CN113571280A - Neodymium iron boron magnet coarse powder auxiliary agent, preparation method and application thereof, and preparation method of magnet - Google Patents
Neodymium iron boron magnet coarse powder auxiliary agent, preparation method and application thereof, and preparation method of magnet Download PDFInfo
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- CN113571280A CN113571280A CN202110836464.6A CN202110836464A CN113571280A CN 113571280 A CN113571280 A CN 113571280A CN 202110836464 A CN202110836464 A CN 202110836464A CN 113571280 A CN113571280 A CN 113571280A
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- boron magnet
- coarse powder
- iron boron
- neodymium iron
- rare earth
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- 229910001172 neodymium magnet Inorganic materials 0.000 title claims abstract description 203
- 239000000843 powder Substances 0.000 title claims abstract description 166
- 239000012752 auxiliary agent Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 98
- 239000000126 substance Substances 0.000 claims abstract description 47
- 239000004327 boric acid Substances 0.000 claims abstract description 40
- -1 boric acid ester Chemical class 0.000 claims abstract description 34
- 239000000654 additive Substances 0.000 claims abstract description 32
- 230000000996 additive effect Effects 0.000 claims abstract description 31
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims description 56
- 230000008569 process Effects 0.000 claims description 42
- 229910045601 alloy Inorganic materials 0.000 claims description 38
- 239000000956 alloy Substances 0.000 claims description 38
- 239000002994 raw material Substances 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 238000005245 sintering Methods 0.000 claims description 17
- 238000000227 grinding Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 238000003825 pressing Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 9
- 238000000462 isostatic pressing Methods 0.000 claims description 9
- 150000005215 alkyl ethers Chemical class 0.000 claims description 8
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910004299 TbF3 Inorganic materials 0.000 claims description 7
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 claims description 7
- 229910016468 DyF3 Inorganic materials 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- LKNRQYTYDPPUOX-UHFFFAOYSA-K trifluoroterbium Chemical compound F[Tb](F)F LKNRQYTYDPPUOX-UHFFFAOYSA-K 0.000 claims description 5
- 229910005693 GdF3 Inorganic materials 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 28
- 230000005291 magnetic effect Effects 0.000 description 21
- 238000001816 cooling Methods 0.000 description 15
- 229910052786 argon Inorganic materials 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
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- 238000009792 diffusion process Methods 0.000 description 9
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 238000003723 Smelting Methods 0.000 description 7
- 238000011049 filling Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910052692 Dysprosium Inorganic materials 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910052771 Terbium Inorganic materials 0.000 description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 6
- HQKMJHAJHXVSDF-UHFFFAOYSA-L magnesium stearate Chemical compound [Mg+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O HQKMJHAJHXVSDF-UHFFFAOYSA-L 0.000 description 6
- LDVVTQMJQSCDMK-UHFFFAOYSA-N 1,3-dihydroxypropan-2-yl formate Chemical compound OCC(CO)OC=O LDVVTQMJQSCDMK-UHFFFAOYSA-N 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000006247 magnetic powder Substances 0.000 description 5
- 238000003801 milling Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 229910052688 Gadolinium Inorganic materials 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 230000001050 lubricating effect Effects 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 229920005862 polyol Polymers 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 238000001132 ultrasonic dispersion Methods 0.000 description 4
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 description 3
- WHIVNJATOVLWBW-PLNGDYQASA-N (nz)-n-butan-2-ylidenehydroxylamine Chemical compound CC\C(C)=N/O WHIVNJATOVLWBW-PLNGDYQASA-N 0.000 description 3
- 229910052689 Holmium Inorganic materials 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
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- 150000002148 esters Chemical class 0.000 description 3
- 230000005294 ferromagnetic effect Effects 0.000 description 3
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- 238000010902 jet-milling Methods 0.000 description 3
- 235000019359 magnesium stearate Nutrition 0.000 description 3
- 230000005389 magnetism Effects 0.000 description 3
- 230000005415 magnetization Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 150000003077 polyols Chemical class 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical group [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 229910052691 Erbium Inorganic materials 0.000 description 2
- 229910052765 Lutetium Inorganic materials 0.000 description 2
- 229910052775 Thulium Inorganic materials 0.000 description 2
- 229910052769 Ytterbium Inorganic materials 0.000 description 2
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 238000007723 die pressing method Methods 0.000 description 2
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- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 2
- 238000002074 melt spinning Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000005298 paramagnetic effect Effects 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 2
- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000005619 boric acid group Chemical group 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 229910052743 krypton Inorganic materials 0.000 description 1
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
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- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
-
- 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
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Hard Magnetic Materials (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention discloses a neodymium iron boron magnet coarse powder auxiliary agent, a preparation method and application thereof, and a preparation method of a magnet. The neodymium iron boron magnet coarse powder auxiliary agent comprises 0.01-0.1 g of boric acid, 0.001-0.1 ml of boric acid ester and 0.1-0.85 g of substances containing heavy rare earth elements in terms of 1g of neodymium iron boron magnet coarse powder auxiliary agent; wherein the substance containing the heavy rare earth elements is selected from one or more of a heavy rare earth metal simple substance, a heavy rare earth metal hydride or a heavy rare earth metal halide. The neodymium iron boron magnet coarse powder additive can improve the intrinsic coercive force of a neodymium iron boron magnet without reducing remanence.
Description
Technical Field
The invention relates to a neodymium iron boron magnet coarse powder auxiliary agent, a preparation method and application thereof, and a preparation method of a magnet.
Background
The neodymium iron boron magnet is used as a basic functional material and is widely applied to the fields of electric vehicles, hybrid electric vehicles, wind power generation, variable frequency air conditioners, medical equipment, elevators, sound equipment, mineral separation and the like due to excellent magnetic performance. With the accelerated development of science and technology and low-carbon economy, the fields of hybrid vehicles, wind power generation, variable frequency air conditioners and the like have new requirements on the neodymium iron boron magnet, namely the neodymium iron boron magnet is required to provide higher remanence and coercive force so as to provide enough magnetic energy storage and ensure the normal operation of the product at high temperature.
