magnetic steel containing the high-abundance rare earth element;
(9) the magnetic steel containing the high-abundance rare earth element also comprises a grain boundary phase; the grain boundary phase preferably comprises Fe, al, cu, ga, zr, ti and B;
the anisotropy fields of R, the main phase epitaxial layer, the main phase center and the main phase outer layer are sequentially reduced;
preferably, said magnetic steel containing rich rare earth element simultaneously satisfies conditions (1) to (r).
10. Use of a magnetic steel containing a high-abundance rare earth element as an electronic component in a motor, wherein the magnetic steel containing a high-abundance rare earth element is as defined in any one of claims 6 to 9.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211543719.0A CN115798850A (en) | 2022-11-30 | 2022-11-30 | Magnetic steel containing high-abundance rare earth elements and preparation method and application thereof |
| PCT/CN2023/090162 WO2024113657A1 (en) | 2022-11-30 | 2023-04-23 | Magnetic steel containing high-abundance rare earth elements, preparation method therefor, and use thereof |
Applications Claiming Priority (1)
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| CN202211543719.0A CN115798850A (en) | 2022-11-30 | 2022-11-30 | Magnetic steel containing high-abundance rare earth elements and preparation method and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024113657A1 (en) * | 2022-11-30 | 2024-06-06 | 福建省金龙稀土股份有限公司 | Magnetic steel containing high-abundance rare earth elements, preparation method therefor, and use thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105170976A (en) * | 2015-10-23 | 2015-12-23 | 北京科技大学 | Method for preparing high-coercivity neodymium iron boron by means of low-temperature sintering after blank compacting permeation |
| CN107958760B (en) * | 2016-10-17 | 2020-02-14 | 中国科学院宁波材料技术与工程研究所 | Rare earth permanent magnetic material and preparation method thereof |
| CN107578870B (en) * | 2017-09-13 | 2019-03-12 | 内蒙古科技大学 | A method of permanent-magnet material is prepared using high abundance rare earth element |
| CN115798850A (en) * | 2022-11-30 | 2023-03-14 | 福建省长汀金龙稀土有限公司 | Magnetic steel containing high-abundance rare earth elements and preparation method and application thereof |
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- 2022-11-30 CN CN202211543719.0A patent/CN115798850A/en active Pending
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2024113657A1 (en) * | 2022-11-30 | 2024-06-06 | 福建省金龙稀土股份有限公司 | Magnetic steel containing high-abundance rare earth elements, preparation method therefor, and use thereof |
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| WO2024113657A1 (en) | 2024-06-06 |
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Address after: 366300 new industrial zone, Changting Economic Development Zone, Longyan City, Fujian Province Applicant after: Fujian Jinlong Rare Earth Co.,Ltd. Address before: 366300 new industrial zone, Changting Economic Development Zone, Longyan City, Fujian Province Applicant before: FUJIAN CHANGTING GOLDEN DRAGON RARE-EARTH Co.,Ltd. |