CN105006328A - High-performance Ga containing cast sheet magnet and preparation method thereof - Google Patents
High-performance Ga containing cast sheet magnet and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-performance Ga containing cast sheet magnet and a preparation method thereof. The high-performance Ga containing cast sheet magnet comprises the following components by weight: 6.0-9.0 percent of Pr, 20.0-25.0 percent of Nd, 0.5-1.5 percent of B, 0.05-0.3 percent of Al, 0.10-0.2 percent of Cu, 0.1-0.2 percent of Zr, 0.15-0.25 percent of Ga, 0.1-0.5 percent of Co, and the balance of Fe. The preparation method comprises the following steps: cast sheet smelting, hydrogen decrepitation, jet milling grinding, magnetic field oriented moulding, isopressing and sintering. The high-performance Gd containing cast sheet magnet and the preparation method thereof have the advantages that on one hand, in the cast sheet smelting process, no alpha-Fe crystals exist in a cast sheet structure, and a cast sheet is broken more easily, so that the production period is shortened; on the other hand, Zr, Ga and Co metal elements are added, so that the corrosion resistance of the magnet are improved when the magnetism of the magnet is enhanced.
Description
Technical field
The invention belongs to permanent magnetic material technical field, be specifically related to a kind of high-performance containing gallium slab magnet and preparation method thereof.
Background technology
Nd-Fe-B rare earth permanent magnetic material, is the permanent magnetic material that the magnetic property that finds up to now is the strongest, and is more and more applied with its excellent magnetic property, be widely used in medical Magnetic resonance imaging, computer hard disc driver, sound equipment, mobile phone etc.; Along with energy-conservation and requirement that is low-carbon economy, Nd-Fe-B rare earth permanent magnetic material starts again at auto parts and components, household electrical appliance, energy-conservation and control motor, hybrid vehicle, and the field such as wind power generation, Aero-Space is applied, and causes its consumption increasing.
The manufacturing process of now conventional sintered Nd-Fe-B permanent magnet generally comprises: raw material preparation → ingot casting melting → broken powder process → die mould → sintering → timeliness → detection.Wherein in ingot casting melting step, the quality of slab tissue not only has impact to follow-up powder process, orientation, sintering process, and also has extreme influence to powder properties and final sintering magnetic property.Do not have excellent slab tissue, just can not produce high performance sintered permanent magnet, slab tissue is one of key technology of restriction magnet performance, and whether excellent slab tissue depend on the alloy composition of permanent magnet and content and ingot casting thickness to a great extent.At present, ingot casting thickness prepared by ingot casting smelting technology mostly is about 20mm, easily has α-Fe dendrite to separate out, because the plasticity of α-Fe dendrite is better, make ingot casting be difficult to fragmentation, bring inconvenience to follow-up pulverizing process, also need to extend sintering time to obtain uniform Nd2Fe14B crystal.
In addition, existing rubidium iron boron magnet corrosion-resistant, has the magnet of strong corrosion resistant, and magnetic force is not strong, seriously constrains the fast development of rubidium iron boron magnetic industry.
Summary of the invention
The object of the present invention is to provide a kind of high-performance containing gallium slab magnet and preparation method thereof, this magnet and preparation method thereof, slab smelting technology makes slab tissue not have α-Fe crystal on the one hand, slab fragmentation is easier, follow-up powder process is also easier, thus saved manpower and materials, shorten the production cycle, another aspect with the addition of zirconium, gallium, cobalt metal element increasing is ferromagnetic adds corrosion resistance simultaneously.