In order to improve the remanence and coercive force of the ndfeb magnet, a method of adding a small amount of heavy rare earth elements (such as Dy, Tb, etc.) is generally used. The price of heavy rare earth is higher. In order to reduce the production cost, the use amount of heavy rare earth needs to be reduced. The current method for reducing the use amount of heavy rare earth mainly comprises a double-alloy process and a grain boundary diffusion process. The double-alloy process includes smelting main alloy and auxiliary alloy containing heavy RE element, crushing to form powder, mixing the main alloy powder and the auxiliary alloy powder in certain proportion, orientation pressing and sintering. The process has high use amount of heavy rare earth elements. The grain boundary diffusion process is to form a covering layer containing heavy rare earth elements on the surface of the neodymium iron boron magnet by means of smearing, spraying, dipping, coating and the like, and to diffuse the heavy rare earth elements into the magnet under the high-temperature condition, so as to achieve the purposes of improving the coercive force of the magnet and reducing the use of the heavy rare earth. The heavy rare earth element has limited diffusion depth, is only suitable for a thin-sheet magnet and has a small application range.
CN110767401A discloses a method for improving the performance of a sintered neodymium-iron-boron magnet, which comprises the following process steps: firstly, coarsely crushing the neodymium iron boron alloy sheet; carrying out hydrogen absorption treatment on the alloy sheet after coarse crushing, then carrying out dehydrogenation treatment, adding a conventional ester lubricant into the neodymium iron boron alloy sheet after dehydrogenation treatment, and grinding the mixture by using a jet mill through a nitrogen medium to obtain magnetic powder; and (3) mixing the conventional ester lubricant into the magnetic powder, and performing the processes of magnetic field orientation, molding, isostatic pressing, sintering, aging and the like to obtain the neodymium iron boron sintered magnet. The method adds conventional ester lubricants to facilitate milling, rather than to increase coercivity. Therefore, no report has been made on the addition of heavy rare earth elements at the milling stage to improve the coercive force of the magnet. In addition, the selection of which additives to use with heavy rare earth elements to achieve the improvement in coercivity of the magnet still requires further investigation.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a neodymium iron boron magnet coarse powder additive, which can improve the intrinsic coercivity of a neodymium iron boron magnet without reducing remanence.
The invention also aims to provide a preparation method of the neodymium iron boron magnet coarse powder auxiliary agent, which is simple in process and can obtain the auxiliary agent capable of improving the intrinsic coercive force of the neodymium iron boron magnet without reducing remanence.
The invention further aims to provide the application of the neodymium iron boron magnet coarse powder additive in improving the intrinsic coercivity of the neodymium iron boron magnet.
It is still another object of the present invention to provide a method for manufacturing a magnet, which can improve the intrinsic coercive force of a neodymium iron boron magnet without reducing remanence.
On one hand, the invention provides a neodymium iron boron magnet coarse powder auxiliary agent which contains 0.01-0.1 g of boric acid, 0.001-0.1 ml of boric acid and 0.1-0.85 g of substances containing heavy rare earth elements, calculated by 1g of the neodymium iron boron magnet coarse powder auxiliary agent;
wherein the substance containing the heavy rare earth elements is selected from one or more of a heavy rare earth metal simple substance, a heavy rare earth metal hydride or a heavy rare earth metal halide.
The neodymium iron boron magnet coarse powder additive has the advantages ofOptionally, the heavy rare earth element-containing substance is selected from GdF3、TbF3、DyF3One or more of (a).
According to the neodymium iron boron magnet coarse powder auxiliary agent, the average particle diameter D of the heavy rare earth element-containing substance is preferably500.5 to 10 μm.
According to the neodymium iron boron magnet coarse powder auxiliary agent, preferably, the neodymium iron boron magnet coarse powder auxiliary agent further contains 0.01-0.15 g of oxime compound in terms of 1g of neodymium iron boron magnet coarse powder auxiliary agent.
According to the neodymium iron boron magnet coarse powder auxiliary agent provided by the invention, preferably, the neodymium iron boron magnet coarse powder auxiliary agent further contains alkyl alcohol, alkyl ether or petroleum ether as a solvent.
On the other hand, the invention provides a preparation method of the neodymium iron boron magnet coarse powder auxiliary agent, which comprises the following steps:
and ultrasonically dispersing the raw materials comprising boric acid, boric acid ester and the substance containing the heavy rare earth elements for 5-80 min.
On the other hand, the invention provides the application of the neodymium iron boron magnet coarse powder additive in improving the intrinsic coercivity of a neodymium iron boron magnet.
In another aspect, the present invention provides a method for preparing a magnet, comprising the steps of:
mixing the neodymium iron boron magnet coarse powder additive with neodymium iron boron magnet coarse powder, and grinding the mixture into powder to form neodymium iron boron magnet fine powder;
wherein the dosage of the neodymium iron boron magnet coarse powder additive is 0.05-5 wt% of the neodymium iron boron magnet coarse powder; average particle diameter D of neodymium iron boron magnet coarse powder5010 to 1000 μm; average particle diameter D of fine powder of neodymium-iron-boron magnet500.5 to 5 μm.
The preparation method according to the present invention preferably further comprises the steps of:
melting raw materials consisting of 13-35 wt% of Nd, 0.1-1 wt% of Al, 0.5-10 wt% of Co, 0.05-0.5 wt% of Cu, 0.05-0.5 wt% of Zr, 0.3-8 wt% of B and the balance of Fe based on the total weight of the raw materials to form an alloy sheet; and (3) carrying out a hydrogen crushing process on the alloy sheet to obtain neodymium iron boron magnet coarse powder.
The preparation method according to the present invention preferably further comprises the steps of:
pressing and forming the fine powder of the neodymium iron boron magnet and performing isostatic pressing to obtain a blank;
and sintering and aging the blank to obtain the magnet.
The neodymium iron boron magnet coarse powder additive is added into neodymium iron boron magnet coarse powder in the grinding process, so that heavy rare earth elements can enter the neodymium iron boron magnet fine powder through grain boundary diffusion, the intrinsic coercive force of the neodymium iron boron magnet can be improved, and the remanence is not reduced. The neodymium iron boron magnet coarse powder additive is particularly suitable for improving the intrinsic coercive force of a blocky neodymium iron boron magnet.
Detailed Description
The present invention will be further described with reference to specific embodiments, but the scope of the present invention is not limited thereto.
In the present invention, intrinsic coercivity is the magnetic field strength at which the magnetization is reduced from the saturation magnetization state of the magnet to zero along the saturation hysteresis loop by monotonically decreasing the magnetic field to zero and increasing it in the opposite direction, and is generally denoted as HcjIn oersted (Oe). 1Oe ≈ 79.6A/m.
