CN108806910A - Improve the coercitive method of neodymium-iron-boron magnetic material - Google Patents
Improve the coercitive method of neodymium-iron-boron magnetic material Download PDFInfo
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- CN108806910A CN108806910A CN201710310266.XA CN201710310266A CN108806910A CN 108806910 A CN108806910 A CN 108806910A CN 201710310266 A CN201710310266 A CN 201710310266A CN 108806910 A CN108806910 A CN 108806910A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
- H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
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- 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
Abstract
The invention discloses a kind of coercitive methods of raising neodymium-iron-boron magnetic material, including：Sintered NdFeB magnetic powder is provided as major phase material；Heavy rare earth-ferroalloy ingot casting is provided, and HDDR processing is carried out to the heavy rare earth-ferroalloy ingot casting, obtains the heavy rare earth manocrystalline powders as auxiliary phase material；The sintered NdFeB magnetic powder is uniformly mixed with heavy rare earth manocrystalline powders, is sintered, makes annealing treatment later, obtains the neodymium-iron-boron magnetic material of high-coercive force.The heavy rare earth manocrystalline powders that the present invention is handled using HDDR are as structurally-modified alloy, regulate and control the distribution of heavy rare earth element while improving crystal ingedient and structure, using the grain growth of liquid sintering process the shell structurre of heavy rare earth is formed on the surface layer of crystal grain, so as to greatly improve the coercivity of magnet under the premise of ensureing high remanent magnetism, and improve the utilization rate of heavy rare earth element.
Description
Technical field
Present invention relates particularly to a kind of coercitive methods of raising neodymium-iron-boron magnetic material, belong to magnetic material technology neck
Domain.
Background technology
Neodymium-iron-boron magnetic material is can to realize the best magnetic material of the magnetic property of industrialized production at present, extensively
Applied to the every field in production and living.However it is limited by its lower Curie temperature (310 DEG C~510 DEG C), in some height
Magnetic property drastically deteriorates in warm environment, can no longer meet usage requirement.And the coercivity of neodymium-iron-boron magnetic material is improved, it can disappear
Remove or reduce its magnetic loss of energy at relatively high temperatures.
The raising coercitive method of sintered NdFeB magnet, which is mainly included in molten alloy, at present directly adds heavy rare earth
The methods of element, crystal grain refinement and diffusion.
Wherein, although directly addition heavy rare earth element can promote coercivity, it is in Nd2Fe14B (referred to as 2:14:1) main
Antiferromagnetic coupling is formed with Fe in phase, its remanent magnetism is caused to significantly reduce.On the other hand, melting addition heavy rare earth element promotes coercive
The efficiency of power is not high, and by taking Dy as an example, every 1% mass ratio addition coercivity promotes about 2kOe.
Diffusion is to improve another important method of coercivity of sintered ndfeb, and principle is mainly by atom in high temperature
Under travel motion realize different location atomic concentration change.It is dilute that rich weight can be formed in Grain Surface using the method for diffusion
Soil 2:14:The shell structurre of 1 phase package, reduces the magnetic reversal forming core of grain boundary, in the premise for influencing very little on remanent magnetism
Under coercivity is substantially improved.However, being limited to diffusion depth, diffusion is normally only used for processing thin slice magnet sample, to big
The coercitive promotion of block magnet is without positive effect.
Invention content
It is existing to overcome the main purpose of the present invention is to provide a kind of coercitive method of raising neodymium-iron-boron magnetic material
Deficiency in technology.
For realization aforementioned invention purpose, the technical solution adopted by the present invention includes：
An embodiment of the present invention provides a kind of coercitive methods of raising neodymium-iron-boron magnetic material comprising：
Sintered NdFeB magnetic powder as major phase material is provided；
Heavy rare earth-ferroalloy ingot casting is provided, and HDDR processing is carried out to the heavy rare earth-ferroalloy ingot casting, it is dilute to obtain weight
Native manocrystalline powders, HDDR processing include the hydrogenation carried out successively, disproportionation, dehydrogenation and combined processing again；
The sintered NdFeB magnetic powder is uniformly mixed with heavy rare earth manocrystalline powders, is sintered, makes annealing treatment later,
Obtain the neodymium-iron-boron magnetic material of high-coercive force.