Technical scheme of the present invention is: a kind of high-performance is containing cerium slab magnet and preparation method thereof, and the described component containing cerium slab magnet and weight percentage are: Pr:6.0 ~ 9.0%, Nd:20.0 ~ 25.0%, B:0.5 ~ 1.5%, Al:0.05 ~ 0.3%, Cu:0.10 ~ 0.2%, Zr:0.1 ~ 0.2%, Ga:0.15 ~ 0.25%, Co:0.1 ~ 0.5%, surplus Fe supplement;
The component and the weight percentage that also preferably contain cerium slab magnet are:
Pr:7.0 ~ 8.0%, Nd:22.0 ~ 23.0%, B:0.8 ~ 1.2%, Al:0.08 ~ 0.1%, Cu:0.15 ~ 0.2%, Zr:0.18 ~ 0.2%, Ga:0.18 ~ 0.22%, Co:0.2 ~ 0.4%, surplus Fe supplements;
The preferred component containing cerium slab magnet and weight percentage are:
Pr:7.5%, Nd:22.5%, B:1.0%, Al:0.1%, Cu:0.18%, Zr:0.2%, Ga:0.20%, Co:0.3%, surplus Fe supplements;
Prepare this preparation method containing cerium slab magnet to comprise the following steps:
1) slab melting: the raw metal of proportioning is in proportion dropped into vacuum induction rapid hardening slab stove, vacuumize, melting at 800 ~ 1000 DEG C, be heated to metal Pr when starting to melt, be filled with high-purity argon gas, through ultrasonic mixing after raw metal melts, when after the conjunctiva of alloy molten solution surface, be poured on the water-cooled copper rod of rotation, through being cooled to the slab that thickness is 0.25 ~ 0.35mm fast;
2) hydrogen is pulverized: by step 1) slab that obtains drops into hydrogen crushing furnace, and dehydrogenation at 500 ~ 540 DEG C, obtains the alloying pellet of 100 ~ 110 μm;
3) airflow milling is pulverized: by step 2) alloying pellet that obtains adds in airflow milling under nitrogen protection, is ground into the alloy powder of 3.4 ~ 4.4 μm through airflow milling;
4) magnetic field orientating is shaping: by step 3) alloy powder that obtains drops into Magnetic field press, and oriented moulding under the magnetic field of 1.9T, obtains pressed compact;
5) isostatic pressed: will through step 4) shaping after pressed compact, reinstall in the high pressure chest of isostatic pressing machine, under the pressure of 190-200MPa, keep 10-20s;
6) sinter: will through step 5) pressed compact drop in vacuum sintering furnace, vacuumize, at 1055 ~ 1110 DEG C, constant temperature 2.5 ~ 3.5 hours; One-level temperature is 860 ~ 960 DEG C, constant temperature 1.5 ~ 2.5 hours; Second annealing temperature is 460 ~ 660 DEG C, constant temperature 2.5 ~ 4.5 hours; Finally obtain sintered magnet;
7) detect: the magnetic parameter of test products.
Adopt alloy component of the present invention to be raw material, adopt this slab smelting technology, excellent slab tissue can be obtained, slab thickness is 0.25 ~ 0.35mm, the appearance of α-Fe crystal can be suppressed completely, be conducive to the carrying out of follow-up powder process, orientation, sintering, and high performance permanent magnet can be obtained.
Described step 1) in, raw metal also can mix through electromagnetic agitation after melting.
Described step 6) in sintering temperature be 1060 DEG C, constant temperature 3 hours; One-level temperature is 850 DEG C, constant temperature 2 hours; Second annealing temperature is 500 DEG C, constant temperature 3 hours.
Beneficial effect of the present invention is:
(1) slab smelting technology makes slab tissue not have α-Fe crystal, and slab fragmentation is easier, and follow-up powder process is also easier, thus has saved manpower and materials, shortens the production cycle.
(2) corrosion resistance is added while with the addition of zirconium, gallium, cobalt metal element increase magnetic.
