CN104821226A - Method for making high-square-degree sintered NdFeB permanent magnets with cerium, titanium, cobalt and zirconium compound additive - Google Patents

Method for making high-square-degree sintered NdFeB permanent magnets with cerium, titanium, cobalt and zirconium compound additive Download PDF

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Publication number
CN104821226A
CN104821226A CN201510230486.2A CN201510230486A CN104821226A CN 104821226 A CN104821226 A CN 104821226A CN 201510230486 A CN201510230486 A CN 201510230486A CN 104821226 A CN104821226 A CN 104821226A
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sintered
temperature
alloy
zirconium compound
permanent magnets
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张亚波
何进
史世文
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Anhui One Magnet Electronic Co Ltd
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Anhui One Magnet Electronic Co Ltd
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Abstract

The invention discloses a method for making high-square-degree sintered NdFeB permanent magnets with a cerium, titanium, cobalt and zirconium compound additive. The method comprises the steps that raw materials are prepared with 27.0% to 29.0% of Nd, 2.5% to 4.0% of Ce, 63.5% to 67.5% of Fe, 1.0% to 1.2% of B, 0.5% to 1.0% of Nb, 1.0% to 3.0% of Co, 0.1% to 0.3% of Zr, 10.5% to 1.0% of A, 0.1% to 0.3% of Cu, and 0.1% to 0.3% of Ti, the raw materials are smelted under the temperature of 1380 DEG with a vacuum induction rapid-hardening casting strip furnace, smelted alloy liquid is processed through electromagnetic stirring to be uniform, and is poured to a rotating water-cooling copper stick, and the alloy liquid is rapidly cooled to form alloy slices with the thickness ranging from 0.2 mm to 0.5 mm; NdFeB alloy slices are broken into NdFeB alloy particles with the length ranging from 120 microns to 200 microns with a hydrogen breaking furnace; the particles are further broken into NdFeB alloy powder with the length ranging from 3.0 microns to 4.5 microns by an air-current mill; the powder is formed in a forming press, and is further densified through isostatic cool pressing; formed initial blanks are sintered, and sintered permanent magnets are finally obtained. With the method for making high-square-degree sintered NdFeB permanent magnets with the cerium, titanium, cobalt and zirconium compound additive, the squre degree of the permanent magnets can be improved, and the production cost can be greatly reduced.

