CN115359988A - High-performance cerium-containing rare earth permanent magnet and preparation method thereof - Google Patents
High-performance cerium-containing rare earth permanent magnet and preparation method thereof Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 49
- 229910052684 Cerium Inorganic materials 0.000 title claims abstract description 47
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 42
- 239000000956 alloy Substances 0.000 claims abstract description 42
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000004678 hydrides Chemical class 0.000 claims abstract description 3
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 65
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 60
- 238000005245 sintering Methods 0.000 claims description 46
- 230000032683 aging Effects 0.000 claims description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims description 36
- 238000004321 preservation Methods 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 34
- 239000001257 hydrogen Substances 0.000 claims description 34
- 229910052757 nitrogen Inorganic materials 0.000 claims description 32
- 238000000227 grinding Methods 0.000 claims description 30
- 238000003723 Smelting Methods 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 238000005266 casting Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000000748 compression moulding Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 230000006698 induction Effects 0.000 claims description 10
- 238000000462 isostatic pressing Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 229910000568 zirconium hydride Inorganic materials 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- -1 hydride Chemical compound 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000013078 crystal Substances 0.000 abstract description 7
- 238000013461 design Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 230000002411 adverse Effects 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 4
- 238000005204 segregation Methods 0.000 abstract description 4
- 239000012071 phase Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 11
- 229910052779 Neodymium Inorganic materials 0.000 description 5
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 5
- QSGNKXDSTRDWKA-UHFFFAOYSA-N zirconium dihydride Chemical group [ZrH2] QSGNKXDSTRDWKA-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 229910052777 Praseodymium Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910001172 neodymium magnet Inorganic materials 0.000 description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 3
- 239000007790 solid phase Substances 0.000 description 3
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
- H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
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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
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0573—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes obtained by reduction or by hydrogen decrepitation or embrittlement
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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
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
- H01F1/0576—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together pressed, e.g. hot working
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- 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
- H01F41/0253—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 for manufacturing permanent magnets
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- 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
- H01F41/0253—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 for manufacturing permanent magnets
- H01F41/0266—Moulding; Pressing
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- Powder Metallurgy (AREA)
Abstract
The invention relates to a high-performance cerium-containing rare earth permanent magnet and a preparation method thereof, wherein the high-performance cerium-containing rare earth permanent magnet comprises a master alloy and a crystal boundary addition alloy; wherein the master alloy comprises the following components: (R, ce, dy) a Fe b M c B d (ii) a The grain boundary addition alloy is at least one of an oxide and a hydride of zirconium. The formula design of the invention can improve and strengthen the grain boundary of the cerium-containing rare earth permanent magnet, inhibit the adverse effect caused by cerium distribution segregation, and refine crystal grains, thereby being capable of preparing the high-performance cerium-containing rare earth permanent magnet.
Description
Technical Field
The invention belongs to the field of permanent magnet materials, and particularly relates to a high-performance cerium-containing rare earth permanent magnet and a preparation method thereof.
Background
The cerium-containing rare earth permanent magnet material is a hotspot of the research in the field of rare earth permanent magnet materials in recent years in China, and the rare earth element cerium with high abundance and low cost is used for replacing the rare earth element praseodymium and neodymium in the neodymium-iron-boron rare earth permanent magnet, so that the cost of the neodymium-iron-boron rare earth permanent magnet can be reduced, the rare earth resources in China can be comprehensively utilized, and the balanced utilization of the rare earth elements is realized, thereby having important strategic position and function. Ce in rare earth permanent magnet 2 Fe 14 B has lower saturation magnetic polarization strength and lower anisotropy field than Nd 2 Fe 14 And B, the residual magnetism and the coercive force of the rare earth permanent magnet prepared by cerium replacing praseodymium and neodymium are reduced, so that the cerium-containing rare earth permanent magnet in the industry can only be used for preparing a magnet with low magnetic energy product and low coercive force at present.