Embodiment
Embodiment 1
Get and containing the component of cerium slab magnet and weight percentage be: Pr:6.0 ~ 9.0%, Nd:20.0 ~ 25.0%, B:0.5 ~ 1.5%, Al:0.05 ~ 0.3%, Cu:0.10 ~ 0.2%, Zr:0.1 ~ 0.2%, Ga:0.15 ~ 0.25%, Co:0.1 ~ 0.5%, surplus Fe supplement;
Prepare this preparation method containing cerium slab magnet to comprise the following steps:
1) slab melting: the raw metal of proportioning is in proportion dropped into vacuum induction rapid hardening slab stove, vacuumize, melting at 600 ~ 800 DEG C, be heated to metal Pr when starting to melt, be filled with high-purity argon gas, through ultrasonic mixing after raw metal melts, when after the conjunctiva of alloy molten solution surface, be poured on the water-cooled copper rod of rotation, through being cooled to the slab that thickness is 0.25 ~ 0.35mm fast;
2) hydrogen is pulverized: by step 1) slab that obtains drops into hydrogen crushing furnace, and dehydrogenation at 400 ~ 500 DEG C, obtains the alloying pellet of 100 ~ 110 μm;
3) airflow milling is pulverized: by step 2) alloying pellet that obtains adds in airflow milling under nitrogen protection, is ground into the alloy powder of 3.4 ~ 4.4 μm through airflow milling;
4) magnetic field orientating is shaping: by step 3) alloy powder that obtains drops into Magnetic field press, and oriented moulding under the magnetic field of 1.9T, obtains pressed compact;
5) isostatic pressed: will through step 4) shaping after pressed compact, reinstall in the high pressure chest of isostatic pressing machine, under the pressure of 180-190MPa, keep 10-20s;
6) sinter: will through step 5) pressed compact drop in vacuum sintering furnace, vacuumize, at 1040 ~ 1100 DEG C, constant temperature 2.5 ~ 3.5 hours; One-level temperature is 800 ~ 900 DEG C, constant temperature 1.5 ~ 2.5 hours; Second annealing temperature is 400 ~ 600 DEG C, constant temperature 2.5 ~ 4.5 hours; Finally obtain sintered magnet.
7) detect: the magnetic parameter of test products.
After testing, its key technical indexes reaches following parameter:
Remanent magnetism (Br) 1.40 ~ 1.45T
Magnetic induction coercive force (Hcb) >=1082Ka/m
HCJ (Hcj) >=955Ka/m
Maximum magnetic energy product (BH) max:348 ~ 400KJ/m
3
Embodiment 2
Get and containing the component of cerium slab magnet and weight percentage be:
Pr:7.0 ~ 8.0%, Nd:22.0 ~ 23.0%, B:0.8 ~ 1.2%, Al:0.08 ~ 0.1%, Cu:0.15 ~ 0.2%, Zr:0.18 ~ 0.2%, Ga:0.18 ~ 0.22%, Co:0.2 ~ 0.4%, surplus Fe supplements;
Prepare this preparation method containing cerium slab magnet to comprise the following steps:
1) slab melting: the raw metal of proportioning is in proportion dropped into vacuum induction rapid hardening slab stove, vacuumize, melting at 600 ~ 800 DEG C, be heated to metal Pr when starting to melt, be filled with high-purity argon gas, through ultrasonic mixing after raw metal melts, when after the conjunctiva of alloy molten solution surface, be poured on the water-cooled copper rod of rotation, through being cooled to the slab that thickness is 0.25 ~ 0.35mm fast;
2) hydrogen is pulverized: by step 1) slab that obtains drops into hydrogen crushing furnace, and dehydrogenation at 400 ~ 500 DEG C, obtains the alloying pellet of 100 ~ 110 μm;
3) airflow milling is pulverized: by step 2) alloying pellet that obtains adds in airflow milling under nitrogen protection, is ground into the alloy powder of 3.4 ~ 4.4 μm through airflow milling;
4) magnetic field orientating is shaping: by step 3) alloy powder that obtains drops into Magnetic field press, and oriented moulding under the magnetic field of 1.9T, obtains pressed compact;
5) isostatic pressed: will through step 4) shaping after pressed compact, reinstall in the high pressure chest of isostatic pressing machine, under the pressure of 180-190MPa, keep 10-20s;
6) sinter: will through step 5) pressed compact drop in vacuum sintering furnace, vacuumize, at 1040 ~ 1100 DEG C, constant temperature 2.5 ~ 3.5 hours; One-level temperature is 800 ~ 900 DEG C, constant temperature 1.5 ~ 2.5 hours; Second annealing temperature is 400 ~ 600 DEG C, constant temperature 2.5 ~ 4.5 hours; Finally obtain sintered magnet.
7) detect: the magnetic parameter of test products.
