CN104599802B - Rare earth permanent-magnetic material and preparation method thereof - Google Patents
Rare earth permanent-magnetic material and preparation method thereof Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 90
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 88
- 239000000696 magnetic material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000000843 powder Substances 0.000 claims abstract description 68
- 238000002156 mixing Methods 0.000 claims abstract description 33
- 239000000126 substance Substances 0.000 claims abstract description 17
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 11
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 10
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 9
- 238000003856 thermoforming Methods 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 4
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 4
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 29
- 238000007731 hot pressing Methods 0.000 claims description 25
- 238000010791 quenching Methods 0.000 claims description 17
- 230000000171 quenching effect Effects 0.000 claims description 14
- 229910045601 alloy Inorganic materials 0.000 claims description 12
- 239000000956 alloy Substances 0.000 claims description 12
- 238000005496 tempering Methods 0.000 claims description 10
- 238000002844 melting Methods 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910016959 Fe1-bCob Inorganic materials 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- 238000002791 soaking Methods 0.000 claims description 5
- 238000010891 electric arc Methods 0.000 claims description 4
- 238000007499 fusion processing Methods 0.000 claims description 4
- 230000006698 induction Effects 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 239000000463 material Substances 0.000 description 19
- 239000013078 crystal Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 229910052684 Cerium Inorganic materials 0.000 description 8
- 230000005389 magnetism Effects 0.000 description 8
- 229910001172 neodymium magnet Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005415 magnetization Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910000714 At alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 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
- 238000007885 magnetic separation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 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
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
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- Hard Magnetic Materials (AREA)
- Powder Metallurgy (AREA)
Abstract
The present invention relates to a kind of preparation method of rare earth permanent-magnetic material, it includes that it is comprised the following steps：(1) Re Fe B quenched powders and Ce base quenched powders are provided respectively, wherein the Re Fe B quenched powder middle rare earth Re is one or more in Nd, Pr, Dy, Tb, the chemical formula of the Ce bases quenched powder is CexFe(100‑x‑y‑z)ByMz, M is selected from one or more in Ga, Co, Al, Zn, Cu, Nb and Zr, and x, y and z are the weight/mass percentage composition of corresponding element, and 28%≤x≤35%, 0.8%≤y≤1.5%, 0%≤z≤2%；(2) the Ce bases quenched powder is well mixed with the Re Fe B quenched powders and obtains mixing magnetic, wherein, the mass percent described in the mixing magnetic shared by Ce base quenched powders is 10%~50%；(3) the mixing magnetic is carried out into hot-forming, thermoforming and temper successively, obtain rare earth permanent-magnetic material, rare earth permanent-magnetic material is many principal phase structures, and it is mainly made up of nano-grade crystalline substance.The present invention also provides a kind of rare earth permanent-magnetic material obtained using above-mentioned preparation method.
Description
Technical field
The present invention relates to rare earth permanent magnet technical field, more particularly to a kind of lower-cost rare earth permanent-magnetic material and its preparation
Method.
Background technology
Rare earth permanent-magnetic material is the intermetallic compound formed with thulium and magnesium-yttrium-transition metal as matrix
Permanent-magnet material.Nd-Fe-B permanent magnet material (also referred to as NdFeB permanent-magnet materials) has excellent magnetic characteristic, is widely used to social life
Produce, life and the field such as national defence and space flight, as the critical function material for supporting social progress.In NdFeB permanent-magnet materials,
The cost of rare earth Nd accounts for more than the 90% of the cost of raw material.With industrial expansion and the progress of society, NdFeB permanent-magnet materials
Usage amount increase year by year, therefore, it is necessary to develop a kind of new cheap Re-Fe-B compounds (Re represents rare earth element), with
The consumption of Nd is reduced, production cost is reduced, balance rare earth is utilized.
Often the rare earth element of addition has praseodymium (Pr), dysprosium (Dy), terbium (Tb) in NdFeB permanent-magnet materials, but, these are dilute
Earth metal is expensive, and Dy and Tb proportions in rare earth resources are few, and price is costly.The expensive price of rare earth with
The shortage of part rare earth resources, promotes researcher to generate interest to Ce.However, Ce2Fe14The saturation magnetization of B with it is each to
Different in nature field is below Nd2Fe14B phases, Ce2Fe14The mono- principal phase compounds of B are difficult to be provided simultaneously with remanent magnetism and HCJ high.Example
The patent application (Publication No. CN102779602A) as disclosed in China discloses Ce-Fe-B fast quenching permanent-magnet materials, and it is first by original
Material and then is made quenched powder at alloy molten via fast quenching, because the permanent-magnet material is isotropic magnetic, therefore coercivity with
Remanent magnetism is relatively low, and magnetic property is poor.
