CN104599802A - 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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- CN104599802A CN104599802A CN201410725480.8A CN201410725480A CN104599802A CN 104599802 A CN104599802 A CN 104599802A CN 201410725480 A CN201410725480 A CN 201410725480A CN 104599802 A CN104599802 A CN 104599802A
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 94
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 92
- 239000000696 magnetic material Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000000843 powder Substances 0.000 claims abstract description 69
- 239000000126 substance Substances 0.000 claims abstract description 22
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 13
- 238000005496 tempering Methods 0.000 claims abstract description 13
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 10
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 9
- 229910052771 Terbium Inorganic materials 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
- 229910052733 gallium 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
- 238000002156 mixing Methods 0.000 claims description 31
- 238000000034 method Methods 0.000 claims description 30
- 238000007731 hot pressing Methods 0.000 claims description 26
- 239000000203 mixture Substances 0.000 claims description 16
- 238000010791 quenching Methods 0.000 claims description 14
- 230000000171 quenching effect Effects 0.000 claims description 14
- 229910045601 alloy Inorganic materials 0.000 claims description 13
- 239000000956 alloy Substances 0.000 claims description 13
- 238000002844 melting Methods 0.000 claims description 10
- 230000008018 melting Effects 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000003856 thermoforming Methods 0.000 claims description 8
- 230000006698 induction Effects 0.000 claims description 6
- 230000014759 maintenance of location Effects 0.000 claims description 6
- 238000010891 electric arc Methods 0.000 claims description 4
- 238000007499 fusion processing Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 238000009413 insulation Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 abstract description 9
- 239000006247 magnetic powder Substances 0.000 abstract 3
- 238000000465 moulding Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 230000005389 magnetism Effects 0.000 description 8
- 229910052684 Cerium Inorganic materials 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910001172 neodymium magnet Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 3
- 238000000280 densification Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method 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
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect 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
- 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
- 230000005415 magnetization Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- 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
Abstract
The invention relates to a preparation method of a rare earth permanent magnetic material. The preparation method comprises the steps that 1, Re-Fe-B quenched powder and Ce-based quenched powder are provided respectively, wherein rare earth Re in the Re-Fe-B quenched powder is one or more of Nd, Pr, Dy and Tb, the chemical formula of the Ce-based quenched powder is CexFe<100-x-y-z)>ByMz, M is one or more of Ga, Co, Al, Zn, Cu, Nb and Zr, x, y and z are the mass percentage content of corresponding elements, x is greater than or equal to 28% and less than or equal to 35%, y is greater than or equal to 0.8% and less than or equal to 1.5%, and z is greater than or equal to 0% and less than or equal to 2%; 2, the Ce-based quenched powder and the Re-Fe-B quenched powder are evenly mixed to obtain mixed magnetic powder, wherein the Ce-based quenched powder accounts for 10%-50% of the mass percent of the mixed magnetic powder; 3, the mixed magnetic powder is subjected to hot press molding, thermal deformation forming and tempering in sequence, and then the rare earth permanent magnetic material is obtained, wherein the rare earth permanent magnetic material is of a multiple main phase structure and is mainly composed of nanoscale plate crystals. The invention further provides the rare earth permanent magnetic material obtained through the preparation method.
Description
Technical field
The present invention relates to rare earth permanent magnet technical field, particularly relate to a kind of lower-cost rare earth permanent-magnetic material and preparation method thereof.
Background technology
The permanent magnetic material that rare earth permanent-magnetic material is the intermetallic compound that formed with thulium and magnesium-yttrium-transition metal is matrix.Nd-Fe-Bo permanent magnet material (also claiming NdFeB permanent magnetic material) has excellent magnetic characteristic, has been widely used in social production, life and the field such as national defence and space flight, has become the critical function material supporting social progress.In NdFeB permanent magnetic material, the cost of rare earth Nd accounts for more than 90% of the cost of raw material.Along with industrial expansion and the progress of society, the use amount of NdFeB permanent magnetic material increases year by year, therefore, be necessary to develop a kind of cheap Re-Fe-B compound (Re represents rare earth element) newly, to reduce the consumption of Nd, reduce production cost, balance rare earth utilizes.
The rare earth element often added in NdFeB permanent magnetic material has praseodymium (Pr), dysprosium (Dy), terbium (Tb), but, these rare earth metals are expensive, and Dy and Tb proportion in rare earth resources is few, and price costly.The price of rare earth costliness and the shortage of part rare earth resources, impel researcher to create interest to Ce.But, Ce
2fe
14the saturation magnetization of B and anisotropy field are all lower than Nd
2fe
14b phase, Ce
2fe
14b mono-principal phase compound is difficult to possess high remanent magnetism and HCJ simultaneously.The disclosed patent application (publication number is CN102779602A) of such as China discloses Ce-Fe-B fast quenching permanent magnetic material, then raw alloy melting is first made quenched powder via fast quenching by it, because this permanent magnetic material is isotropic magnetic, therefore coercive force and remanent magnetism are all lower, and magnetic property is poor.
Summary of the invention
In view of this, necessaryly provide a kind of cost lower and good rare earth permanent-magnetic material of magnetic property and preparation method thereof.