After testing, its key technical indexes reaches following parameter:
Remanent magnetism (Br) 1.40 ~ 1.45T
Magnetic induction coercive force (Hcb) >=1082Ka/m
HCJ (Hcj) >=955Ka/m
Maximum magnetic energy product (BH) max:348 ~ 400KJ/m
3
Embodiment 3
Get and containing the component of cerium slab magnet and weight percentage be:
Pr:7.5%, Nd:22.5%, B:1.0%, Al:0.1%, Cu:0.18%, Zr:0.2%, Ga:0.20%, Co:0.3%, surplus Fe supplements;
Prepare this preparation method containing cerium slab magnet to comprise the following steps:
1) slab melting: the raw metal of proportioning is in proportion dropped into vacuum induction rapid hardening slab stove, vacuumize, melting at 600 ~ 800 DEG C, be heated to metal Pr when starting to melt, be filled with high-purity argon gas, through electromagnetic agitation mixing after raw metal melts, when after the conjunctiva of alloy molten solution surface, be poured on the water-cooled copper rod of rotation, through being cooled to the slab that thickness is 0.25 ~ 0.35mm fast;
2) hydrogen is pulverized: by step 1) slab that obtains drops into hydrogen crushing furnace, and dehydrogenation at 400 ~ 500 DEG C, obtains the alloying pellet of 100 ~ 110 μm;
3) airflow milling is pulverized: by step 2) alloying pellet that obtains adds in airflow milling under nitrogen protection, is ground into the alloy powder of 3.4 ~ 4.4 μm through airflow milling;
4) magnetic field orientating is shaping: by step 3) alloy powder that obtains drops into Magnetic field press, and oriented moulding under the magnetic field of 1.9T, obtains pressed compact;
5) isostatic pressed: will through step 4) shaping after pressed compact, reinstall in the high pressure chest of isostatic pressing machine, under the pressure of 180-190MPa, keep 10-20s;
6) sinter: will through step 5) pressed compact drop in vacuum sintering furnace, vacuumize, at 1040 ~ 1100 DEG C, constant temperature 2.5 ~ 3.5 hours; One-level temperature is 800 ~ 900 DEG C, constant temperature 1.5 ~ 2.5 hours; Second annealing temperature is 400 ~ 600 DEG C, constant temperature 2.5 ~ 4.5 hours; Finally obtain sintered magnet.
7) detect: the magnetic parameter of test products.
After testing, its key technical indexes reaches following parameter:
Remanent magnetism (Br) 1.40 ~ 1.45T
Magnetic induction coercive force (Hcb) >=1082Ka/m
HCJ (Hcj) >=955Ka/m
Maximum magnetic energy product (BH) max:348 ~ 400KJ/m
3
Embodiment 4
Get and containing the component of cerium slab magnet and weight percentage be:
Pr:6.0%, Nd:20.0%, B:1.5%, Al:0.3%, Cu:0.10%, Zr:0.2%, Ga:0.15%, Co:0.1%, surplus Fe supplements;
Prepare this preparation method containing cerium slab magnet to comprise the following steps:
1) slab melting: the raw metal of proportioning is in proportion dropped into vacuum induction rapid hardening slab stove, vacuumize, melting at 800 DEG C, be heated to metal Pr when starting to melt, be filled with high-purity argon gas, through electromagnetic agitation mixing after raw metal melts, when after the conjunctiva of alloy molten solution surface, be poured on the water-cooled copper rod of rotation, through being cooled to the slab that thickness is 0.25 ~ 0.35mm fast;
2) hydrogen is pulverized: by step 1) slab that obtains drops into hydrogen crushing furnace, and dehydrogenation at 540 DEG C, obtains the alloying pellet of 100 ~ 110 μm;
3) airflow milling is pulverized: by step 2) alloying pellet that obtains adds in airflow milling under nitrogen protection, is ground into the alloy powder of 3.4 ~ 4.4 μm through airflow milling;
4) magnetic field orientating is shaping: by step 3) alloy powder that obtains drops into Magnetic field press, and oriented moulding under the magnetic field of 1.9T, obtains pressed compact;
5) isostatic pressed: will through step 4) shaping after pressed compact, reinstall in the high pressure chest of isostatic pressing machine, under the pressure of 190-200MPa, keep 10-20s;
6) sinter: will through step 5) pressed compact drop in vacuum sintering furnace, vacuumize, at 1100 DEG C, constant temperature 3 hours; One-level temperature is 800 DEG C, constant temperature 2 hours; Second annealing temperature is 600 DEG C, constant temperature 3 hours; Finally obtain sintered magnet.
7) detect: the magnetic parameter of test products.