Cerium-containing rare earth permanent magnet prepared by rare earth element cerium replacing praseodymium and neodymium, and microstructure thereofThe phase composition of (1) is the main phase ((NdCe) 2 Fe 14 B) Crystal boundary phase (CeFe) 2 ) Boron-rich phase, which is different from the main phase (Nd) of the traditional neodymium iron boron 2 Fe 14 B) And a grain boundary phase (neodymium-rich phase), a boron-rich phase. In (NdCe) 2 Fe 14 The existence of cerium in the B main phase greatly reduces the melting point of the main phase, and solid phase sintering is easily generated in the sintering process, so that the coercive force is reduced. In addition, the crystal boundary phase is changed from the neodymium-rich phase to CeFe 2 And the heat treatment temperature is also greatly different from that of the prior art. Therefore, the development of a new heat treatment process for the cerium-containing rare earth permanent magnet is necessary.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a high-performance cerium-containing rare earth permanent magnet and a preparation method thereof, the formula design can improve and strengthen the grain boundary of the cerium-containing rare earth permanent magnet, inhibit the adverse effect caused by cerium distribution and segregation, and simultaneously can refine grains, and the optimal heat treatment process is adopted, so that the high-performance cerium-containing rare earth permanent magnet can be prepared.
The invention provides a high-performance cerium-containing rare earth permanent magnet, which comprises a master alloy and a crystal boundary addition alloy; wherein the master alloy comprises the following components: (R, ce, dy) a Fe b M c B d (ii) a R is one or more of other rare earth elements except Ce and Dy and must contain Nd, M is at least one of Al, si, ti, V, cr, mn, ni, co, cu, zn, ga, zr, nb, W, O, C, S, N and H elements, fe is an iron element and B is a boron element; the grain boundary addition alloy is at least one of an oxide and a hydride of zirconium.
The master alloy comprises the following components in percentage by mass: a is more than or equal to 29wt% and less than or equal to 33wt%, c is more than or equal to 0.1wt% and less than or equal to 3wt%, d is more than or equal to 0.9wt% and less than or equal to 1wt%, and the rest is b.
The mass percentage of the Ce in the master alloy is 1-10%.
The mass percentage of Dy in the master alloy is 0.1-0.5%.
The addition amount of the grain boundary addition alloy is 0.1-0.5%, and the average grain size is 1-10 um.
The invention provides a preparation method of a high-performance cerium-containing rare earth permanent magnet, which comprises the following steps:
(1) Proportioning the components, smelting by using a vacuum induction smelting furnace at 1400-1500 ℃, casting into a cast piece with the thickness of 0.1-0.5 mm, carrying out hydrogen crushing by using a hydrogen crushing furnace, wherein the hydrogen pressure of the hydrogen crushing reaction is 0.05-0.2 MPa, and crushing the cast piece into master alloy coarse powder;
(2) Adding at least one powder of zirconium oxide and hydride into the master alloy coarse powder, wherein the added mass percent is 0.1-0.5%;
(3) Grinding the coarse powder uniformly mixed in the step (2) into fine powder by adopting an airflow mill, wherein the grinding gas is nitrogen, the average particle size is controlled to be 2-5 mu m, and mixing the fine powder after grinding;
(4) And (4) carrying out magnetic field orientation and compression molding on the fine powder obtained from the step (3) and mixed uniformly in a press under the protection of nitrogen, carrying out isostatic pressing to obtain a pressed compact, then loading the pressed compact into a sintering furnace under the protection of nitrogen for high-temperature sintering, and finally carrying out heat treatment by adopting first-stage aging and second-stage aging.
The high-temperature sintering temperature in the step (4) is 1000-1080 ℃, the heat preservation time is 3-6 hours, and the temperature is continuously 10-15 ℃ higher than the sintering temperature after the heat preservation is finished, and the heat preservation time is 1-2 hours.
The temperature of the first stage aging heat treatment in the step (4) is 630-880 ℃, and the temperature is kept for 1-2 hours; the temperature of the second stage aging heat treatment is 400-620 ℃, and the heat preservation time is 3-6 hours.
The grain boundary addition alloy is zirconium hydride or oxide, and is prepared into powder by a known method.
Advantageous effects
(1) The formula design of the invention can improve and strengthen the grain boundary of the cerium-containing rare earth permanent magnet and inhibit the adverse effect caused by distribution segregation of cerium, thereby being capable of preparing the high-performance cerium-containing rare earth permanent magnet.
(2) The crystal boundary addition alloy is an innovative design aiming at the cerium-containing rare earth permanent magnet which is easy to carry out solid phase sintering in the sintering process, can inhibit the solid phase sintering, refine product crystal grains and further improve the coercive force of the magnet.
(3) The sintering and heat treatment process is a new process developed aiming at the new microstructure and phase composition of the cerium-containing rare earth permanent magnet, and can further improve the coercive force of the magnet.