The content of the invention
In view of this, it is necessory to provide, a kind of cost is relatively low and the preferable rare earth permanent-magnetic material of magnetic property and its preparation side
Method.
The present invention provides a kind of preparation method of rare earth permanent-magnetic material, and it is comprised the following steps：
(1) Re-Fe-B quenched powders and Ce base quenched powders are provided respectively, wherein the Re-Fe-B quenched powders middle rare earth Re is
One or more in Nd, Pr, Dy, Tb, the chemical formula of the Ce bases quenched powder is CexFe(100-x-y-z)ByMz, M be selected from Ga, Co,
One or more in Al, Zn, Cu, Nb and Zr, x, y and z are the weight/mass percentage composition of corresponding element, and 28%≤x≤
35%, 0.8%≤y≤1.5%, 0%≤z≤2%；
(2) the Ce bases quenched powder is well mixed with the Re-Fe-B quenched powders and obtains mixing magnetic, wherein, described
Mass percent described in mixing magnetic shared by Ce base quenched powders is 10%~50%；
(3) the mixing magnetic is carried out into hot-forming, thermoforming and temper successively, obtain rare earth permanent magnet material
Material, the rare earth permanent-magnetic material is many principal phase structures, and the rare earth permanent-magnetic material is mainly made up of nano-grade crystalline substance.
Wherein, the mass percent described in the mixing magnetic shared by Ce base quenched powders is 10%~20%.
Wherein, step (1) described in Ce base quenched powders preparation method it is as follows：First, using electric arc or induction melting
Method melting Ce-Fe--B-M foundry alloys, the fusion process is carried out under an inert atmosphere；Then, in an inert atmosphere will melting
State Ce-Fe--B-M foundry alloys are sprayed to water-cooled disk roller carries out fast quenching, obtains Ce base rapid tempering belts, wherein roll surface speed be 10m/s~
50m/s, fast quenching temperature is 1200 DEG C~1500 DEG C, and injection pressure is 0.01MPa~0.1MPa；Finally, by the Ce bases fast quenching
Band carries out Mechanical Crushing, forms the Ce base quenched powders that particle diameter is 50 microns~300 microns.
Wherein, step (3) described in hot-forming process be specially：Mixing magnetic is put into the first mould,
Carry out being heated to the first temperature to mixing magnetic in vacuum environment, and first pressure applied to the first mould, obtain hot pressing blank,
Wherein, first temperature is 650 DEG C~700 DEG C, and the first pressure is 150MPa~200MPa, and the vacuum environment
Vacuum is not less than 5 × 10-2Pa。
Wherein, step (3) described in the process of thermoforming be specially：The hot pressing blank is put into the second mould
In, in an inert atmosphere the hot pressing blank is carried out being heated to second temperature, make the hot pressing blank carry out degree of deformation to be
30%~95% deformation, then second pressure is applied to the hot pressing blank after deformation, heat distortion magnet is obtained, wherein described second
Temperature is 800 DEG C~900 DEG C, and the second pressure is 30MPa~100MPa.
Wherein, step (3) described in the process of temper be specially：By the heat distortion magnet in vacuum environment
It is heated to the 3rd temperature and is incubated, and the chilling that quenched after insulation terminates, wherein the 3rd temperature is 500 DEG C~800 DEG C, during insulation
Between be 1 hour~10 hours, during heating heating rate be 5 DEG C/min~20 DEG C/min.
The present invention also provides a kind of rare earth permanent-magnetic material obtained using above-mentioned preparation method, and the rare earth permanent-magnetic material is
Many principal phase structures, the rare earth permanent-magnetic material is mainly made up of nano-grade crystalline substance, and the brilliant chemical formula of the nano-grade is
(Re1-aCea)2(Fe1-bCob)14B, wherein, rare earth Re is one or more in Nd, Pr, Dy, Tb, and a and b is corresponding element
Atomic ratio, 0≤a≤1,0≤b≤0.5.
Wherein, the brilliant length of the nano-grade is 200nm~1000nm, and thickness is 50nm~100nm.