In some preferred embodiments, the method includes：It is 1 according to the atomic ratio of heavy rare earth element and ferro element:2
~1:3, heavy rare earth metal simple substance and iron simple substance are subjected to melting under inert gas protection, and cooling, obtain heavy rare earth-iron and close
Golden ingot casting.
Further, the heavy rare earth element includes dysprosium and/or terbium.
Compared with prior art, advantages of the present invention at least that：
1. the coercitive method of raising neodymium-iron-boron magnetic material provided by the invention uses HDDR reaction treatment rare-earth-irons
Object is closed, heavy rare earth manocrystalline powders are obtained, compared to the preparation process of other particles containing rare-earth nano-crystal, process equipment letter
Single, condition easily meets and can prepare on a large scale；
2. the heavy rare earth nanometer provided by the invention for improving the coercitive method of neodymium-iron-boron magnetic material and utilizing HDDR processing
Crystalline substance is used as structurally-modified alloy, and the distribution of heavy rare earth element can be regulated and controled while improving crystal ingedient and structure.Using receiving
The tiny feature of the brilliant particle of rice enhances its dispersibility around magnetic powder particle, it is made to realize that weight is dilute in liquid sintering process
Uniform diffusion of the native atom to main phase superficial layer forms the shell structurre of heavy rare earth element enriched surface layer, reaches and is ensureing high remain
The coercivity of magnet is improved under the premise of magnetic, and then improves the utilization rate of heavy rare earth element；
3. the coercitive method of raising neodymium-iron-boron magnetic material provided by the invention uses HDDR techniques, product to be had
Nanocrystalline structure and easily separated.In practical applications, it may be used airflow milling, the general industries mode of production such as ball milling, or even
Hand lapping under gas is protected to detach；
4. the coercitive method of raising neodymium-iron-boron magnetic material provided by the invention is with obvious effects for coercitive promotion,
By taking dysprosium as an example, every 1% mass fraction dysprosium addition can promote 3.59kOe.
Description of the drawings
Fig. 1 is magnet after original magnet and the Dy-Fe nanometer crystal powders of the different Dy contents of addition in the embodiment of the present invention 1
Magnetism testing curve graph；
Fig. 2 is magnet after original magnet and the Dy-Fe nanometer crystal powders of the different Dy contents of addition in the embodiment of the present invention 2
Magnetism testing curve graph；
Fig. 3 is magnet after original magnet and the Tb-Fe nanometer crystal powders of the different Tb contents of addition in the embodiment of the present invention 3
Magnetism testing curve graph；
Fig. 4, Fig. 5 are the SEM figures for handling heavy rare earth nano-crystalline granule obtained in the embodiment of the present invention 1 by HDDR.
Specific implementation mode
In recent years, there are many promote coercitive report about using the non magnetic auxiliary phase modification crystal boundary of intergranular addition low melting point
Road.Its mechanism of action can simply be summarized as fusing point and form liquid phase in sintering process less than the auxiliary phase of nonferromagnetic of sintering temperature,
While lubricating crystal grain, eliminating Grain Surface defect and corner angle, good separated magnetic effect is formed in intercrystalline, is carried to reach
Rise coercitive effect.As it can be seen that suitable intergranular additive enough in sintering process can play preferably magnet microstructure
Modification.
For many defects of the prior art, inventor proposes the skill of the present invention through studying for a long period of time and largely putting into practice
Art scheme as follows will be further explained the technical solution, its implementation process and principle etc..It is understood, however, that
Within the scope of the present invention, above-mentioned each technical characteristic of the invention and each technical characteristic for specifically describing in (embodiment) below it
Between can be combined with each other, to constitute new or preferred technical side's scheme.Due to space limitations, I will not repeat them here.