In the present invention, remanence is a value of magnetic flux density corresponding to a place where the magnetic field strength is zero on the saturation hysteresis line, and is generally referred to as BrIn units of Tesla (T) or Gauss (Gs). 1Gs is 0.0001T.
In the present invention, the squareness is the knee point coercive force HkAnd intrinsic coercivity HcjThe ratio of (A) to (B) is generally referred to as Q.
In the present invention, the heavy rare earth element is also called "yttrium group element", and includes nine elements, namely yttrium (Y), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), etc., and is called Re.
In the present invention, the inert atmosphere means an atmosphere which does not react with the magnet and does not affect the magnetic properties thereof. The inert gas atmosphere includes an atmosphere formed of nitrogen or an inert gas (helium, neon, argon, krypton, xenon).
In the present invention, the vacuum means an absolute degree of vacuum, and its value is 0.01Pa or less, and more preferably 0.001Pa or less. The smaller the value of the absolute vacuum degree, the higher the vacuum degree.
In the present invention, the average particle diameter D50The equivalent diameter of the largest particle at a cumulative distribution of 50% in the particle size distribution curve is shown.
The Nd-Fe-B magnet of the invention is expressed as Nd2Fe14B is a magnet of the main phase. According to different forming modes of the neodymium iron boron magnet, the neodymium iron boron magnet can be classified into a bonded neodymium iron boron magnet or a sintered neodymium iron boron magnet. The neodymium iron boron magnet of the present invention is preferably a sintered neodymium iron boron magnet.
The ndfeb magnet of the present invention includes magnets of various shapes, such as a sheet-shaped ndfeb magnet or a block-shaped ndfeb magnet. The sheet neodymium iron boron magnet means a magnet having a thickness much smaller than a width, for example, a ratio of the thickness to the width is 1/8 or less, preferably 1/10 or less. By block neodymium iron boron magnet is meant a magnet having a thickness close to or slightly greater than the width, for example, a thickness to width ratio equal to or greater than 1/2, preferably equal to or greater than 2/3. The neodymium iron boron magnet of the present invention is preferably a bulk neodymium iron boron magnet.
According to one embodiment of the invention, the neodymium iron boron magnet of the invention is a bulk sintered neodymium iron boron magnet.
< coarse powder auxiliary for Nd-Fe-B magnet >
The neodymium iron boron magnet coarse powder auxiliary agent contains boric acid, boric acid ester and substances containing heavy rare earth elements. The neodymium iron boron magnet coarse powder auxiliary agent also contains oxime compounds. According to one embodiment of the present invention, the neodymium iron boron magnet coarse powder additive further contains an alkyl alcohol, an alkyl ether or a petroleum ether as a solvent. In order to avoid the reduction of magnetic performance, the neodymium iron boron magnet coarse powder additive does not contain stearic acid and stearate. The stearate may be magnesium stearate. As described in detail below.
The invention discovers that the substance containing the heavy rare earth element, boric acid and boric acid ester are mutually promoted, so that the substance containing the heavy rare earth element is uniformly dispersed on the surface of the fine powder of the neodymium iron boron magnet. In the grinding process, the heavy rare earth elements in the substance containing the heavy rare earth elements can also be properly diffused into the fine powder of the neodymium-iron-boron magnet. The magnetic powder formed in this way is very beneficial to the even dispersion of heavy rare earth elements in the formed magnet, thereby being beneficial to improving the intrinsic coercive force of the neodymium iron boron magnet without reducing the remanence. For bulk magnets, it is difficult for conventional methods to uniformly disperse the heavy rare earth elements in the magnet. The auxiliary agent can realize the uniform dispersion of heavy rare earth elements in the bulk magnet, so the auxiliary agent is particularly suitable for improving the intrinsic coercive force of the bulk neodymium iron boron magnet.
In the invention, the boric acid has lubricating effect and antioxidation effect, and also has the effect of promoting the diffusion of the heavy rare earth element. The amount of the boric acid is 0.01-0.1 g, preferably 0.01-0.08 g, and more preferably 0.01-0.05 g based on 1g of the neodymium iron boron magnet coarse powder auxiliary agent. The using amount of the boric acid is less than 0.01g, and the lubricating and antioxidant effects are poor; the use amount of boric acid is more than 0.1g, which can hinder the diffusion of heavy rare earth elements.
In the invention, the borate has a lubricating effect, can avoid the introduction of carbon elements and other impurity elements, and has the effect of promoting the diffusion of heavy rare earth elements. Compared with other conventional lubricants, the borate has a more remarkable promotion effect on the diffusion of heavy rare earth elements. The amount of the borate is 0.001-0.1 ml, preferably 0.001-0.08 ml, and more preferably 0.001-0.05 ml based on 1g of the neodymium iron boron magnet coarse powder auxiliary agent. The lubricating effect is poor when the using amount of the borate is less than 0.001 ml; the using amount of the borate is more than 0.1ml, and the heavy rare earth elements are prevented from diffusing into the fine powder of the neodymium iron boron magnet.
The borate esters of the present invention may be borate esters formed by reacting boric acid with a polyol. The polyol may be an alkyl polyol or a polyol containing ether linkages. The polyhydric alcohol may be a dihydric alcohol, a trihydric alcohol, a tetrahydric alcohol, a pentahydric alcohol, or the like, depending on the number of hydroxyl groups. According to one embodiment of the invention, the borate ester is triethylene glycol methyl ether borate triester, boric acid monoglyceride or boric acid diglyceride.
In the invention, the dosage of the substance containing heavy rare earth elements is 0.1-0.85 g based on 1g of neodymium iron boron magnet coarse powder auxiliary agent; preferably 0.1 to 0.8g, more preferably 0.2 to 0.7 g. Remanence is determined by saturation magnetic polarization, and intrinsic coercivity is determined by the anisotropy field. The anisotropy field of the heavy rare earth element is high, the anisotropy field of the magnet can be improved by adding the substance containing the heavy rare earth element, so that the intrinsic coercive force of the magnet is improved, but the molecular magnetic moment and the saturation magnetization of the magnet are reduced due to the fact that the atomic magnetic moment of the heavy rare earth element is opposite to the atomic magnetic moment of Fe, and the remanence of the magnet is reduced due to the fact that the substance containing the heavy rare earth element is added. The dosage of the substance containing the heavy rare earth elements is less than 0.1g, and the substance cannot be uniformly dispersed on the fine powder of the neodymium iron boron magnet, so that the improvement of the intrinsic coercive force is not significant; the use amount of the substance containing the heavy rare earth elements is more than 2g, which results in the waste of the heavy rare earth elements and reduces the residual magnetism of the magnet.