After testing, its key technical indexes reaches following parameter:
Remanent magnetism (Br) 1.40 ~ 1.45T
Magnetic induction coercive force (Hcb) >=1082Ka/m
HCJ (Hcj) >=955Ka/m
Maximum magnetic energy product (BH) max:348 ~ 400KJ/m
3
Embodiment 5
Get and containing the component of cerium slab magnet and weight percentage be: Pr:8.0%, Nd:23.0%, B:0.8%, Al:0.08%, Cu:0.2%, Zr:0.18%, Ga:0.18%, Co:0.4%, surplus Fe supplement;
Prepare this preparation method containing cerium slab magnet to comprise the following steps:
1) slab melting: the raw metal of proportioning is in proportion dropped into vacuum induction rapid hardening slab stove, vacuumize, melting at 1000 DEG C, be heated to metal Pr when starting to melt, be filled with high-purity argon gas, through ultrasonic mixing after raw metal melts, when after the conjunctiva of alloy molten solution surface, be poured on the water-cooled copper rod of rotation, through being cooled to the slab that thickness is 0.25 ~ 0.35mm fast;
2) hydrogen is pulverized: by step 1) slab that obtains drops into hydrogen crushing furnace, and dehydrogenation at 540 DEG C, obtains the alloying pellet of 100 ~ 110 μm;
3) airflow milling is pulverized: by step 2) alloying pellet that obtains adds in airflow milling under nitrogen protection, is ground into the alloy powder of 3.4 ~ 4.4 μm through airflow milling;
4) magnetic field orientating is shaping: by step 3) alloy powder that obtains drops into Magnetic field press, and oriented moulding under the magnetic field of 1.9T, obtains pressed compact;
5) isostatic pressed: will through step 4) shaping after pressed compact, reinstall in the high pressure chest of isostatic pressing machine, under the pressure of 190-200MPa, keep 10-20s;
6) sinter: will through step 5) pressed compact drop in vacuum sintering furnace, vacuumize, at 1040 DEG C, constant temperature 3.5 hours; One-level temperature is 800 DEG C, constant temperature 1.5 hours; Second annealing temperature is 400 DEG C, constant temperature 2.5 hours; Finally obtain sintered magnet.
7) detect: the magnetic parameter of test products.
After testing, its key technical indexes reaches following parameter:
Remanent magnetism (Br) 1.40 ~ 1.45T
Magnetic induction coercive force (Hcb) >=1082Ka/m
HCJ (Hcj) >=955Ka/m
Maximum magnetic energy product (BH) max:348 ~ 400KJ/m
3
Above content is in conjunction with concrete preferred implementation further description made for the present invention; can not assert that the specific embodiment of the present invention is only limitted to this; for general technical staff of the technical field of the invention; without departing from the inventive concept of the premise; some simple deduction or replace can also be made, all should be considered as belonging to the present invention by submitted to claims determination scope of patent protection.
Claims (6)
1. containing a gallium slab magnet, it is characterized in that: slab magnet component and weight percentage are: Pr:6.0 ~ 9.0%, Nd:20.0 ~ 25.0%, B:0.5 ~ 1.5%, Al:0.05 ~ 0.3%, Cu:0.10 ~ 0.2%, Zr:0.1 ~ 0.2%, Ga:0.15 ~ 0.25%, Co:0.1 ~ 0.5%, surplus Fe supplement.
2. a kind of containing gallium slab magnet according to claim 1, it is characterized in that: slab magnet component and weight percentage are: Pr:7.0 ~ 8.0%, Nd:22.0 ~ 23.0%, B:0.8 ~ 1.2%, Al:0.08 ~ 0.1%, Cu:0.15 ~ 0.2%, Zr:0.18 ~ 0.2%, Ga:0.18 ~ 0.22%, Co:0.2 ~ 0.4%, surplus Fe supplement.
3. a kind of containing gallium slab magnet according to claim 1, it is characterized in that: slab magnet component and weight percentage are: Pr:7.5%, Nd:22.5%, B:1.0%, Al:0.1%, Cu:0.18%, Zr:0.2%, Ga:0.20%, Co:0.3%, surplus Fe supplement.