A kind of coercitive method of raising neodymium-iron-boron magnetic material of the offer of the embodiment of the present invention includes：
Sintered NdFeB magnetic powder as major phase material is provided；
Heavy rare earth-ferroalloy ingot casting is provided, and HDDR processing is carried out to the heavy rare earth-ferroalloy ingot casting, it is dilute to obtain weight
Native manocrystalline powders, HDDR processing include the hydrogenation carried out successively, disproportionation, dehydrogenation and combined processing again；
The sintered NdFeB magnetic powder is uniformly mixed with heavy rare earth manocrystalline powders, is sintered, makes annealing treatment later,
Obtain the neodymium-iron-boron magnetic material of high-coercive force.
Further, aforementioned HDDR processes include inhaling hydrogen-disproportionation-dehydrogenation-(hydrogenation-compound again
Disproportionation-desorption-recombination, abbreviation HDDR) four-stage, dominant mechanism is
Rare earth atom reacts at high temperature with hydrogen generates tiny hydride and other object phase little particles, in dehydrogenation again recombination process
The nanocrystalline of size uniformity is generated in such a way that forming core is grown up.
One of preferably, the method includes：It is 1 according to the atomic ratio of heavy rare earth element and ferro element:2~1:
3, heavy rare earth metal simple substance and iron simple substance are subjected to melting under inert gas protection, and cooling, obtain heavy rare earth-ferroalloy casting
Ingot.
Preferably, the temperature-gravity rare earth metal simple substance of the melting and the single-phase liquidus curve of iron simple substance be higher by 50 DEG C with
On.
Preferably, the heavy rare earth element can be dysprosium, terbium etc..
Wherein, the heavy rare earth melted under inert gas protection-ferroalloy ingot casting should be quickly cooled down as far as possible, or follow-up
Segregation is eliminated in annealing heat-treats.
Preferably, the melting and cooling technique include near quick setting slab or the cooling of induction melting copper mold.
Wherein, using in the hydrogenation process of hydrogen heat-treatment furnace counterweight rare earth-iron alloy ingot casting progress, at least ensure hydrogen pressure
In 50kPa or more, to ensure enough suction hydrogen.
In some preferred embodiments, in HDDR processing procedures, the heavy rare earth-ferroalloy ingot casting can be placed in
Pressure is saturated in the hydrogen atmosphere of 50kPa or more inhales hydrogen, completes hydrogenation treatment, obtains heavy rare earth-ferroalloy powder.
More specifically, the aforementioned heavy rare earth-ferroalloy ingot casting provided in the present invention passes through saturation in HDDR reaction process
The powder to form about 10~100 μm or so of grain size can be crushed to completely by inhaling hydrogen, thick there is no need to carry out any early period to ingot casting
It is broken.
In some preferred embodiments, in HDDR processing procedures, hydrogenated treated heavy rare earth-iron can be closed
Bronze end handles 2h or more in the hydrogen atmosphere that pressure is 50kPa~150kPa in 700 DEG C~900 DEG C, completes disproportionation processing.
Preferably, the time of the disproportionation processing is 2~3h.
Further, by taking dysprosium and terbium as an example, more preferred hydrogen pressure is 100kPa, and furnace body temperature is 780 DEG C~840 DEG C,
The disproportionated reaction time is 3h.
In some preferred embodiments, in HDDR processing procedures, it can will be closed through disproportionation treated heavy rare earth-iron
Bronze end carries out Dehydroepiandrosterone derivative in the vacuum environment that pressure is 50~100Pa under 700~900 DEG C of temperature condition, i.e., low true
De- multiple (slow dehydrogenation) processing of sky.
Preferably, the temperature of the Dehydroepiandrosterone derivative be 780 DEG C~840 DEG C, pressure be 50~100Pa, the time be 1~
1.5h。
It, can be by heavy rare earth-iron after low vacuum treatment in HDDR processing procedures in some preferred embodiments
Alloy powder is 10 in Hydrogen Vapor Pressure-130min or more is handled in environment below under 700 DEG C~900 DEG C of temperature condition, it is complete
At combined processing again, the heavy rare earth manocrystalline powders are obtained.