Compared with traditional sintering techniques, in the preparation method of the rare earth permanent-magnetic material that the present invention is provided, using being hot pressed into
Type and thermoforming technique, alloy is densified by hot-forming, obtains hot pressing blank；In thermal deformation process, hot pressing
Blank moderate pressure high effect under, (Nd, Ce)2(Fe,Co)14B phases crystal grain forms edge by dissolving-mass transfer-recrystallization process
The flake crystalline that easy magnetizing axis c-axis are consistently oriented, therefore heat distortion magnet has remanent magnetism higher；Because forming temperature is low, soaking time
It is short, therefore crystal grain is tiny, coercivity is high, and rare earth permanent-magnetic material has coercivity and remanent magnetism higher, magnetic property obtained from
It is excellent.Also, the rare earth permanent-magnetic material is many principal phase structures, and it is mainly made up of nano-grade crystalline substance, corrosion resistance is strong,
With preferable practicality.
It is additionally, since using rare earth metals such as cheap Rare-Earth Ce part substitution expensive Nd, Pr, Ce maximum levels can be with
The 50% of total amount of rare earth is reached, thus reduces production cost, balance rare earth is utilized.
Further, the mixed proportion of the Ce bases quenched powder and the Re-Fe-B quenched powders can be also as needed adjusted, is entered
And adjust the content of Ce in the rare earth material and adjust its magnetic characteristic, to meet in different product the need for magnetic property.It is described
Preparation method is easily achieved newly net forming, and material recovery rate is high, process is simple, is adapted to industrialized production.
Brief description of the drawings
Fig. 1 is that the X- of each rare earth permanent-magnetic material that the present invention is prepared using the Ce base quenched powders of different quality containing is penetrated
Line diffraction (XRD) figure, wherein, the mass fraction of Ce base quenched powders refers to that the (2) Ce bases are fast in step mixing magnetic in preparation method
The mass percent quenched shared by powder.
Fig. 2 is the scanning of the rare earth permanent-magnetic material for using mass fraction to be prepared for 20% Ce base quenched powders of the invention
Electronic Speculum (SEM) photo.
Fig. 3 is the scanning of the rare earth permanent-magnetic material for using mass fraction to be prepared for 30% Ce base quenched powders of the invention
Electronic Speculum (SEM) photo.
Specific examples below will further illustrate the present invention with reference to above-mentioned accompanying drawing.
Specific embodiment
The preparation method of the rare earth permanent-magnetic material provided the present invention below with reference to accompanying drawing is described further.
The present invention provides a kind of preparation method of rare earth permanent-magnetic material, and it includes following steps：
S1, provides Re-Fe-B quenched powders and Ce base quenched powders, wherein the Re-Fe-B quenched powders middle rare earth Re respectively
It is one or more in Nd, Pr, Dy, Tb, the chemical formula of the Ce bases quenched powder is CexFe(100-x-y-z)ByMz, M be selected from Ga,
One or more in Co, Al, Zn, Cu, Nb and Zr, x, y and z are the weight/mass percentage composition of corresponding element, and 28%≤x
≤ 35%, 0.8%≤y≤1.5%, 0%≤z≤2%；
S2, the Ce bases quenched powder is well mixed with the Re-Fe-B quenched powders and obtains mixing magnetic, wherein, in institute
It is 10%~50% to state the mass percent described in mixing magnetic shared by Ce base quenched powders；And
S3, hot-forming, thermoforming and temper are carried out by the mixing magnetic successively, obtain main by nanometer
The rare earth permanent-magnetic material of level flake crystalline composition.
In step sl, the preparation method of the Ce bases quenched powder is specific as follows：
S111, using electric arc or the method melting Ce-Fe- of induction melting-B-M foundry alloys, the fusion process is in inertia
Carried out under atmosphere；
S112, in an inert atmosphere by molten state Ce-Fe--B-M foundry alloys are sprayed to water-cooled disk roller carries out fast quenching, obtains
Ce base rapid tempering belts, wherein roll surface speed are 10m/s~50m/s, and fast quenching temperature is 1200 DEG C~1500 DEG C, and injection pressure is
0.01MPa~0.1MPa；
S113, Mechanical Crushing is carried out by the Ce bases rapid tempering belt, forms the Ce base fast quenchings that particle diameter is 50 microns~300 microns
Powder.