Description

A kind of cerium titanium cobalt zirconium compound adds the method for the high squareness sintered Nd-Fe-B permanent magnet of preparation
Technical field
The present invention relates to technical field of magnetic materials, be specifically related to a kind of method that cerium titanium cobalt zirconium compound adds the high squareness sintered Nd-Fe-B permanent magnet of preparation.
Background technology
NdFeB series permanent magnetic material is the practical permanent magnetic material that the magnetic property that finds up to now is the highest.Current China neodymium iron boron output accounts for more than 60% of the whole world, estimate that its range of application following and the market demand will continuous enlargement, the demand of neodymium iron boron industry to rare earth element nd is large, and annual about to go up with the speed of amplification 20%, seek the alternative metals of Nd or to explore permanent magnet of new generation extremely urgent.
The reserves of occurring in nature Ce element far more than Nd element, Nd, Ce element mainly with mineral intergrowth form exist, industrial separation purify cost compared with high, difficulty is large.Rare earth metal Ce is lower than the rare earth metal Nd-Pr alloy market price, and thus CeFeB permanent-magnet alloy has obvious price advantage compared with (Pr, Nd) FeB permanent-magnet alloy.Research shows, Ce 2fe 14b at room temperature has higher ferromagnetism, and the rich Ce in Nd-rich phase compares rich-Nd phase has better mobility, can prepare the permanent magnet that density is high, structural integrity is good.This fundamentally improves the squareness of permanent magnet J-H demagnetization curve.Squareness as one of the magnetic parameter of sintered Nd-Fe-B permanent magnet, by magnet chemical composition, crystal structure crystal orientation degree, microstructure alloy, etc. affect.
But Ce 2fe 14the magnetic moment J of B swith anisotropy field H aall far below Nd 2fe 14b, strictly must control the doping of cerium, the magnetic property that guarantee permanent magnet is higher.The present invention, by the cerium of doping suitable dose, while guarantee magnetic property is up to standard, reduces the consumption of praseodymium neodymium, prepares the permanent magnet that squareness is very high.
Summary of the invention
A kind of cerium titanium cobalt zirconium compound is the object of the present invention is to provide to add the method for the high squareness sintered Nd-Fe-B permanent magnet of preparation, substantially improve the squareness (Hk/Hcj >=97%) of sintered Nd-Fe-B permanent magnet, the sintered Nd-Fe-B permanent magnet density of preparation is high, structural integrity good.
For achieving the above object, the technical solution adopted in the present invention is:
Cerium titanium cobalt zirconium compound adds a method for the high squareness sintered Nd-Fe-B permanent magnet of preparation, comprises the following steps:
(1) utilize vacuum induction rapid hardening slab stove that raw material metal good for proportioning is carried out melting at 1200-400 DEG C of temperature; before melting, furnace chamber first vacuumizes; be filled with protective gas high-purity argon gas again; aluminium alloy after raw material fusing is even through electromagnetic agitation; be poured on the water-cooled copper rod of rotation, alloy solution is 10 2-10 4dEG C/cooling rate of s under cooling forms thickness is fast the alloy sheet of 0.2-0.5mm;
(2) utilize hydrogen crushing furnace, under 0.1MPa hydrogen-pressure, inhale hydrogen, dehydrogenation at 550 DEG C of temperature, Nd Fe B alloys thin slice is broken into the Nd Fe B alloys particle of 120-200 μm;
(3) particle step (2) obtained is broken into the Nd Fe B alloys powder of 3.0-4.5 μm further across airflow milling;
(4) utilize Magnetic field press, by powder oriented moulding under the magnetic field of 1.8T in step (3), then through isostatic cool pressing, pressure is 200MPa, and the first base density obtained is 4.5-5.0g/cm 3;
(5) pressed compact is placed in vacuum sintering furnace, at 1060-1100 DEG C of sintered heat insulating 3-4 hour; One-level temperature is 850-950 DEG C, insulation 1-2 hour; Second annealing temperature is 500-600 DEG C, insulation 3-4 hour; Final acquisition sintered permanent magnet.