Preferably, the Hydrogen Vapor Pressure is 10-2~10-1Pa, processing time are 30~45min.
Further, by taking dysprosium and terbium as an example, more preferred hydrogen pressure is 10-2Pa, heat treatment time 45min.
In some embodiments, the high vacuum system of hydrogen heat-treatment furnace can be opened after the completion of the HDDR is handled
System extracts remaining hydrogen out, and is cooled down to boiler tube by air-cooled.
In the present invention, by HDDR processing procedures above-mentioned, it is 100nm~1 μm that may finally obtain crystallite dimension,
Heavy rare earth manocrystalline powders of the grain average-size SMD 10~100 μm or so (before separation).
In some preferred embodiments, after the completion of HDDR processing procedures, the nanocrystalline intercrystalline of obtained heavy rare earth is utilized
The weaker feature of binding force can detach the heavy rare earth manocrystalline powders in the way of physical grinding, finally may be used
The auxiliary phase heavy rare earth manocrystalline powders that average grain diameter SMD is 0.5~1.5 μm are obtained, and the size of crystal grain contained therein is
100nm~1 μm.
Preferably, the mode of the physical grinding include high-energy ball milling, hydrogen it is broken-techniques such as airflow milling.
In some preferred embodiments, the method further includes：By the sintered NdFeB magnetic powder and heavy rare earth nanometer
Crystalline flour end is uniformly mixed, and is sintered 2~4h under the conditions of 980~1100 DEG C later, then respectively at 850~900 DEG C and 450~500
2~3h is made annealing treatment under the conditions of DEG C, obtains the neodymium-iron-boron magnetic material of high-coercive force.
In some more specific embodiment, the HDDR processing can specifically include：
Heavy rare earth-ferroalloy ingot casting is placed in hydrogen heat-treatment furnace, and makes heavy rare earth-ferroalloy ingot casting in hydrogen atmosphere
Middle saturation inhales hydrogen, completes to inhale hydrogen processing；
So that hydrogen heat-treatment furnace cavity temperature is risen to 700 DEG C~900 DEG C with the heating rate of 5~10 DEG C/min, and keeps
Hydrogen Vapor Pressure is 50kPa~150kPa in furnace chamber, and 2~3h of heat-insulation pressure keeping completes disproportionation processing；
Vacuumize process is carried out to hydrogen heat-treatment furnace furnace chamber, until Hydrogen Vapor Pressure is 50~100Pa in furnace chamber, and 700
DEG C~900 DEG C of heat preservation 1h, Hydrogen Vapor Pressure in hydrogen heat-treatment furnace furnace chamber is adjusted to 10 later-1Hereinafter, at 700 DEG C~900 DEG C
45min is kept the temperature, the de- multiple processing of high vacuum is completed；
The hydrogen in hydrogen heat-treatment furnace furnace chamber is excluded, and cooling, obtains crystallite dimension 100nm~1 μm, and particle is average
The heavy rare earth manocrystalline powders that size is 10~100 μm；
The heavy rare earth manocrystalline powders are detached in a manner of physical grinding, the heavy rare earth nanometer crystal powder after separation
The average grain diameter at end is 0.5~1.5 μm, and the size of crystal grain contained therein is 100nm~1 μm.
Further, the sintered NdFeB magnetic powder includes with Nd2Fe14B phases (referred to as 2:14:1 phase) be main phase neodymium iron
Boron magnetic material.
Wherein, the sintered NdFeB magnetic powder may include being applicable in by what the techniques such as near quick setting and ingot casting obtained
In magnetic powder prepared by sintered NdFeB.
Preferably, the quality of the heavy rare earth manocrystalline powders is the 1%~4% of the sintered NdFeB magnetic powder quality.
In conclusion the heavy rare earth manocrystalline powders that the present invention is handled using HDDR are improving as structurally-modified alloy
While crystal ingedient and structure regulate and control heavy rare earth element distribution, using liquid sintering process grain growth crystal grain table
Layer uniformly diffusion, forms the shell structurre of heavy rare earth, reaches the coercivity that magnet is improved under the premise of ensureing high remanent magnetism, in turn
Improve the utilization rate of heavy rare earth element.