The heavy rare earth element-containing substance of the present invention may be selected from one or more of a heavy rare earth simple substance, a heavy rare earth hydride or a heavy rare earth halide. Examples of heavy rare earth metal halides include, but are not limited to, heavy rare earth metal fluorides or heavy rare earth metal chlorides. According to one embodiment of the invention, the heavy rare earth element-containing substance of the invention is a heavy rare earth metal fluoride.
The heavy rare earth elements comprise yttrium (Y), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb) and lutetium (Lu). Preferably, the heavy rare earth element may be selected from one or more of Gd, Tb, Dy, Ho. Curie temperature, refers to the temperature at which a material can change between a ferromagnetic and a paramagnetic body, i.e., the phase transition temperature at which a ferromagnetic body changes from a ferromagnetic phase to a paramagnetic phase. The curie temperature determines the maximum use temperature and temperature stability of the material. The curie temperature is higher, and the material can show better temperature stability. In view of the stability of the magnet, the heavy rare earth element in the heavy rare earth element-containing substance is preferably one or more of Gd, Tb, and Dy, which have a high curie temperature. According to some preferred embodiments of the present invention, the heavy rare earth element in the heavy rare earth element-containing substance is more preferably Tb and/or Dy. The addition of Tb and Dy with higher Curie temperature is helpful to improve the Curie temperature of the magnet, can better improve the intrinsic coercivity of the magnet, maintains good temperature stability of the material, and meets the requirement of normal operation of the product at higher temperature.
According toIn one embodiment of the present invention, the heavy rare earth element-containing substance is selected from GdF3、TbF3、DyF3One or more of (a). The substance containing the heavy rare earth elements is very suitable for being matched with boric acid and boric acid ester for use, and the substances containing the heavy rare earth elements are promoted to be uniformly dispersed on the surface of the fine powder of the neodymium iron boron magnet and the heavy rare earth elements are properly diffused into the fine powder of the neodymium iron boron magnet in the grinding process.
Average particle diameter D of the heavy rare earth element-containing substance of the invention50It may be 0.5 to 10 μm, preferably 1 to 8 μm, and more preferably 2 to 6 μm. The particle size range enables the stability of the auxiliary agent to be good, and the auxiliary agent is beneficial to uniformly dispersing substances containing heavy rare earth elements on the surface of the fine powder of the neodymium iron boron magnet and properly dispersing the heavy rare earth elements into the fine powder of the neodymium iron boron magnet in the powder grinding process. It should be noted that, in the milling process, the average particle size of the heavy rare earth element-containing substance is also reduced, which is favorable for the heavy rare earth element-containing substance to be uniformly dispersed on the surface of the fine powder of the neodymium iron boron magnet and also favorable for the diffusion of the heavy rare earth element.
In the invention, the dosage of the oxime compound is 0.01-0.15 g based on 1g of the neodymium iron boron magnet coarse powder auxiliary agent; preferably 0.02 to 0.1g, more preferably 0.03 to 0.05 g. The oxime compound has good oxygen removal performance in a wide temperature and pressure range, the optimum temperature is 138-336 ℃, and the optimum pressure range is 0.3-13.7 MPa. Under high temperature and high pressure, the oxime compound has certain protection effect on the magnet. The dosage of the oxime compound is less than 0.01g, the oxygen removing effect is not obvious, and the performance of the magnet is reduced; and if the dosage of the oxime compound is more than 0.15g, the diffusion of the heavy rare earth element is blocked, and the intrinsic coercive force of the magnet is reduced. The oxime is an organic compound produced by reacting aldehyde or ketone compound containing a carbonyl group with hydroxylamine. The oxime compound of the invention can be aldoxime or ketoxime. The aldehyde of the present invention may contain 2 to 8 carbon atoms; such as acetaldehyde. The ketones of the present invention may contain 3 to 9 carbon atoms; such as acetone or butanone. According to one embodiment of the invention, the oxime compound is acetaldoxime, acetoxime or butanone oxime.
In the present invention, an alkyl alcohol, an alkyl ether or a petroleum ether is used as a solvent. The alkyl alcohol may contain 1 to 8 carbon atoms. According to one embodiment of the invention, the alkyl alcohol is methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol. The alkyl ether may contain 2 to 9 carbon atoms. According to one embodiment of the invention, the alkyl ether is diethyl ether, dimethyl ether or the like. In order to achieve better dispersion, the solvent of the present invention is selected from methanol, ethanol, n-propanol, isopropanol, n-butanol or isobutanol.
According to a preferred embodiment of the present invention, the neodymium iron boron magnet coarse powder additive comprises 0.01 to 0.1g of boric acid, 0.001 to 0.1ml of borate, 0.1 to 0.85g of heavy rare earth element-containing substance, 0.01 to 0.15g of oxime compound and the balance of solvent based on 1g of neodymium iron boron magnet coarse powder additive. The borate is boric acid monoglyceride or boric acid diglyceride; the heavy rare earth element-containing substance is selected from GdF3、TbF3、DyF3One or more of; the oxime compound is selected from one or more of acetaldoxime, acetoxime and butanone oxime; the solvent is n-butanol or isobutanol.
< preparation method of neodymium iron boron magnet coarse powder adjuvant >
The preparation method of the neodymium iron boron magnet coarse powder auxiliary agent is described below. Carrying out ultrasonic dispersion on raw materials comprising boric acid, boric acid ester and a substance containing heavy rare earth elements to obtain the neodymium iron boron magnet coarse powder auxiliary agent. According to one embodiment of the invention, the neodymium iron boron magnet coarse powder auxiliary agent is obtained by ultrasonically dispersing raw materials comprising boric acid, boric acid ester, a substance containing heavy rare earth elements and alkyl alcohol, alkyl ether or petroleum ether serving as a solvent. According to one embodiment of the invention, the neodymium iron boron magnet coarse powder auxiliary agent is obtained by ultrasonically dispersing raw materials comprising boric acid, boric acid ester, a substance containing heavy rare earth elements, an oxime compound and alkyl alcohol, alkyl ether or petroleum ether serving as a solvent. The types and the amounts of boric acid, boric acid ester, heavy rare earth element-containing substance, oxime compound and solvent are as described above, and are not described herein again.