4. prepare the arbitrary a kind of described method containing gallium slab magnet of claim 1-3, comprise the following steps:
1) slab melting: the raw metal of proportioning is in proportion dropped into vacuum induction rapid hardening slab stove, vacuumize, melting at 600 ~ 800 DEG C, be heated to metal Pr when starting to melt, be filled with high-purity argon gas, through ultrasonic mixing after raw metal melts, when after the conjunctiva of alloy molten solution surface, be poured on the water-cooled copper rod of rotation, through being cooled to the slab that thickness is 0.25 ~ 0.35mm fast;
2) hydrogen is pulverized: by step 1) slab that obtains drops into hydrogen crushing furnace, and dehydrogenation at 400 ~ 500 DEG C, obtains the alloying pellet of 100 ~ 110 μm;
3) airflow milling is pulverized: by step 2) alloying pellet that obtains adds in airflow milling under nitrogen protection, is ground into the alloy powder of 3.4 ~ 4.4 μm through airflow milling;
4) magnetic field orientating is shaping: by step 3) alloy powder that obtains drops into Magnetic field press, and oriented moulding under the magnetic field of 1.9T, obtains pressed compact;
5) isostatic pressed: will through step 4) shaping after pressed compact, reinstall in the high pressure chest of isostatic pressing machine, under the pressure of 180-190MPa, keep 10-20s;
6) sinter: will through step 5) pressed compact drop in vacuum sintering furnace, vacuumize, at 1040 ~ 1100 DEG C, constant temperature 2.5 ~ 3.5 hours; One-level temperature is 800 ~ 900 DEG C, constant temperature 1.5 ~ 2.5 hours; Second annealing temperature is 400 ~ 600 DEG C, constant temperature 2.5 ~ 4.5 hours; Finally obtain sintered magnet.
5. a kind of preparation method containing gallium slab magnet according to claim 4, is characterized in that: described step 1) in, raw metal mixes through electromagnetic agitation after melting.
6. a kind of preparation method containing gallium slab magnet according to claim 4, is characterized in that: described step 6) in sintering temperature be 1060 DEG C, constant temperature 3 hours; One-level temperature is 850 DEG C, constant temperature 2 hours; Second annealing temperature is 500 DEG C, constant temperature 3 hours.
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Cited By (2)
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CN105741995A (en) * | 2016-04-27 | 2016-07-06 | 宁波耐力誉磁业科技有限公司 | High-performance sintered neodymium-iron-boron permanent magnet and preparation method thereof |
CN110257724A (en) * | 2019-07-16 | 2019-09-20 | 宁德市星宇科技有限公司 | A kind of preparation method of the neodymium iron boron magnetic body containing lanthanum and cerium |
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US20130038159A1 (en) * | 2011-08-09 | 2013-02-14 | Jinfang Liu | Methods for sequentially laminating rare earth permanent magnets with suflide-based dielectric layer |
CN104143403A (en) * | 2014-07-31 | 2014-11-12 | 宁波科田磁业有限公司 | Manufacturing method for improving magnetic performance of sintered neodymium-iron-boron magnet |
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US20130038159A1 (en) * | 2011-08-09 | 2013-02-14 | Jinfang Liu | Methods for sequentially laminating rare earth permanent magnets with suflide-based dielectric layer |
CN102592777A (en) * | 2012-03-15 | 2012-07-18 | 宁德市星宇科技有限公司 | Low-cost sintered neodymium iron boron magnet and production method thereof |
CN104143403A (en) * | 2014-07-31 | 2014-11-12 | 宁波科田磁业有限公司 | Manufacturing method for improving magnetic performance of sintered neodymium-iron-boron magnet |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
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CN105741995A (en) * | 2016-04-27 | 2016-07-06 | 宁波耐力誉磁业科技有限公司 | High-performance sintered neodymium-iron-boron permanent magnet and preparation method thereof |
CN105741995B (en) * | 2016-04-27 | 2017-07-28 | 宁波耐力誉磁业科技有限公司 | A kind of high performance sintered neodymium-iron-boron permanent magnet and preparation method thereof |
CN110257724A (en) * | 2019-07-16 | 2019-09-20 | 宁德市星宇科技有限公司 | A kind of preparation method of the neodymium iron boron magnetic body containing lanthanum and cerium |
CN110257724B (en) * | 2019-07-16 | 2020-05-22 | 宁德市星宇科技有限公司 | Preparation method of neodymium-iron-boron magnet containing lanthanum and cerium |
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