(4) The magnetic performance requirements of the invention are as follows: (BH) max (MGOe) + Hcj (kOe) > 60, and has excellent performance.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
This example provides a high performance cerium-containing rare earth permanent magnet with Nd as a component 21.0 Pr 7.0 Ce 2.0 Dy 0.1 Co 0.3 Al 0.05 Cu 0.1 Ga 0.1 Nb 0.1 B 0.95 Fe 68.3 。
(1) Proportioning the components, smelting by using a vacuum induction smelting furnace at 1460-1480 ℃, casting into cast pieces with the average thickness of 0.28-0.30 mm, carrying out hydrogen crushing by using a hydrogen crushing furnace at the hydrogen pressure of 0.05-0.2 MPa, and crushing the cast pieces into master alloy coarse powder;
(2) Adding zirconium hydride ZrH into mother alloy coarse powder 2 Powder, the added mass percentage is 0.2%;
(3) Grinding the coarse powder uniformly mixed in the step (2) into fine powder by adopting an air flow mill, wherein the grinding gas is nitrogen, the average particle size is controlled to be 3.0-3.1 mu m, and mixing the fine powder after grinding;
(4) And (4) carrying out magnetic field orientation and compression molding on the fine powder obtained from the step (3) and mixed uniformly in a press under the protection of nitrogen, carrying out isostatic pressing to obtain a pressed compact, then loading the pressed compact into a sintering furnace under the protection of nitrogen for high-temperature sintering, and finally carrying out heat treatment by adopting first-stage aging and second-stage aging. The high-temperature sintering temperature is 1060 ℃, the heat preservation time is 4 hours, and the heat preservation is continuously carried out at the sintering temperature of 1070 ℃ for 1 hour after the heat preservation is finished. The temperature of the first-stage aging heat treatment is 840 ℃, and the temperature is kept for 1.5 hours; the temperature of the secondary aging heat treatment is 510 ℃, and the holding time is 4 hours.
Example 2
This example provides a high performance cerium-containing rare earth permanent magnet with Nd as a component 19.3 Pr 6.4 Ce 5.0 Dy 0.3 Co 0.5 Al 0.1 Cu 0.15 Ga 0.15 Ti 0.1 B 0.92 Fe 67.08 。
(1) Proportioning the components, smelting by using a vacuum induction smelting furnace at 1440-1460 ℃, casting into cast pieces with the average thickness of 0.25-0.27 mm, performing hydrogen crushing by using a hydrogen crushing furnace at the hydrogen pressure of 0.05-0.2 MPa, and crushing the cast pieces into master alloy coarse powder;
(2) Adding zirconium oxide ZrO into mother alloy coarse powder 2 The added mass percentage of the powder of (4) is 0.1%;
(3) Grinding the coarse powder uniformly mixed in the step (2) into fine powder by adopting an airflow mill, wherein the grinding gas is nitrogen, the average particle size is controlled to be 2.9-3.0 mu m, and mixing the fine powder after grinding;
(4) And (4) carrying out magnetic field orientation and compression molding on the fine powder obtained from the step (3) and mixed uniformly in a press under the protection of nitrogen, carrying out isostatic pressing to obtain a pressed compact, then loading the pressed compact into a sintering furnace under the protection of nitrogen for high-temperature sintering, and finally carrying out heat treatment by adopting first-stage aging and second-stage aging. The high-temperature sintering temperature is 1065 ℃, the heat preservation time is 3 hours, and the high-temperature sintering temperature is 1075 ℃ and the heat preservation time is 2 hours after the heat preservation is finished. The temperature of the first stage aging heat treatment is 820 ℃, and the temperature is kept for 2 hours; the temperature of the second stage aging heat treatment is 600 ℃, and the heat preservation time is 4 hours.
Example 3
This example provides a high performance cerium-containing rare earth permanent magnet with Nd as the component 20.7 Pr 6.8 Ce 3.0 Dy 0.5 Co 0.5 Al 0.3 Cu 0.15 Ga 0.15 Ti 0.1 B 0.91 Fe 66.89 。
(1) Proportioning the components, smelting by using a vacuum induction smelting furnace at 1440-1460 ℃, casting into cast pieces with the average thickness of 0.25-0.27 mm, carrying out hydrogen crushing by using a hydrogen crushing furnace, wherein the hydrogen pressure of the hydrogen crushing reaction is 0.05-0.2 MPa, and crushing the cast pieces into master alloy coarse powder;
(2) Adding zirconium hydride ZrH into mother alloy coarse powder 2 Powder, the added mass percentage is 0.4%;
(3) Grinding the coarse powder uniformly mixed in the step (2) into fine powder by adopting an air flow mill, wherein the grinding gas is nitrogen, the average particle size is controlled to be 2.9-3.0 mu m, and mixing the fine powder after grinding;
(4) And (4) carrying out magnetic field orientation and compression molding on the fine powder obtained from the step (3) and mixed uniformly in a press under the protection of nitrogen, carrying out isostatic pressing to obtain a pressed compact, then loading the pressed compact into a sintering furnace under the protection of nitrogen for high-temperature sintering, and finally carrying out heat treatment by adopting first-stage aging and second-stage aging. The high-temperature sintering temperature is 1070 ℃, the heat preservation time is 3 hours, and the heat preservation is continuously carried out at the sintering temperature of 1082 ℃ for 2 hours after the heat preservation is finished. The temperature of the first-stage aging heat treatment is 820 ℃, and the temperature is kept for 2 hours; the temperature of the secondary aging heat treatment is 580 ℃, and the heat preservation time is 4 hours.