The ultrasonic dispersion process may be carried out in conventional ultrasonic equipment. The time for ultrasonic dispersion may be 5 to 80min, preferably 10 to 70min, and more preferably 20 to 60 min. The ultrasonic dispersion process can ensure that all raw materials are quickly and uniformly mixed, simultaneously avoid the raw materials from agglomerating and contribute to forming stable suspension.
< use of Neodymium iron boron magnet coarse powder adjuvant >
The neodymium iron boron magnet coarse powder additive is used in the process of crushing neodymium iron boron magnet coarse powder into neodymium iron boron magnet fine powder, so that the intrinsic coercive force of the neodymium iron boron magnet can be improved, and the remanence is reduced. Therefore, the invention also provides the application of the neodymium iron boron magnet coarse powder additive in improving the intrinsic coercivity of the neodymium iron boron magnet. The dosage of the neodymium iron boron magnet coarse powder additive is 0.5 to 5 weight percent of the neodymium iron boron magnet coarse powder; preferably 0.6 wt% to 4.5 wt%; more preferably 0.6 to 2.5 wt%. The neodymium iron boron magnet coarse powder additive is less than 0.5 wt%, so that substances containing heavy rare earth elements cannot be uniformly dispersed on the neodymium iron boron magnet fine powder, and the intrinsic coercive force is not remarkably improved; when the additive of the neodymium iron boron magnet coarse powder is higher than 5 wt%, heavy rare earth elements are wasted, and the residual magnetism of the magnet is reduced.
The types and the use amounts of the raw materials in the neodymium iron boron magnet coarse powder additive are as described above, and are not described again here. The neodymium iron boron magnet coarse powder additive is suitable for the process of forming neodymium iron boron magnet fine powder by grinding neodymium iron boron magnet coarse powder.
The neodymium iron boron magnet coarse powder can be obtained by various methods, such as a hydrogen crushing process. Average particle diameter D of neodymium iron boron magnet coarse powder50May be 10 to 1000 μm, preferably 50 to 600 μm, and more preferably 200 to 400 μm. The invention finds that the neodymium iron boron magnet coarse powder with the particle size range is more beneficial to the neodymium iron boron magnet coarse powder auxiliary agent to play a role. The coarse powder of the neodymium iron boron magnet is too small, the grinding time is reduced, and heavy rare earth elements cannot be uniformly dispersed on the fine powder of the neodymium iron boron magnet; the coarse powder size of the neodymium iron boron magnet is too large, the grinding time is increased, and the oxidation degree of the magnetic powder is increased. According to one embodiment of the invention, the neodymium iron boron magnet coarse powder is neodymium iron boron magnet coarse powder obtained by a hydrogen crushing process.
The fine powder of the neodymium iron boron magnet can be obtained by various methods. The milling process is preferably a jet milling process. Average of fine powder of NdFeB magnetParticle diameter D50Can be 0.5 to 10 μm; preferably 1-8 μm; more preferably 3 to 5 μm. The invention finds that the fine powder of the neodymium iron boron magnet with the particle size range is beneficial to the neodymium iron boron magnet coarse powder auxiliary agent to play a role. The size of the fine powder of the neodymium iron boron magnet is too small, so that the using amount of the additive of the coarse powder of the neodymium iron boron magnet is too large, otherwise, the heavy rare earth elements cannot be uniformly dispersed on the fine powder of the neodymium iron boron magnet; the size of the fine powder of the neodymium iron boron magnet is too large, so that the diffusion effect of heavy rare earth elements is poor, and the intrinsic coercive force of the formed magnet is not obviously improved.
The neodymium iron boron magnet of the present invention is preferably a bulk neodymium iron boron magnet. By block neodymium iron boron magnet is meant a magnet having a thickness close to or slightly greater than the width, for example, a thickness to width ratio equal to or greater than 1/2, preferably equal to or greater than 2/3. According to one embodiment of the invention, the neodymium iron boron magnet of the invention is a bulk sintered neodymium iron boron magnet.
According to one embodiment of the invention, the neodymium iron boron magnet coarse powder auxiliary agent and the neodymium iron boron magnet coarse powder obtained by hydrogen crushing are uniformly mixed and then are subjected to powder milling through airflow, so as to obtain the neodymium iron boron magnet fine powder. The process can promote the substances containing the heavy rare earth elements to be uniformly dispersed on the surface of the fine powder of the neodymium iron boron magnet, and the heavy rare earth elements in the substances containing the heavy rare earth elements are diffused into the fine powder of the neodymium iron boron magnet.
< method for producing magnet >
The invention also provides a method for preparing the magnet by using the neodymium iron boron magnet coarse powder auxiliary agent. The Nd-Fe-B magnet of the invention is expressed as Nd2Fe14B is a magnet of the main phase. The neodymium iron boron magnet of the present invention is preferably a sintered neodymium iron boron magnet. The neodymium iron boron magnet of the present invention includes magnets of various shapes, preferably a bulk neodymium iron boron magnet. By block neodymium iron boron magnet is meant a magnet having a thickness close to or slightly greater than the width, for example, a thickness to width ratio equal to or greater than 1/2, preferably equal to or greater than 2/3. According to one embodiment of the invention, the neodymium iron boron magnet of the invention is a bulk sintered neodymium iron boron magnet.
The preparation method of the magnet comprises the following steps: material preparation, smelting and melt spinning, crushing, powder grinding, press forming, sintering treatment and aging treatment. As described in detail below.