Below by way of several embodiments technical solution that present invention be described in more detail.However, selected embodiment is only
For illustrating the present invention, and do not limit the scope of the invention.
Embodiment 1
1) raw metal Dy polishings is bright, by the atomic ratio 1 of Dy and Fe:2 weigh simple metal Dy and Fe respectively is total to
1.5kg is put into medium frequency induction melting furnace and pours 0.5MPa argon gas meltings after gas washing, pours and cast from copper mold, obtains Dy-Fe
Alloy cast ingot.
2) Dy-Fe alloy cast ingots are put into hydrogen heat-treatment furnace, 50kPa hydrogen is filled with after gas washing, wait for Dy-Fe alloys
Ingot casting inhales hydrogen, needs that hydrogen is replenished in time therebetween.After Hydrogen Vapor Pressure no longer changes, heating schedule is set, according to 10 DEG C per minute
840 DEG C are warming up to, 2h is kept the temperature, and hydrogen is maintained to press 50kPa.In the low vacuum stage, maintain hydrogen that 100Pa, 840 DEG C of temperature is pressed to stop
30min.In high vacuum stage of Fig, diffusion pump dehydrogenation is opened, maintains 840 DEG C of temperature, stops 30min.Heating system is closed, argon is filled with
Gas, and furnace body is cooled down using fan.Under nitrogen protection, Dy-Fe manocrystalline powders are taken out using transition glove box,
SEM figures are referring to shown in Fig. 4 and Fig. 5.Dy-Fe manocrystalline powders are further crushed using airflow milling, average grain diameter is made
(SMD) the Dy-Fe manocrystalline powders for being 1.58 μm.
3) according to mass ratio (Pr0.2Nd0.8)30Fe67.3B0.95Al0.75Co0.9Cu0.1Dispensing 2.5kg is smelted with rapid hardening furnace and is cast
Piece；Hydrogen is made using hydrogen broken furnace and breaks powder, the magnetic powder without heavy rare earth that average grain diameter (SMD) is 2.3 μm is made by airflow milling.
4) it is 0%, 1%, 2% difference according to Dy total contents by the magnetic powder of above-mentioned no heavy rare earth and Dy-Fe manocrystalline powders
Mix magnetic powder；Under nitrogen protection, the orientation to magnetic powder and precompressed are completed in die mould glove box；To blank in cold isostatic press
Apply 200MPa pressure, maintains pressure 13s.
5) under nitrogen protection, the blank pressed is put into vacuum drying oven, sets sintering temperature as 1030 DEG C of time 2h；It burns
Applying argon gas after the completion of knot, it is air-cooled, the tempering process of 900 DEG C and 500 DEG C of each 2h is carried out respectively.
6) magnet obtained is prepared into sample according to associated test standards, is completed in NIM-500C magnetism testing systems
The test of demagnetizing curve.Test result is shown in Table 1, and magnetic property curve is shown in Fig. 1.
Difference Dy contents add magnetic property in 1 embodiment 1 of table
| Dy contents | Remanent magnetism (kGs) | Coercivity (kOe) | Maximum magnetic energy product (MGOe) | Squareness |
| 0%Dy | 13.45 | 15.07 | 42.59 | 0.92 |
| 1%Dy | 13.59 | 18.63 | 43.99 | 0.91 |
| 2%Dy | 13.34 | 21.34 | 42.28 | 0.85 |
Embodiment 2
1) according to mass ratio Nd29Fe69.93Cu0.1B0.97Dispensing 2.5kg smelts sequin with rapid hardening furnace；It is made using hydrogen broken furnace
Hydrogen breaks powder, and the magnetic powder of 3 μm of average grain diameter (SMD) is made by airflow milling.
2) it is according to Dy total contents with the Dy-Fe manocrystalline powders prepared in embodiment 1 by the magnetic powder of above-mentioned no heavy rare earth
0%, 2% magnetic powder is mixed respectively；Under nitrogen protection, the orientation to magnetic powder and precompressed are completed in die mould glove box；Cold etc.