In step S111, first according to the proportioning preparation raw material of each element in Ce base quenched powders, then carry out melting and melted
Melt state Ce-Fe--B-M foundry alloys.During melting, each atom in raw material can occur a series of chemical change, and shape
Into principal phase and richness Ce phases with certain proportioning.The inert atmosphere refers to the atmosphere such as nitrogen, argon gas, neon, Krypton.
In step S112, by fast quenching, amorphous state or the nanocrystalline Ce base rapid tempering belts coexisted with amorphous are obtained, so as to
In rare earth material of the preparation with high magnetic characteristics.
In step S113, the Ce bases rapid tempering belt forms Ce base quenched powders by Mechanical Crushing, in order to follow-up
Formed with Re-Fe-B quenched powders in hot-forming and preferably contacted.
The preparation method that the Re-Fe-B quenched powders can refer to above-mentioned Ce bases quenched powder is prepared, also can directly from city
Field is bought, and will not be repeated here.
In step s 2, mix with the Re-Fe-B quenched powders by by the Ce bases quenched powder so that the Ce bases are fast
Powder of quenching is uniformly distributed in the Re-Fe-B quenched powders.The mixing can be carried out in three-dimensional material mixer.In the mixing magnetic
Described in mass ratio shared by Ce base quenched powders be 10%~50%.Described in the mixing magnetic shared by Ce base quenched powders
Mass ratio be preferably 10%~20%, the magnet magnetic energy product of the rare earth permanent-magnetic material for now obtaining is more than 39MGOe, interior
Report coercivity and be more than 12kOe, remanent magnetism is more than 12.6kGs.
In step s3, by described hot-forming dilute with thermoforming technique is prepared into sheet crystal structure many principal phases
Native permanent-magnet material.Specially：It is hot-forming to be densified alloy, obtain hot pressing blank；In thermal deformation process, hot pressing blank exists
Under moderate pressure effect high, (Nd, Ce)2(Fe,Co)14B phases crystal grain is formed along easy magnetization by dissolving-mass transfer-recrystallization process
The flake crystalline that axle c-axis are consistently oriented, therefore heat distortion magnet has remanent magnetism higher；Because forming temperature is low, soaking time is short, therefore
Crystal grain is tiny, and coercivity is high.
The hot-forming process is specially：Mixing magnetic is put into the first mould, to mixing in vacuum environment
Magnetic carries out being heated to the first temperature, and applies first pressure to the first mould, obtains hot pressing blank.Wherein, first temperature
It is 650 DEG C~700 DEG C to spend, and the first pressure is 150MPa~200MPa, and the vacuum of the vacuum environment be not less than 5 ×
10-2Pa。
The process of the thermoforming is specially：The hot pressing blank is put into the second mould, in an inert atmosphere
The hot pressing blank is carried out being heated to second temperature, the hot pressing blank is carried out the deformation that degree of deformation is 30%~95%,
Second pressure is applied to the hot pressing blank after deformation again, heat distortion magnet is obtained.Wherein described second temperature is 800 DEG C~900
DEG C, the second pressure is 30MPa~100MPa.
The process of the temper is specially：The heat distortion magnet is heated to the 3rd temperature simultaneously in vacuum environment
Insulation, and the chilling that quenched after insulation terminates.3rd temperature is 500 DEG C~800 DEG C, and soaking time is 1 hour~10 small
When, heating rate is 5 DEG C/min~20 DEG C/min during heating.It should be noted that heat distortion magnet is by temper, heat becomes
By temper, by atoms permeating, mutually there is a certain degree of change, but grain shaped in composition to shape magnet with crystal grain into branch
Looks are not changed in substantially with size.
The present invention also provides a kind of rare earth permanent-magnetic material, and the rare earth permanent-magnetic material is prepared by the above method.Institute
Rare earth permanent-magnetic material is stated for many principal phase structures, it is mainly made up of nano-grade crystalline substance.The brilliant chemical formula of the nano-grade
It is (Re1-aCea)2(Fe1-bCob)14B.Wherein, rare earth Re is one or more in Nd, Pr, Dy, Tb, and a and b is corresponding element
Atomic ratio, 0≤a≤1,0≤b≤0.5.The brilliant length of the nano-grade is 200nm~1000nm, and thickness is 50nm
~100nm.