Ingredients
The magnet raw materials and the proportion thereof have important influence on the magnetic performance. The raw material for forming the magnet may include 13 wt% to 35 wt% of Nd, 0.1 wt% to 1 wt% of Al, 0.5 wt% to 10 wt% of Co, 0.05 wt% to 0.5 wt% of Cu, 0.05 wt% to 0.5 wt% of Zr, 0.3 wt% to 8 wt% of B, and 50 wt% to 78 wt% of Fe. According to an embodiment of the present invention, a raw material forming the magnet may be composed of 13 wt% to 35 wt% of Nd, 0.1 wt% to 1 wt% of Al, 0.5 wt% to 10 wt% of Co, 0.05 wt% to 0.5 wt% of Cu, 0.05 wt% to 0.5 wt% of Zr, 0.3 wt% to 8 wt% of B, and the balance of Fe. The above weight percentages are based on the total weight of the raw materials forming the magnet. Preferably, the raw material forming the magnet consists of 15 wt% to 33 wt% of Nd, 0.1 wt% to 0.5 wt% of Al, 0.5 wt% to 5 wt% of Co, 0.05 wt% to 0.35 wt% of Cu, 0.05 wt% to 0.3 wt% of Zr, 0.3 wt% to 6 wt% of B, and the balance of Fe. More preferably, the raw material forming the magnet consists of 20 to 30 wt% of Nd, 0.2 to 0.5 wt% of Al, 0.5 to 3 wt% of Co, 0.08 to 0.25 wt% of Cu, 0.1 to 0.25 wt% of Zr, 0.5 to 4 wt% of B, and the balance of Fe. The raw materials forming the magnet may contain inevitable impurities.
Smelting melt-spun belt
Smelting the raw materials for forming the magnet, and pouring the raw materials on a cooling roller to obtain an alloy sheet with the thickness of 0.1-0.8 mm. The thickness of the alloy sheet may be 0.1 to 0.8mm, preferably 0.2 to 0.5mm, and more preferably 0.25 to 0.35 mm.
In order to prevent oxidation of the raw materials forming the magnet and of the alloy sheet produced therefrom, the melt spinning is preferably carried out in a vacuum or inert atmosphere, for example in a vacuum flash hardening induction furnace. The smelting temperature can be 1350-1550 ℃, and is preferably 1450-1500 ℃. The cooling roll according to the invention can be a rotating cooled copper roll, for example with a free-surface cooling device. Cooling rolls known in the art may be used and will not be described in further detail herein.
According to one embodiment of the invention, raw materials for forming the magnet are smelted under the protection of argon gas of 0.04-0.06 MPa and at 1450-1500 ℃, and the alloy melt is poured on a cooling roller to obtain an alloy sheet with the thickness of 0.1-0.8 mm.
According to a specific embodiment of the invention, the raw materials for forming the magnet are placed in a vacuum intermediate frequency rapid hardening induction furnace, the vacuum is pumped to below 1Pa, argon (Ar) is filled to 0.04-0.06 MPa, then heating and smelting are carried out, and the alloy melt is poured on a cooling roller to obtain an alloy sheet with the thickness of 0.2-0.5 mm.
Crushing
Crushing the alloy pieces into an average particle diameter D50Is 10-1000 μm neodymium-iron-boron magnet coarse powder. Average particle diameter D of the coarse powder obtained by crushing5010 to 1000 μm, preferably 50 to 600 μm, and more preferably 200 to 400 μm.
In order to prevent oxidation of the alloy sheet and the coarse powder of the neodymium iron boron magnet prepared by crushing the alloy sheet, the crushing of the alloy sheet is preferably carried out in vacuum or inert atmosphere. The alloy sheet can be crushed into neodymium iron boron magnet coarse powder by adopting a mechanical crushing process and/or a hydrogen crushing process. The mechanical crushing process is to crush the alloy sheet into alloy powder by using a mechanical crushing device. The mechanical crushing device may be selected from a jaw crusher or a hammer crusher. The hydrogen crushing process includes the first low temperature hydrogen absorption of the alloy sheet, the reaction of the alloy sheet with hydrogen to initiate the volume expansion of the alloy lattice to crush the alloy sheet into alloy powder, and the subsequent heating of the alloy powder to dehydrogenate at high temperature.
According to a preferred embodiment of the present invention, the hydrogen fragmentation process of the present invention is preferably carried out in a hydrogen fragmentation furnace. In the hydrogen crushing process, the hydrogen absorption temperature is 20-400 ℃, preferably 100-300 ℃, the hydrogen absorption pressure is 50-600 kPa, preferably 100-500 kPa, and the dehydrogenation temperature is 400-850 ℃, preferably 500-700 ℃.
Milling powder
And mixing the neodymium iron boron magnet coarse powder additive with neodymium iron boron magnet coarse powder, and grinding the mixture into powder to form neodymium iron boron magnet fine powder. The dosage of the neodymium iron boron magnet coarse powder additive is neodymium iron boron magnet0.05-5 wt% of coarse powder; preferably 0.1 wt% to 4.5 wt%; more preferably 0.6 to 2.5 wt%. The neodymium iron boron magnet coarse powder additive is less than 0.05 wt%, so that substances containing heavy rare earth elements cannot be uniformly dispersed on the neodymium iron boron magnet fine powder, and the intrinsic coercive force is not remarkably improved; when the additive of the neodymium iron boron magnet coarse powder is higher than 5 wt%, heavy rare earth elements are wasted, and the residual magnetism of the magnet is reduced. Average particle diameter D of fine powder of neodymium-iron-boron magnet50Can be 0.5 to 10 μm; preferably 1-8 μm; more preferably 3 to 5 μm.
The mixing apparatus may be a conventional mixing apparatus. In order to improve the mixing efficiency, a 3D mixer is preferred. In the invention, the process of crushing the coarse powder of the neodymium iron boron magnet into the fine powder of the neodymium iron boron magnet can adopt an air flow mill or a high-energy ball mill. The invention preferably adopts the jet milling process for crushing. The jet milling process is to make the alloy powder collide with each other and break up after accelerating by the air current. The gas stream may be a nitrogen stream, preferably a high purity nitrogen stream. N in the high-purity nitrogen stream2The content may be 99.0 wt% or more, preferably 99.9 wt% or more. The pressure of the air flow can be 0.1-2.0 MPa, preferably 0.5-1.0 MPa, and more preferably 0.6-0.7 MPa.
Press forming
And placing the fine powder of the neodymium iron boron magnet in an oriented magnetic field, and pressing and molding to obtain a blank. The orientation magnetic field direction and the magnetic powder pressing direction are oriented in parallel or perpendicular to each other. In the present invention, the strength of the orienting magnetic field is at least 2 Tesla (T), preferably at least 2.5T.
In order to prevent the fine powder of the neodymium-iron-boron magnet from being oxidized, the magnetic field orientation molding is preferably performed in a vacuum or inert atmosphere. The press forming process preferably employs a die pressing process and/or an isostatic pressing process. The isostatic pressing process of the present invention may be carried out in an isostatic press.