200MPa pressure is applied to blank in static pressure machine, maintains pressure 13s.
3) under nitrogen protection, the blank pressed is put into vacuum drying oven, sets sintering temperature as 1080 DEG C of time 2h；It burns
Applying argon gas after the completion of knot, it is air-cooled, the tempering process of 900 DEG C and 500 DEG C of each 2h is carried out respectively.
4) magnet of system is prepared into sample according to associated test standards, completes to move back in NIM-500C magnetism testing systems
The test of magnetic curve.Test result is shown in Table 2, and magnetic property curve is shown in Fig. 2.
Difference Dy contents add magnetic property in 2 embodiment 2 of table
| Dy contents | Remanent magnetism (kGs) | Coercivity (kOe) | Maximum magnetic energy product (MGOe) | Squareness |
| 0%Dy | 14.4 | 11.23 | 50.03 | 0.92 |
| 2%Dy | 13.79 | 18.4 | 46.15 | 0.93 |
Embodiment 3
1) raw metal Tb polishings is bright, by the atomic ratio 1 of Tb and Fe:2 weigh simple metal Tb and the total 1kg of Fe respectively,
It is put into gas washing 2 times to 10 in Medium frequency induction rapid hardening furnace-2Pa hereinafter, after be filled with 0.5MPa argon gas, open heating system and be slowly increased
Power to liquidus temperature reaches 1260 DEG C and keeps the temperature 5min at this temperature.Suitable copper rod speed is adjusted, cooling system is opened, it will
Liquid phase is poured down by certain speed, obtains rapid-hardening flake of the thickness between 150-200 μm.
2) Tb-Fe rapid-hardening flakes are put into hydrogen heat-treatment furnace, 50kPa hydrogen is filled with after gas washing, wait for the casting of Tb-Fe alloys
Ingot inhales hydrogen, needs that hydrogen is replenished in time therebetween.After Hydrogen Vapor Pressure no longer changes, heating schedule is set, is risen according to 10 DEG C per minute
Temperature keeps the temperature 2h to 860 DEG C, and hydrogen is maintained to press 50kPa.In the low vacuum stage, maintain hydrogen that 100Pa, 860 DEG C of temperature is pressed to stop
30min.In high vacuum stage of Fig, diffusion pump dehydrogenation is opened, maintains 860 DEG C of temperature, stops 30min.Heating system is closed, argon is filled with
Gas, and furnace body is cooled down using fan.Under nitrogen protection, Tb-Fe manocrystalline powders are taken out using transition glove box.Make
Tb-Fe manocrystalline powders be further crushed with airflow milling and obtain manocrystalline powders.
3) according to mass ratio Nd30Fe66.B1Al0.75Co0.9Cu0.1Dispensing 2.5kg smelts slab with rapid hardening furnace；It is broken using hydrogen
Stove is made hydrogen and breaks powder, and the magnetic powder without heavy rare earth that average grain diameter (SMD) is 2.5 μm is made by airflow milling.
4) magnetic powder of above-mentioned no heavy rare earth is mixed according to Tb total contents for 0%, 2% respectively with Tb-Fe manocrystalline powders
Magnetic powder；Under nitrogen protection, the orientation to magnetic powder and precompressed are completed in die mould glove box；Blank is applied in cold isostatic press
200MPa pressure maintains pressure 13s.
5) under nitrogen protection, the blank pressed is put into vacuum drying oven, sets sintering temperature as 1050 DEG C of time 2h；It burns
Applying argon gas after the completion of knot, it is air-cooled, the tempering process of 900 DEG C and 500 DEG C of each 2h is carried out respectively.
6) magnet obtained is prepared into sample according to associated test standards, is completed in NIM-500C magnetism testing systems
The test of demagnetizing curve.Test result is shown in Table 3, and magnetic property curve is shown in Fig. 3.