The composition proportion of raw material metal described in step (1) is Nd be 27.0-29.0%, Ce be 2.5-4.0%, Fe be 63.5-67.5%, B be 1.0-1.2%, Nb be 0.5-1.0%, Co be 1.0-3.0%, Zr be 0.1-0.3%, Al be 0.5-1.0%, Cu be 0.1-0.3%, Ti is 0.1-0.3%.
Described in step (5), sintering temperature is preferably 1060 DEG C, and sintering time is preferably 4 hours; One-level temperature is preferably 850 DEG C, and temperature retention time is preferably 1.5 hours; Second annealing temperature is preferably 460 DEG C, and temperature retention time is preferably 4 hours.
Compared with prior art, the invention has the beneficial effects as follows:
The present invention discloses the positive role of cerium in NbFeB sintered permanent magnet, and substantially improve the squareness (Hk/Hcj >=97%) of permanent magnet, the permanent magnet density of preparation is high, structural integrity good.By the cerium of suitable dose of adulterating, while guarantee magnetic property is up to standard, reduces the consumption of praseodymium neodymium, prepare the permanent magnet that squareness is very high.
Embodiment
Embodiments of the invention are only for illustration of technical scheme of the present invention, and non-limiting the present invention.
Embodiment one
The nominal mass percentage of the present embodiment neodymium iron boron magnetic body is Nd 25.5%, Ce 4.0%, Fe 65.55%, B 1%, Nb 0.75%, Co 2%, Zr 0.1%, Al 0.7%, Cu 0.1%, Ti 0.3%.Utilize vacuum induction rapid hardening slab stove that raw material metal good for proportioning is carried out vacuum melting at the temperature of 1380 DEG C.Before melting, furnace chamber first vacuumizes, then is filled with protective gas high-purity argon gas.Aluminium alloy after raw material fusing is even through electromagnetic agitation, and be poured on the water-cooled copper rod of rotation, alloy solution is 10 2-10 4dEG C/cooling rate of s under cooling forms thickness is fast the alloy sheet of 0.2-0.5mm.Utilize hydrogen crushing furnace, under 0.1MPa hydrogen-pressure, inhale hydrogen, dehydrogenation at 550 DEG C of temperature, Nd Fe B alloys thin slice is broken into the Nd Fe B alloys particle of about 120-200 μm.Particle after hydrogen fragmentation is broken into the Nd Fe B alloys powder of 3.0-4.5 μm further across airflow milling.Utilize Magnetic field press, by the oriented moulding under the magnetic field of 1.8T of the powder after airflow milling, then through isostatic cool pressing, pressure is 200MPa, and the first base density obtained is 4.5-5.0g/cm 3.Pressed compact is placed in vacuum sintering furnace, 1060 DEG C of sintered heat insulatings 4 hours; One-level temperature is 850 DEG C, is incubated 1.5 hours; Second annealing temperature is 460 DEG C, is incubated 4 hours; Final acquisition sintered permanent magnet.
Embodiment two
The nominal mass percentage of the present embodiment neodymium iron boron magnetic body is Nd 27%, Ce 2.5%, Fe 65.55%, B1%, Nb 0.75%, Co 2%, Zr 0.1%, Al 0.7%, Cu 0.1%, Ti 0.3%.Utilize vacuum induction rapid hardening slab stove that raw material metal good for proportioning is carried out vacuum melting at the temperature of 1380 DEG C.Before melting, furnace chamber first vacuumizes, then is filled with protective gas high-purity argon gas.Aluminium alloy after raw material fusing is even through electromagnetic agitation, and be poured on the water-cooled copper rod of rotation, alloy solution is 10 2-10 4dEG C/cooling rate of s under cooling forms thickness is fast the alloy sheet of 0.2-0.5mm.Utilize hydrogen crushing furnace, under 0.1MPa hydrogen-pressure, inhale hydrogen, dehydrogenation at 550 DEG C of temperature, Nd Fe B alloys thin slice is broken into the Nd Fe B alloys particle of about 120-200 μm.Particle after hydrogen fragmentation is broken into the Nd Fe B alloys powder of 3.0-4.5 μm further across airflow milling.Utilize Magnetic field press, by the oriented moulding under the magnetic field of 1.8T of the powder after airflow milling, then through isostatic cool pressing, pressure is 200MPa, and the first base density obtained is 4.5-5.0g/cm 3.Pressed compact is placed in vacuum sintering furnace, 1060 DEG C of sintered heat insulatings 4 hours; One-level temperature is 850 DEG C, is incubated 1.5 hours; Second annealing temperature is 460 DEG C, is incubated 4 hours; Final acquisition sintered permanent magnet.