In preparation method of the present invention, alloy is densified by hot press forming technology, obtains hot pressing blank；Become in heat
During shape, hot pressing blank moderate pressure high effect under, (Nd, Ce)2(Fe,Co)14B phases crystal grain is by dissolving-mass transfer-tie again
Brilliant process, the flake crystalline that formation is consistently oriented along easy magnetizing axis c-axis, therefore heat distortion magnet has remanent magnetism higher；Due to shaping temperature
Degree is low, and soaking time is short, therefore crystal grain is tiny, and coercivity is high, and the magnetic property of the rare earth permanent-magnetic material for obtaining is excellent.And
And, the rare earth permanent-magnetic material is many principal phase structures, and it is mainly made up of nano-grade crystalline substance, and corrosion resistance is strong, with preferable
Practicality.
It is additionally, since using rare earth metals such as cheap Rare-Earth Ce part substitution expensive Nd, Pr, Ce maximum levels can be with
The 50% of total amount of rare earth is reached, thus reduces production cost, balance rare earth is utilized.
Further, the mixed proportion of the Ce bases quenched powder and the Re-Fe-B quenched powders can be also as needed adjusted, is entered
And adjust the content of Ce in the rare earth material and adjust its magnetic characteristic, to meet in different product the need for magnetic property.It is described
Preparation method is easily achieved newly net forming, and material recovery rate is high, process is simple, is adapted to industrialized production.
Hereinafter, will further illustrate in conjunction with specific embodiments.
Embodiment (1)
According to Ce base quenched powders (Ce31Fe68B1) in each element dispensing accurate in scale, prepared through electric arc or induction furnace melting
Into Ce31Fe68B1Foundry alloy, fusion process is carried out under argon gas protection.By Ce in argon gas atmosphere31Fe68B1Foundry alloy remelting,
Fill-before-fire to water-cooled copper roller carries out fast quenching, obtains Ce31Fe68B1Rapid tempering belt, wherein roll surface speed are 35m/s, and fast quenching temperature is
1350 DEG C, injection pressure is 0.02MPa.By Ce31Fe68B1It is 50 microns~300u microns that rapid tempering belt is broken into particle diameter
Ce31Fe68B1Quenched powder.
After magnetic separation, by Ce31Fe68B1(composition is Nd to quenched powder with MQP-F powder29.8Pr0.4Fe64.41Co4B0.93Ga0.46) three
Mixing obtains mixing magnetic for 3 hours in dimension batch mixer.Wherein Ce31Fe68B1Quenched powder accounts for the 10% of mixing magnetic gross mass.
Mixing magnetic is put into the first mould, the sensing heating in vacuum environment, when temperature is upgraded to 200 DEG C, started
First pressure is applied to the first mould, and maximum temperature is controlled to 670 DEG C, obtains hot pressing blank.Wherein highest is raised to from room temperature
The time of temperature is 5 minutes~6 minutes, and first pressure is 150MPa, and vacuum is not less than 5 × 10 in hot pressing-2Pa。
Hot pressing blank is put into the second mould being relatively large in diameter, carrying out sensing to hot pressing blank in argon gas atmosphere adds
Heat, makes the hot pressing blank carry out the deformation that degree of deformation is 70%.1.5 minutes are incubated after temperature reaches 840 DEG C of maximum temperature,
Then apply second pressure, obtain heat distortion magnet.Wherein, the time that maximum temperature is raised to from room temperature is 6 minutes~7 minutes,
Second pressure is 50MPa.
By heat distortion magnet in vacuum environment, 700 DEG C are tempered 3.5 hours.Be machined to after cooling size for Φ 10 ×
10 rare earth permanent-magnetic material.
More preferably to analyze the composition of the rare earth permanent-magnetic material for obtaining, XRD (see Fig. 1) points is also carried out to rare earth permanent-magnetic material
Analysis.
Obtained rare earth permanent-magnetic material is carried out into test magnetic property at room temperature, test result is shown in Table 1.Wherein, BrRepresent
Remanent magnetism, unit is kGs；HcjCoercivity is represented, unit is kOe；(BH)mMagnetic energy product is represented, unit is MGOe.
The magnetic property of rare earth permanent-magnetic material obtained in the embodiment 1 and 2 of table 1
Embodiment (2)
The process that embodiment (2) prepares rare earth permanent-magnetic material is essentially identical with embodiment (1), and difference is, in system
During standby mixing magnetic, wherein Ce31Fe68B1Quenched powder accounts for the 20% of mixing magnetic gross mass, and heat distortion magnet is returned
Tempering time is 2.5 hours during fire treatment.