Difference Tb contents add magnetic property in 3 embodiment 2 of table
| Tb contents | Remanent magnetism (kGs) | Coercivity (kOe) | Maximum magnetic energy product (MGOe) | Squareness |
| 0%Tb | 13.57 | 15.25 | 44.36 | 0.95 |
| 2%Tb | 13.29 | 24.05 | 43.08 | 0.94 |
By embodiment 1-3 it can be found that being received using the HDDR heavy rare earth handled by the above-mentioned technical proposal of the present invention
Rice crystalline flour end regulates and controls the distribution of heavy rare earth element as structurally-modified alloy while improving crystal ingedient and structure, utilizes
The grain growth of liquid sintering process is uniformly spread on the surface layer of crystal grain, forms the shell structurre of heavy rare earth, is reached and is being ensured height
The coercivity of magnet is improved under the premise of remanent magnetism, and then improves the utilization rate of heavy rare earth element.
In addition, mode of the inventor referring also to embodiment 1- embodiments 3, with the other raw materials listed in this specification
It is tested with condition etc., and the neodymium-iron-boron magnetic material with higher coercivity has equally been made.
It should be understood that the technical concepts and features of above-described embodiment only to illustrate the invention, ripe its object is to allow
The personage for knowing technique cans understand the content of the present invention and implement it accordingly, and the protection model of the present invention can not be limited with this
It encloses.Any equivalent change or modification in accordance with the spirit of the invention should be covered by the protection scope of the present invention.
Claims (10)
1. a kind of coercitive method of raising neodymium-iron-boron magnetic material, it is characterised in that including：
Sintered NdFeB magnetic powder as major phase material is provided；
Heavy rare earth-ferroalloy ingot casting is provided, and HDDR processing is carried out to the heavy rare earth-ferroalloy ingot casting, heavy rare earth is obtained and receives
Rice crystalline flour end, HDDR processing include the hydrogenation carried out successively, disproportionation, dehydrogenation and combined processing again；
The sintered NdFeB magnetic powder is uniformly mixed with heavy rare earth manocrystalline powders, is sintered, makes annealing treatment later, is obtained
The neodymium-iron-boron magnetic material of high-coercive force.
2. the coercitive method of raising neodymium-iron-boron magnetic material according to claim 1, it is characterised in that：The heavy rare earth
The average grain diameter of manocrystalline powders is 0.5~1.5 μm, and the size of crystal grain contained therein is 100nm~1 μm；And/or the burning
It includes with Nd to tie NdFeB magnetic powder2Fe14B phases are the sintered NdFeB magnetic powder of main phase.
3. the coercitive method of raising neodymium-iron-boron magnetic material according to claim 1, it is characterised in that：The heavy rare earth
The mass ratio of manocrystalline powders and sintered NdFeB magnetic powder is 1~4：100.
4. the coercitive method of raising neodymium-iron-boron magnetic material according to claim 1, it is characterised in that including：According to weight
The atomic ratio of rare earth element and ferro element is 1:2~1:3, by heavy rare earth metal simple substance and iron simple substance under inert gas protection into
Row melting, and it is cooling, obtain heavy rare earth-ferroalloy ingot casting；Preferably, the temperature-gravity rare earth metal simple substance and iron of the melting
The single-phase liquidus curve of simple substance is higher by 50 DEG C or more；Preferably, the heavy rare earth element includes dysprosium and/or terbium；Preferably, described molten
Refining and cooling technique include near quick setting slab or the cooling of induction melting copper mold.
5. the coercitive method of raising neodymium-iron-boron magnetic material according to claim 1, it is characterised in that including：It will be described
Heavy rare earth-ferroalloy ingot casting, which is placed in pressure and is saturated in the hydrogen atmosphere of 50kPa or more, inhales hydrogen, completes hydrogenation treatment, is weighed
Rare earth-iron alloy powder；Preferably, the average grain diameter of the heavy rare earth-ferroalloy powder is 10~100 μm.
6. the coercitive method of raising neodymium-iron-boron magnetic material according to claim 1, it is characterised in that further include：It will be through
Heavy rare earth-ferroalloy powder after hydrogenation treatment is in the hydrogen atmosphere that pressure is 50kPa~150kPa at 700~900 DEG C
2h or more is managed, disproportionation processing is completed；Preferably, the time of the disproportionation processing is 2~3h, and temperature is 780~840 DEG C.