According to a preferred embodiment of the invention, the fine powder of the neodymium iron boron magnet is pressed and formed by a mould pressing process to prepare a green body; and then carrying out secondary compression molding by adopting an isostatic pressing process to obtain a blank. Preferably, pressing and forming the fine powder of the neodymium iron boron magnet by adopting a die pressing process to prepare a green body; taking out the green body and carrying out vacuum packaging; and then carrying out secondary pressing forming by adopting an isostatic pressing process to obtain a blank.
The pressure of the isostatic pressing process may be 10 to 300MPa, preferably 50 to 250MPa, and more preferably 100 to 250 MPa. The pressure maintaining time of the isostatic pressing process is 5-100 s, preferably 5-80 s, and more preferably 10-30 s.
In the process of compression molding, because the fine powder of the neodymium iron boron magnet has poor flowability, friction in different degrees exists between particles and the wall of a mold, and the orientation of the fine powder of the neodymium iron boron magnet is influenced. During molding, agglomeration caused by the magnetostatic effect affects the uniformity of product density and the final magnetic properties. The neodymium iron boron magnet coarse powder additive can improve the uniformity and magnetic property of a magnet, and can promote the diffusion of heavy rare earth elements so as to improve the intrinsic coercive force of the neodymium iron boron magnet and improve the remanence and squareness.
Sintering treatment and aging treatment
And sintering and aging the blank under a vacuum condition to obtain the neodymium iron boron magnet. The sintering treatment and the aging treatment are preferably carried out under temperature-programmed conditions. In order to prevent the green body from being oxidized during sintering, the sintering treatment and the aging treatment are preferably performed in a vacuum or an inert atmosphere. The degree of vacuum may be less than 1.0X 10-1Pa, preferably less than 1.0X 10- 3Pa. According to a preferred embodiment of the invention, the green body is sintered in a vacuum sintering furnace.
According to one embodiment of the invention, the green body is subjected to a vacuum of 1X 10-2And (3) starting heating sintering below Pa, carrying out temperature programming to 1000-1150 ℃, preserving heat for 1-6 h, filling argon, and carrying out air cooling to below 150 ℃. Preferably, the green body is subjected to a vacuum of 1X 10-2And (3) starting temperature rise sintering below Pa, preserving heat for 1-2 h at 300-350 ℃, preserving heat for 1-2 h at 500-650 ℃, preserving heat for 3-5 h at 800-900 ℃, preserving heat for 2-6 h at 1020-1120 ℃, filling argon, and cooling to below 150 ℃. More preferably, the green compact is subjected to a vacuum of 1X 10-2Starting temperature rising sintering below Pa, keeping the temperature for 1-1.5 h at 300-330 ℃, and keeping the temperature at 55 DEG CPreserving heat for 1.5-2 h at 0-600 ℃, preserving heat for 4-5 h at 850-900 ℃, then preserving heat for 4-5 h at 1050-1100 ℃, filling argon, and cooling to below 100 ℃ by air.
The aging treatment is preferably a secondary annealing treatment. According to one embodiment of the invention, the green body is subjected to a vacuum of 1X 10-2Heating below Pa, preserving heat for 2-6 h at 800-950 ℃, filling argon, and cooling to below 150 ℃; and then preserving the heat for 2-6 h at 400-600 ℃, filling argon, and cooling the air to below 70 ℃. Preferably, the temperature is kept at 850-930 ℃ for 3.5-5.5 h, argon is filled, and the air is cooled to be below 100 ℃; then preserving the heat for 4.5-5 h at 450-550 ℃, filling argon, and cooling the air to below 60 ℃.
The performance tests of the magnets in the following examples and comparative examples were carried out according to the method specified in GB/T3217-2013.
Preparation examples 1 to 4 and preparation comparative examples 1 to 2
The composition of the neodymium iron boron magnet coarse powder additive is shown in table 1. Weighing raw materials according to the composition of the neodymium iron boron magnet coarse powder auxiliary agent shown in the table 1; mixing the raw materials to form a mixture; and ultrasonically dispersing the mixture for 30min to form stable suspension, namely the neodymium iron boron magnet coarse powder auxiliary agent.
TABLE 1
| Numbering | Preparation example 1 | Preparation example 2 | Preparation example 3 | Preparation example 4 | Preparation of comparative example 1 | Preparation of comparative example 2 |
| TbF3 | 0.2g | 0.4g | — | — | — | — |
| DyF3 | — | — | 0.4g | 0.6g | — | — |
| Boric acid | 0.02g | 0.02g | 0.03g | 0.02g | 0.02g | 0.02g |
| Butanone oxime | 0.03g | 0.03g | 0.03g | 0.04g | 0.03g | 0.04g |
| Boric acid monoglyceride | 0.01ml | 0.01ml | 0.01ml | 0.01ml | 0.01ml | 0.01ml |
| Butanol | 0.9ml | 0.9ml | 0.9ml | 0.9ml | 0.9ml | 0.9ml |
Note: the dosage of the raw materials is calculated by 1g of neodymium iron boron magnet coarse powder auxiliary agent. TbF3And DyF3D of (A)50Is 3 to 5 μm.
Examples 1 to 4 and comparative examples 1 to 2
A raw material for forming a magnet, which consisted of 30 wt% of Nd, 0.5 wt% of Al, 0.72 wt% of Co, 0.1 wt% of Cu, 0.17 wt% of Zr, 0.94 wt% of B and the balance of Fe, was prepared.
Placing the raw materials for forming the magnet in a vacuum intermediate-frequency rapid hardening induction furnace, vacuumizing to below 1Pa, preheating, and vacuumizing again to below 1 Pa; argon is filled to 0.05MPa, then smelting is carried out at the temperature of 1480 ℃, and the alloy melt is poured on a rotating cooling copper roller to obtain an alloy sheet with the average thickness of 0.3 mm.
Placing the alloy sheet in a hydrogen crushing furnace, crushing the alloy sheet into an average grain diameter D under the hydrogen of 0.08MPa50Is 300 μm coarse powder of neodymium iron boron magnet.