Example 4
This example provides a high performance cerium-containing rare earth permanent magnet with Nd as the component 17.7 Pr 5.8 Ce 7.0 Dy 0.5 Co 0.5 Al 0.1 Cu 0.15 Ga 0.15 Ti 0.1 B 0.93 Fe 67.07 。
(1) Proportioning the components, smelting by using a vacuum induction smelting furnace at 1440-1460 ℃, casting into cast pieces with the average thickness of 0.25-0.27 mm, performing hydrogen crushing by using a hydrogen crushing furnace at the hydrogen pressure of 0.05-0.2 MPa, and crushing the cast pieces into master alloy coarse powder;
(2) Adding zirconium hydride ZrH into mother alloy coarse powder 2 Powder, the added mass percentage is 0.3%;
(3) Grinding the coarse powder uniformly mixed in the step (2) into fine powder by adopting an airflow mill, wherein the grinding gas is nitrogen, the average particle size is controlled to be 2.9-3.0 mu m, and mixing the fine powder after grinding;
(4) And (4) carrying out magnetic field orientation and compression molding on the uniformly mixed fine powder obtained in the step (3) in a press under the protection of nitrogen, carrying out isostatic pressing operation to obtain a pressed compact, then putting the pressed compact into a sintering furnace under the protection of nitrogen for high-temperature sintering, and finally carrying out heat treatment by adopting primary aging and secondary aging. The high-temperature sintering temperature is 1065 ℃, the heat preservation time is 3 hours, and the sintering temperature is 1080 ℃ and the heat preservation time is 2 hours after the heat preservation is finished. The temperature of the first-stage aging heat treatment is 690 ℃, and the temperature is kept for 2 hours; the temperature of the secondary aging heat treatment is 450 ℃, and the heat preservation time is 4 hours.
Comparative example 1
The comparative example provides a high-performance cerium-containing rare earth permanent magnet, the components of which are Nd in percentage by mass 21.0 Pr 7.0 Ce 2.0 Dy 0.1 Co 0.3 Al 0.05 Cu 0.1 Ga 0.1 Nb 0.1 B 0.95 Fe 68.3
(1) Proportioning the components, smelting by using a vacuum induction smelting furnace at 1460-1480 ℃, casting into cast pieces with the average thickness of 0.28-0.30 mm, carrying out hydrogen crushing by using a hydrogen crushing furnace at the hydrogen pressure of 0.05-0.2 MPa, and crushing the cast pieces into master alloy coarse powder;
(2) Grinding the coarse powder in the step (1) into fine powder by adopting an air flow mill, wherein the grinding gas is nitrogen, the average particle size is controlled to be 3.0-3.1 mu m, and mixing the fine powder after grinding;
(3) And (3) carrying out magnetic field orientation and compression molding on the uniformly mixed fine powder obtained in the step (2) in a press under the protection of nitrogen, carrying out isostatic pressing operation to obtain a pressed compact, then putting the pressed compact into a sintering furnace under the protection of nitrogen for high-temperature sintering, and finally carrying out heat treatment by adopting primary aging and secondary aging. The high-temperature sintering temperature is 1060 ℃, the heat preservation time is 4 hours, and the heat preservation is continuously carried out at the sintering temperature of 1070 ℃ for 1 hour after the heat preservation is finished. The temperature of the first-stage aging heat treatment is 840 ℃, and the temperature is kept for 1.5 hours; the temperature of the secondary aging heat treatment is 510 ℃, and the holding time is 4 hours.