Obtained rare earth permanent-magnetic material is carried out into test magnetic property at room temperature, test result is shown in Table 1.
More preferably to analyze the composition and microscopic pattern of the rare earth permanent-magnetic material, also the rare earth permanent-magnetic material is carried out
XRD (see Fig. 1), SEM (see Fig. 2) and X-ray energy spectrum (EDS) (being shown in Table 2) are analyzed.
The EDS results of rare earth permanent-magnetic material prepared by 2 embodiment of table 2
Embodiment (3)
The process that embodiment (3) prepares rare earth permanent-magnetic material is essentially identical with embodiment (1), and difference is, in system
During standby mixing magnetic, wherein Ce31Fe68B1Quenched powder accounts for the 30% of mixing magnetic gross mass.
More preferably to analyze the composition and microscopic pattern of the rare earth permanent-magnetic material, also the rare earth permanent-magnetic material is carried out
XRD (see Fig. 1), SEM (see Fig. 3) and X-ray energy spectrum (EDS) (being shown in Table 3) are analyzed.
The EDS results of rare earth permanent-magnetic material prepared by 3 embodiment of table 3
Embodiment (4)
The process that embodiment (4) prepares rare earth permanent-magnetic material is essentially identical with embodiment (1), and difference is, in system
During standby mixing magnetic, wherein Ce31Fe68B1Quenched powder accounts for the 50% of mixing magnetic gross mass.
The rare earth permanent-magnetic material that will be obtained carries out XRD analysis (see Fig. 1).
Reference examples
The process that reference examples prepare rare earth permanent-magnetic material is essentially identical with embodiment (1), and difference is, only with MQP-
(composition is Nd to F powder29.8Pr0.4Fe64.41Co4B0.93Ga0.46) as raw material, without adding Ce31Fe68B1Quenched powder.
The rare earth permanent-magnetic material that will be obtained carries out XRD analysis (see Fig. 1).
As seen from Figure 1, the principal phase of the rare earth permanent-magnetic material is (Nd, Ce)2(Fe,Co)14B phases.Relative to comparing
For example, Ce is added31Fe68B1The diffraction maximum of the rare earth permanent-magnetic material is moved to right after quenched powder.When in magnetic is mixed
Ce31Fe68B1When mass fraction shared by quenched powder is equal to or more than 30%, a little CeFe is formed in rare earth permanent-magnetic material2Phase.
From Fig. 2, Fig. 3, table 2 and table 3, rare earth permanent-magnetic material is by (Nd1-aCea)2(Fe1-bCob)14The many principal phase groups of B
Into main phase grain is generally flake crystalline, there is also the equiax crystal that part does not deform.The size of the flake crystalline is nanoscale, its
Length and thickness respectively may be about 800nm, 100nm.
The explanation of above example is only intended to help and understands the method for the present invention and its core concept.It should be pointed out that right
For those skilled in the art, under the premise without departing from the principles of the invention, the present invention can also be carried out
Some improvement and modification, these are improved and modification is also fallen into the protection domain of the claims in the present invention.
The foregoing description of the disclosed embodiments, enables professional and technical personnel in the field to realize or uses the present invention.
Various modifications to these embodiments will be apparent for those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention
The embodiments shown herein is not intended to be limited to, and is to fit to and principles disclosed herein and features of novelty phase one
The scope most wide for causing.