Adding the neodymium iron boron magnet coarse powder auxiliary agent into neodymium iron boron magnet coarse powder, mixing the materials in a 3D mixer for 2 hours, and then crushing the neodymium iron boron magnet coarse powder into the average particle size D on an air flow mill50Fine powder of neodymium iron boron magnet of 3.0 μm。
Pressing the fine powder of the neodymium iron boron magnet on a forming press with the magnetic field intensity of 2T to obtain a green body, then vacuumizing and packaging, placing the packaged green body on a cold isostatic press, and pressing for 15s at 200MPa to obtain the green body.
Putting the blank in a vacuum sintering furnace, vacuumizing by 1X 10-2Starting temperature rise sintering below Pa, and respectively keeping the temperature at 300 ℃ for 1h and at 600 ℃ for 2h in the temperature rise process; then preserving heat for 4.5h at 850 ℃, adjusting the sintering temperature to 1050 ℃, preserving heat for 4h, filling argon, and cooling by air below 150 ℃.
In vacuum of 1X 10-2Aging treatment is carried out below Pa. Annealing at 900 deg.C for 5h, introducing argon, and air cooling below 150 deg.C; annealing at 500 deg.C for 5 hr, and introducing argon gas to cool at below 60 deg.C. And discharging the product out of the furnace to obtain the neodymium iron boron magnet. The magnet properties are shown in table 2.
TABLE 2
As can be seen from the above table, examples 1 to 4 have significantly improved intrinsic coercivity without lowering remanence as compared with comparative examples 1 to 2. The remanence of the magnet of the embodiment 2 can reach 14.36kGs, and the intrinsic coercive force can reach 23.95 kOe. The squareness of examples 1 to 4 was almost unchanged as compared with comparative examples 1 to 2, and the Q value was maintained at about 98%.
Preparation example 5 and preparation comparative examples 3 to 6
The composition of the neodymium iron boron magnet coarse powder additive is shown in table 3. The raw materials were weighed according to the compositions of the neodymium iron boron magnet coarse powder aids shown in table 3. The raw materials are mixed to form a mixture. And ultrasonically dispersing the mixture for 30min to form stable suspension, namely the neodymium iron boron magnet coarse powder auxiliary agent.
TABLE 3
Note: the content of the raw materials is 1g, metering an auxiliary agent for the neodymium iron boron magnet coarse powder. TbF3D of (A)50Is 3 to 5 μm.
Example 5 and comparative examples 3 to 6
The same conditions as in example 2 were used except that the neodymium iron boron magnet coarse powder aid shown in table 4 was used. The properties of the obtained magnet are shown in table 4.
TABLE 4
As can be seen from the above table, the neodymium iron boron magnet coarse powder additive has an important influence on the performance of the magnet.
It is understood from example 5 and comparative examples 3 to 4 that the addition of either boric acid or boric acid monoglyceride results in a decrease in remanence and intrinsic coercive force, but the decrease is small.
It is understood from example 5 and comparative example 5 that addition of magnesium stearate alone without boric acid and monoglyceride borate results in a significant decrease in remanence and intrinsic coercivity.
It is understood from example 5 and comparative example 6 that the addition of magnesium stearate in addition to boric acid and monoglycerol borate ester lowers the intrinsic coercive force of the magnet.
The present invention is not limited to the above-described embodiments, and any variations, modifications, and substitutions which may occur to those skilled in the art may be made without departing from the spirit of the invention.
Claims (10)
1. The neodymium iron boron magnet coarse powder auxiliary agent is characterized by comprising 0.01-0.1 g of boric acid, 0.001-0.1 ml of boric acid and 0.1-0.85 g of heavy rare earth element-containing substance, calculated by 1g of neodymium iron boron magnet coarse powder auxiliary agent;
wherein the substance containing the heavy rare earth elements is selected from one or more of a heavy rare earth metal simple substance, a heavy rare earth metal hydride or a heavy rare earth metal halide.
2. The neodymium-iron-boron magnet coarse powder aid as claimed in claim 1, wherein the heavy rare earth element-containing substance is selected from GdF3、TbF3、DyF3One or more of (a).
3. The neodymium-iron-boron magnet coarse powder auxiliary agent according to claim 1, wherein the heavy rare earth element-containing substance has an average particle diameter D500.5 to 10 μm.
4. The neodymium-iron-boron magnet coarse powder auxiliary agent according to claim 1, wherein the neodymium-iron-boron magnet coarse powder auxiliary agent further comprises 0.01-0.15 g of oxime compound based on 1g of neodymium-iron-boron magnet coarse powder auxiliary agent.
5. The ndfeb magnet coarse powder aid according to claim 1, wherein the ndfeb magnet coarse powder aid further comprises an alkyl alcohol, an alkyl ether or a petroleum ether as a solvent.
6. The preparation method of the neodymium iron boron magnet coarse powder auxiliary agent according to any one of claims 1 to 5, characterized by comprising the following steps:
and ultrasonically dispersing the raw materials comprising boric acid, boric acid ester and the substance containing the heavy rare earth elements for 5-80 min.
7. Use of the neodymium iron boron magnet coarse powder additive according to any one of claims 1 to 5 in improving the intrinsic coercivity of a neodymium iron boron magnet.
8. A method for preparing a magnet is characterized by comprising the following steps:
mixing the neodymium-iron-boron magnet coarse powder auxiliary agent of any one of claims 1 to 5 with neodymium-iron-boron magnet coarse powder, and grinding the mixture to form neodymium-iron-boron magnet fine powder;
wherein the dosage of the neodymium iron boron magnet coarse powder additive is 0.05-5 wt% of the neodymium iron boron magnet coarse powder; average particle diameter D of neodymium iron boron magnet coarse powder5010 to 1000 μm; average particle diameter D of fine powder of neodymium-iron-boron magnet500.5 to 5 μm.
9. The method of claim 8, further comprising the steps of:
melting raw materials consisting of 13-35 wt% of Nd, 0.1-1 wt% of Al, 0.5-10 wt% of Co, 0.05-0.5 wt% of Cu, 0.05-0.5 wt% of Zr, 0.3-8 wt% of B and the balance of Fe based on the total weight of the raw materials to form an alloy sheet; the alloy sheet is subjected to a hydrogen crushing process to obtain neodymium iron boron magnet coarse powder.
10. The method of claim 9, further comprising the steps of:
pressing and forming the fine powder of the neodymium iron boron magnet and performing isostatic pressing to obtain a blank;
and sintering and aging the blank to obtain the magnet.
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