Comparative example 2
The comparative example provides a high-performance cerium-containing rare earth permanent magnet, the component of which is Nd by mass percentage 19.3 Pr 6.4 Ce 5.0 Dy 0.3 Co 0.5 Al 0.1 Cu 0.15 Ga 0.15 Ti 0.1 B 0.92 Fe 67.08
(1) Proportioning the components, smelting by using a vacuum induction smelting furnace at 1440-1460 ℃, casting into cast pieces with the average thickness of 0.25-0.27 mm, performing hydrogen crushing by using a hydrogen crushing furnace at the hydrogen pressure of 0.05-0.2 MPa, and crushing the cast pieces into master alloy coarse powder;
(2) Grinding the coarse powder in the step (1) into fine powder by adopting an air flow mill, wherein the grinding gas is nitrogen, the average particle size is controlled to be 2.9-3.0 mu m, and mixing the fine powder after grinding;
(3) And (3) carrying out magnetic field orientation and compression molding on the uniformly mixed fine powder obtained in the step (2) in a press under the protection of nitrogen, carrying out isostatic pressing operation to obtain a pressed compact, then putting the pressed compact into a sintering furnace under the protection of nitrogen for high-temperature sintering, and finally carrying out heat treatment by adopting primary aging and secondary aging. The high-temperature sintering temperature is 1065 ℃, the heat preservation time is 3 hours, and the high-temperature sintering temperature is 1075 ℃ and the heat preservation time is 2 hours after the heat preservation is finished. The temperature of the first-stage aging heat treatment is 820 ℃, and the temperature is kept for 2 hours; the temperature of the second stage aging heat treatment is 600 ℃, and the heat preservation time is 4 hours.
Comparative example 3
Comparative exampleProvides a high-performance cerium-containing rare earth permanent magnet, the mass percentage of the components of which is Nd 20.7 Pr 6.8 Ce 3.0 Dy 0.5 Co 0.5 Al 0.3 Cu 0.15 Ga 0.15 Ti 0.1 B 0.91 Fe 66.89
(1) Proportioning the components, smelting by using a vacuum induction smelting furnace at 1440-1460 ℃, casting into cast pieces with the average thickness of 0.25-0.27 mm, carrying out hydrogen crushing by using a hydrogen crushing furnace, wherein the hydrogen pressure of the hydrogen crushing reaction is 0.05-0.2 MPa, and crushing the cast pieces into master alloy coarse powder;
(2) Grinding the coarse powder uniformly mixed in the step (1) into fine powder by adopting an airflow mill, wherein the grinding gas is nitrogen, the average particle size is controlled to be 2.9-3.0 mu m, and mixing the fine powder after grinding;
(3) And (3) carrying out magnetic field orientation and compression molding on the fine powder obtained from the step (2) and mixed uniformly in a press under the protection of nitrogen, carrying out isostatic pressing to obtain a pressed compact, then loading the pressed compact into a sintering furnace under the protection of nitrogen for high-temperature sintering, and finally carrying out heat treatment by adopting first-stage aging and second-stage aging. The high-temperature sintering temperature is 1070 ℃, the heat preservation time is 3 hours, and the heat preservation is continuously carried out at the sintering temperature of 1082 ℃ for 2 hours after the heat preservation is finished. The temperature of the first-stage aging heat treatment is 820 ℃, and the temperature is kept for 2 hours; the temperature of the secondary aging heat treatment is 580 ℃, and the heat preservation time is 4 hours.
Comparative example 4
The comparative example provides a high-performance cerium-containing rare earth permanent magnet, the components of which are Nd in percentage by mass 17.7 Pr 5.8 Ce 7.0 Dy 0.5 Co 0.5 Al 0.1 Cu 0.15 Ga 0.15 Ti 0.1 B 0.93 Fe 67.07
(1) Proportioning the components, smelting by using a vacuum induction smelting furnace at 1440-1460 ℃, casting into cast pieces with the average thickness of 0.25-0.27 mm, carrying out hydrogen crushing by using a hydrogen crushing furnace, wherein the hydrogen pressure of the hydrogen crushing reaction is 0.05-0.2 MPa, and crushing the cast pieces into master alloy coarse powder;
(2) Adding zirconium hydride ZrH into mother alloy coarse powder 2 Powder, the added mass percentage is 0.3%;
(3) Grinding the coarse powder uniformly mixed in the step (2) into fine powder by adopting an airflow mill, wherein the grinding gas is nitrogen, the average particle size is controlled to be 2.9-3.0 mu m, and mixing the fine powder after grinding;
(4) And (4) carrying out magnetic field orientation and compression molding on the uniformly mixed fine powder obtained in the step (3) in a press under the protection of nitrogen, carrying out isostatic pressing operation to obtain a pressed compact, then putting the pressed compact into a sintering furnace under the protection of nitrogen for high-temperature sintering, and finally carrying out heat treatment by adopting primary aging and secondary aging. The high-temperature sintering temperature is 1075 ℃, and the heat preservation time is 5 hours. The temperature of the first-stage aging heat treatment is 900 ℃, and the temperature is kept for 2 hours; the temperature of the second stage aging heat treatment is 500 ℃, and the heat preservation time is 4 hours.