Claims (3)

1. cerium titanium cobalt zirconium compound adds a method for the high squareness sintered Nd-Fe-B permanent magnet of preparation, it is characterized in that comprising the following steps:
(1) utilize vacuum induction rapid hardening slab stove that raw material metal good for proportioning is carried out melting at 1200-400 DEG C of temperature; before melting, furnace chamber first vacuumizes; be filled with protective gas high-purity argon gas again; aluminium alloy after raw material fusing is even through electromagnetic agitation; be poured on the water-cooled copper rod of rotation, alloy solution is 10 2-10 4dEG C/cooling rate of s under cooling forms thickness is fast the alloy sheet of 0.2-0.5mm;
(2) utilize hydrogen crushing furnace, under 0.1MPa hydrogen-pressure, inhale hydrogen, dehydrogenation at 550 DEG C of temperature, Nd Fe B alloys thin slice is broken into the Nd Fe B alloys particle of 120-200 μm;
(3) particle step (2) obtained is broken into the Nd Fe B alloys powder of 3.0-4.5 μm further across airflow milling;
(4) utilize Magnetic field press, by powder oriented moulding under the magnetic field of 1.8T in step (3), then through isostatic cool pressing, pressure is 200MPa, and the first base density obtained is 4.5-5.0g/cm 3;
(5) pressed compact is placed in vacuum sintering furnace, at 1060-1100 DEG C of sintered heat insulating 3-4 hour; One-level temperature is 850-950 DEG C, insulation 1-2 hour; Second annealing temperature is 500-600 DEG C, insulation 3-4 hour; Final acquisition sintered permanent magnet.
2. add the method for the high squareness sintered Nd-Fe-B permanent magnet of preparation according to a kind of cerium titanium cobalt zirconium compound described in claim 1, it is characterized in that: the composition proportion of raw material metal described in step (1) is Nd be 27.0-29.0%, Ce be 2.5-4.0%, Fe be 63.5-67.5%, B be 1.0-1.2%, Nb be 0.5-1.0%, Co be 1.0-3.0%, Zr be 0.1-0.3%, Al be 0.5-1.0%, Cu be 0.1-0.3%, Ti is 0.1-0.3%.
3. add the method for the high squareness sintered Nd-Fe-B permanent magnet of preparation according to a kind of cerium titanium cobalt zirconium compound described in claim 1, it is characterized in that: described in step (5), sintering temperature is preferably 1060 DEG C, and sintering time is preferably 4 hours; One-level temperature is preferably 850 DEG C, and temperature retention time is preferably 1.5 hours; Second annealing temperature is preferably 460 DEG C, and temperature retention time is preferably 4 hours.
CN201510230486.2A 2015-05-07 2015-05-07 Method for making high-square-degree sintered NdFeB permanent magnets with cerium, titanium, cobalt and zirconium compound additive Pending CN104821226A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105118656A (en) * 2015-09-16 2015-12-02 安徽万磁电子有限公司 Method for preparing low-cost sintered NdFeB permanent magnet containing rare-earth cerium
CN105140020A (en) * 2015-09-16 2015-12-09 安徽万磁电子有限公司 Method for improving machining performance of sintered neodymium iron boron magnet
CN106601460A (en) * 2016-12-09 2017-04-26 京磁材料科技股份有限公司 Cerium- and cobalt-doped sintered NdFeB magnet and preparation method thereof
CN114121473A (en) * 2021-11-15 2022-03-01 江苏科技大学 Sintered neodymium iron boron magnet rapid hardening sheet casting device and method thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101552063A (en) * 2008-12-09 2009-10-07 宁波同创强磁材料有限公司 High-performance neodymium-iron-boron magnet with composite addition of titanium and zirconium
CN104347218A (en) * 2014-10-30 2015-02-11 浙江鑫盛永磁科技有限公司 Novel sintered ndfeb permanent magnet and preparation method thereof
CN104376944A (en) * 2014-11-21 2015-02-25 北矿磁材科技股份有限公司 Rare earth iron boron magnetic powder, rare earth iron boron magnet and preparation method of rare earth iron boron magnetic powder

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101552063A (en) * 2008-12-09 2009-10-07 宁波同创强磁材料有限公司 High-performance neodymium-iron-boron magnet with composite addition of titanium and zirconium
CN104347218A (en) * 2014-10-30 2015-02-11 浙江鑫盛永磁科技有限公司 Novel sintered ndfeb permanent magnet and preparation method thereof
CN104376944A (en) * 2014-11-21 2015-02-25 北矿磁材科技股份有限公司 Rare earth iron boron magnetic powder, rare earth iron boron magnet and preparation method of rare earth iron boron magnetic powder

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105118656A (en) * 2015-09-16 2015-12-02 安徽万磁电子有限公司 Method for preparing low-cost sintered NdFeB permanent magnet containing rare-earth cerium
CN105140020A (en) * 2015-09-16 2015-12-09 安徽万磁电子有限公司 Method for improving machining performance of sintered neodymium iron boron magnet
CN106601460A (en) * 2016-12-09 2017-04-26 京磁材料科技股份有限公司 Cerium- and cobalt-doped sintered NdFeB magnet and preparation method thereof
CN114121473A (en) * 2021-11-15 2022-03-01 江苏科技大学 Sintered neodymium iron boron magnet rapid hardening sheet casting device and method thereof
CN114121473B (en) * 2021-11-15 2024-03-12 江苏科技大学 Sintered NdFeB magnet rapid hardening sheet casting device and method

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Application publication date: 20150805