Claims (5)
1. a kind of preparation method of rare earth permanent-magnetic material, it is comprised the following steps：
Respectively provide Re-Fe-B quenched powders and Ce base quenched powders, wherein the Re-Fe-B quenched powders middle rare earth Re be Nd,
One or more in Pr, Dy, Tb, the chemical formula of the Ce bases quenched powder is CexFe(100-x-y-z)ByMz, M be selected from Ga, Co, Al,
One or more in Zn, Cu, Nb and Zr, x, y and z are the weight/mass percentage composition of corresponding element, and 28%≤x≤
35%, 0.8%≤y≤1.5%, 0%≤z≤2%；
(2) the Ce bases quenched powder is well mixed with the Re-Fe-B quenched powders and obtains mixing magnetic, wherein, in the mixing
Mass percent shared by the quenched powders of Ce bases described in magnetic is 10%~20%；
(3) the mixing magnetic is carried out into hot-forming, thermoforming and temper successively, obtain rare earth permanent-magnetic material, institute
Rare earth permanent-magnetic material is stated for many principal phase structures, the rare earth permanent-magnetic material is mainly made up of nano-grade crystalline substance, the nanoscale
The chemical formula of flake crystalline is (Re1-aCea)2(Fe1-bCob)14B, wherein, rare earth Re is one or more in Nd, Pr, Dy, Tb, a
With b for corresponding element atomic ratio, 0≤a≤1,0≤b≤0.5,
Wherein described hot-forming process is specially：Mixing magnetic is put into the first mould, to mixing in vacuum environment
Magnetic carries out being heated to the first temperature, and applies first pressure to the first mould, obtains hot pressing blank, wherein, first temperature
It is 650 DEG C~700 DEG C to spend, and the first pressure is 150MPa~200MPa, and the vacuum of the vacuum environment be not less than 5 ×
10-2Pa；
The process of the thermoforming is specially：The hot pressing blank is put into the second mould, in an inert atmosphere to institute
Stating hot pressing blank carries out being heated to second temperature, the hot pressing blank is carried out the deformation that degree of deformation is 30%~95%, then right
Hot pressing blank after deformation applies second pressure, obtains heat distortion magnet, wherein the second temperature is 800 DEG C~900 DEG C, institute
Second pressure is stated for 30MPa~100MPa.
2. the preparation method of rare earth permanent-magnetic material as claimed in claim 1, it is characterised in that step (1) described in Ce bases it is fast
Quench powder preparation method it is as follows：
First, using electric arc or the method melting Ce-Fe- of induction melting-B-M foundry alloys, the fusion process is under an inert atmosphere
Carry out；
Then, in an inert atmosphere by molten state Ce-Fe--B-M foundry alloys are sprayed to water-cooled disk roller carries out fast quenching, obtains Ce bases fast
Quench band, wherein roll surface speed is 10m/s~50m/s, fast quenching temperature is 1200 DEG C~1500 DEG C, injection pressure for 0.01MPa~
0.1MPa；
Finally, the Ce bases rapid tempering belt is carried out into Mechanical Crushing, forms the Ce base quenched powders that particle diameter is 50 microns~300 microns.
3. the preparation method of rare earth permanent-magnetic material as claimed in claim 1, it is characterised in that step (3) described at tempering
The process of reason is specially：The heat distortion magnet is heated to the 3rd temperature in vacuum environment and is incubated, and terminated in insulation
After quench chilling, wherein the 3rd temperature is 500 DEG C~800 DEG C, soaking time is 1 hour~10 hours, heating rate during heating
It is 5 DEG C/min~20 DEG C/min.
4. the rare earth permanent-magnetic material that a kind of use preparation method as described in any one of claims 1 to 3 is obtained, it is characterised in that
The rare earth permanent-magnetic material is many principal phase structures, and the rare earth permanent-magnetic material is mainly made up of nano-grade crystalline substance, the nanometer
The chemical formula of level flake crystalline is (Re1-aCea)2(Fe1-bCob)14B, wherein, rare earth Re is the one kind or several in Nd, Pr, Dy, Tb
Kind, a and b is the atomic ratio of corresponding element, 0≤a≤1,0≤b≤0.5.
5. rare earth permanent-magnetic material as claimed in claim 4, it is characterised in that the brilliant length of the nano-grade is 200nm
~1000nm, thickness is 50nm~100nm.
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| CN106964777B (en) * | 2016-01-14 | 2021-06-29 | 罗伯特·博世有限公司 | Method and apparatus for producing thermally deformed magnet |
| CN106548843A (en) * | 2016-10-17 | 2017-03-29 | 中国科学院宁波材料技术与工程研究所 | Rare earth permanent-magnetic material and preparation method thereof |
| CN108242305B (en) * | 2016-12-27 | 2020-03-27 | 有研稀土新材料股份有限公司 | Rare earth permanent magnetic material and preparation method thereof |
| CN108515177B (en) * | 2018-05-18 | 2020-09-01 | 江西理工大学 | Nanocrystalline composite rare earth permanent magnet material with multi-main-phase structure and preparation thereof |
| CN109300680B (en) * | 2018-08-24 | 2023-08-29 | 中国科学院宁波材料技术与工程研究所 | Screening method of rare earth permanent magnet material |
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