The compositions, processes and magnetic performance results of the above examples and comparative examples are shown in the following table:
TABLE 1 ingredients of examples and comparative examples
TABLE 2 Process and magnetic Properties of examples and comparative examples
The experimental results show that the formula design of the invention can improve and strengthen the grain boundary of the cerium-containing rare earth permanent magnet and inhibit the adverse effect caused by cerium distribution and segregation, so that the high-performance cerium-containing rare earth permanent magnet can be prepared, and the coercive force can be further improved by adding alloy into the grain boundary. The sintering and heat treatment process is a new process developed aiming at the new microstructure and phase composition of the cerium-containing rare earth permanent magnet, and can further improve the coercive force of the magnet.
Claims (8)
1. A high-performance cerium-containing rare earth permanent magnet is characterized in that: the alloy comprises a master alloy and a grain boundary addition alloy, wherein the master alloy comprises the following components: (R, ce, dy) a Fe b M c B d (ii) a R is one or more of other rare earth elements except Ce and Dy and must contain Nd, M is at least one of Al, si, ti, V, cr, mn, ni, co, cu, zn, ga, zr, nb, W, O, C, S, N and H elements, fe is an iron element and B is a boron element; the grain boundary addition alloy is at least one of an oxide and a hydride of zirconium.
2. The high performance cerium-containing rare earth permanent magnet of claim 1, wherein: the master alloy comprises the following components in percentage by mass: a is more than or equal to 29 weight percent and less than or equal to 33 weight percent, c is more than or equal to 0.1 weight percent and less than or equal to 3 weight percent, d is more than or equal to 0.9 weight percent and less than or equal to 1 weight percent, and the balance is b.
3. The high performance cerium-containing rare earth permanent magnet of claim 1, wherein: the mass percentage of Ce in the master alloy is 1-10%.
4. The high performance cerium-containing rare earth permanent magnet of claim 1, wherein: the mass percentage of Dy in the master alloy is 0.1-0.5%.
5. The high performance cerium-containing rare earth permanent magnet of claim 1, wherein: the addition amount of the grain boundary addition alloy is 0.1-0.5%, and the average grain size is 1-10 um.
6. A method of making the high performance cerium-containing rare earth permanent magnet of claim 1, comprising:
(1) Proportioning the components of the master alloy, smelting by using a vacuum induction smelting furnace at 1400-1500 ℃, casting into a casting sheet with the thickness of 0.1-0.5 mm, performing hydrogen crushing by using a hydrogen crushing furnace at the hydrogen pressure of 0.05-0.2 MPa, and crushing the casting sheet into master alloy coarse powder;
(2) Adding at least one powder of zirconium oxide and hydride into the master alloy coarse powder, wherein the added mass percent is 0.1-0.5%;
(3) Grinding the coarse powder uniformly mixed in the step (2) into fine powder by adopting an airflow mill, wherein the grinding gas is nitrogen, the average particle size is controlled to be 2-5 mu m, and mixing the fine powder after grinding;
(4) And (4) carrying out magnetic field orientation and compression molding on the fine powder obtained from the step (3) and mixed uniformly in a press under the protection of nitrogen, carrying out isostatic pressing to obtain a pressed compact, then loading the pressed compact into a sintering furnace under the protection of nitrogen for high-temperature sintering, and finally carrying out heat treatment by adopting first-stage aging and second-stage aging.
7. The method of claim 6, wherein: the high-temperature sintering temperature in the step (4) is 1000-1080 ℃, the heat preservation time is 3-6 hours, and the temperature is continuously 10-15 ℃ higher than the sintering temperature after the heat preservation is finished, and the heat preservation time is 1-2 hours.
8. The method of manufacturing according to claim 6, characterized in that: the temperature of the first stage aging heat treatment in the step (4) is 630-880 ℃, and the temperature is kept for 1-2 hours; the temperature of the second stage aging heat treatment is 400-620 ℃, and the heat preservation time is 3-6 hours.
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