7. the coercitive method of raising neodymium-iron-boron magnetic material according to claim 1, it is characterised in that further include：It will be through
Disproportionation treated heavy rare earth-ferroalloy powder is in the vacuum environment that pressure is 50~100Pa in 700~900 DEG C of temperature strip
Dehydroepiandrosterone derivative is carried out under part；Preferably, the temperature of the Dehydroepiandrosterone derivative is 780~840 DEG C, and pressure is 50~100Pa, and the time is
1~1.5h.
8. the coercitive method of raising neodymium-iron-boron magnetic material according to claim 1, it is characterised in that further include：It will be through
Heavy rare earth-ferroalloy powder after Dehydroepiandrosterone derivative is 10 in Hydrogen Vapor Pressure-1In 700 DEG C~900 DEG C of temperature in Pa environment below
Processing time is 30min or more under the conditions of degree, completes combined processing again, obtains the heavy rare earth manocrystalline powders；Preferably, institute
It is 10 to state Hydrogen Vapor Pressure-2~10-1Pa, processing time are 30~45min；
Preferably, the method further includes：The heavy rare earth manocrystalline powders are detached in a manner of physical grinding；It is excellent
Choosing, the mode of the physical grinding includes high-energy ball milling and/or airflow milling.
9. the coercitive method of raising neodymium-iron-boron magnetic material according to claim 1, it is characterised in that further include：By institute
It states sintered NdFeB magnetic powder to be uniformly mixed with heavy rare earth manocrystalline powders, is sintered 2~4h under the conditions of 980~1100 DEG C later,
2~3h is made annealing treatment under the conditions of 850~900 DEG C with 450~500 DEG C respectively again, obtains the Neodymium iron boron magnetic material of high-coercive force
Material.
10. the coercitive method of raising neodymium-iron-boron magnetic material according to claim 1, it is characterised in that specifically include：
Heavy rare earth-ferroalloy ingot casting is placed in hydrogen heat-treatment furnace, and heavy rare earth-ferroalloy ingot casting is made to be embezzled in hydrogen atmosphere
With suction hydrogen, complete to inhale hydrogen processing；
So that hydrogen heat-treatment furnace cavity temperature is risen to 700~900 DEG C with the heating rate of 5~10 DEG C/min, and keeps in furnace chamber
Hydrogen Vapor Pressure is 50kPa~150kPa, and 2~3h of heat-insulation pressure keeping completes disproportionation processing；
Vacuumize process is carried out to hydrogen heat-treatment furnace furnace chamber, until Hydrogen Vapor Pressure is 50~100Pa in furnace chamber, and 700~900
DEG C heat preservation 1h, complete Dehydroepiandrosterone derivative, Hydrogen Vapor Pressure in hydrogen heat-treatment furnace furnace chamber is adjusted to 10 later-1Pa hereinafter, 700~
900 DEG C of heat preservation 30min or more, complete combined processing again；
Cooling furnace body obtains heavy rare earth manocrystalline powders, and the particle size range of the heavy rare earth manocrystalline powders is 10~100
μm；
The heavy rare earth manocrystalline powders are detached in a manner of physical grinding, the heavy rare earth manocrystalline powders after separation
Average grain diameter is 0.5~1.5 μm, and the size of crystal grain contained therein is 100nm~1 μm.
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| CN109616310A (en) * | 2019-01-29 | 2019-04-12 | 中国科学院宁波材料技术与工程研究所 | A kind of high-coercive force sintered Nd-Fe-B permanent magnetic material and its manufacturing method |
| CN113838622A (en) * | 2021-09-26 | 2021-12-24 | 太原理工大学 | High-coercivity sintered neodymium-iron-boron magnet and preparation method thereof |
| WO2022006912A1 (en) * | 2020-07-10 | 2022-01-13 | 瑞声声学科技(深圳)有限公司 | Auxiliary alloy powder for permanent magnet material and preparation method therefor, and permanent magnet material |
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