The invention provides a kind of preparation method of rare earth permanent-magnetic material, it comprises the following steps:
(1) provide Re-Fe-B quenched powder and Ce base quenched powder respectively, wherein said Re-Fe-B quenched powder middle rare earth Re is one or more in Nd, Pr, Dy, Tb, and the chemical formula of described Ce base quenched powder is Ce
xfe
(100-x-y-z)b
ym
z, M be selected from Ga, Co, Al, Zn, Cu, Nb and Zr one or more, x, y and z are the mass percentage of corresponding element, and 28%≤x≤35%, 0.8%≤y≤1.5%, 0%≤z≤2%;
(2) mixed with described Re-Fe-B quenched powder by described Ce base quenched powder and obtain mixing magnetic, wherein, the mass percent described in described mixing magnetic shared by Ce base quenched powder is 10% ~ 50%;
(3) described mixing magnetic is carried out successively hot-forming, thermoforming and temper, obtain rare earth permanent-magnetic material, described rare earth permanent-magnetic material is many principal phases structure, and described rare earth permanent-magnetic material is primarily of nano-grade crystalline substance composition.
Wherein, the mass percent described in described mixing magnetic shared by Ce base quenched powder is 10% ~ 20%.
Wherein, step (1) described in the preparation method of Ce base quenched powder as follows: first, adopt the method melting Ce-Fe-of electric arc or induction melting
-b-M foundry alloy, described fusion process carries out under an inert atmosphere; Then, in an inert atmosphere by molten state Ce-Fe-
-b-M foundry alloy is injected into water-cooled running roller and carries out fast quenching, obtains Ce base rapid tempering belt, and wherein roll surface speed is 10m/s ~ 50m/s, and fast quenching temperature is 1200 DEG C ~ 1500 DEG C, and expulsion pressure is 0.01MPa ~ 0.1MPa; Finally, described Ce base rapid tempering belt is carried out Mechanical Crushing, form the Ce base quenched powder 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, in vacuum environment, the first temperature is heated to mixing magnetic, and the first pressure is applied to the first mould, obtain hot pressing blank, wherein, described first temperature is 650 DEG C ~ 700 DEG C, described first pressure is 150MPa ~ 200MPa, and the vacuum degree of described vacuum environment is not less than 5 × 10
-2pa.
Wherein, step (3) described in the process of thermoforming be specially: described hot pressing blank is put into the second mould, in an inert atmosphere the second temperature is heated to described hot pressing blank, described hot pressing blank is made to carry out the distortion that degree of deformation is 30% ~ 95%, again the second pressure is applied to the hot pressing blank after distortion, obtain heat distortion magnet, wherein said second temperature is 800 DEG C ~ 900 DEG C, and described second pressure is 30MPa ~ 100MPa.
Wherein, step (3) described in the process of temper be specially: in vacuum environment, described heat distortion magnet be heated to the 3rd temperature and be incubated, and terminate rear quenching chilling in insulation, wherein the 3rd temperature is 500 DEG C ~ 800 DEG C, temperature retention time is 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 adopting above-mentioned preparation method to obtain, and described rare earth permanent-magnetic material is many principal phases structure, and described rare earth permanent-magnetic material is primarily of nano-grade crystalline substance composition, and the chemical formula of described nano-grade crystalline substance is (Re
1-ace
a)
2(Fe
1-bco
b)
14b, wherein, rare earth Re is one or more in Nd, Pr, Dy, Tb, a and b is the atomic ratio of corresponding element, 0≤a≤1,0≤b≤0.5.
Wherein, the length of described nano-grade crystalline substance is 200nm ~ 1000nm, and thickness is 50nm ~ 100nm.
Compared with traditional sintering techniques, in the preparation method of rare earth permanent-magnetic material provided by the invention, adopt hot-forming and thermoforming technique, make alloy densification by hot-forming, obtain hot pressing blank; In thermal deformation process, hot pressing blank under high moderate pressure effect, (Nd, Ce)
2(Fe, Co)
14b phase crystal grain, by dissolving-mass transfer-recrystallization process, form the flake crystalline along the consistent orientation of easy magnetizing axis c-axis, therefore heat distortion magnet has higher remanent magnetism; Because forming temperature is low, temperature retention time is short, and therefore crystal grain is tiny, and coercive force is high, thus the rare earth permanent-magnetic material obtained has higher coercive force and remanent magnetism, and magnetic property is excellent.Further, described rare earth permanent-magnetic material is many principal phases structure, and it is primarily of nano-grade crystalline substance composition, and corrosion resistance is strong, has good practicality.
And owing to adopting cheap Rare-Earth Ce part to replace the rare earth metals such as expensive Nd, Pr, Ce maximum level can reach 50% of total amount of rare earth, thus reduces production cost, and balance rare earth utilizes.
Further, also can regulate the mixed proportion of described Ce base quenched powder and described Re-Fe-B quenched powder as required, and then regulate the content of Ce in described rare earth material to adjust its magnetic characteristic, to meet the needs of magnetic property in different product.Described preparation method is easy to realize newly net forming, and material recovery rate is high, and technique is simple, is applicable to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is X-ray diffraction (XRD) figure of each rare earth permanent-magnetic material that the present invention adopts the Ce base quenched powder of different quality mark to prepare, wherein, the mass fraction of Ce base quenched powder to refer in preparation method the mass percent (2) in step mixing magnetic shared by Ce base quenched powder.
Fig. 2 be the present invention adopt mass fraction be 20% ESEM (SEM) photo of rare earth permanent-magnetic material for preparing of Ce base quenched powder.
Fig. 3 be the present invention adopt mass fraction be 30% ESEM (SEM) photo of rare earth permanent-magnetic material for preparing of Ce base quenched powder.
Following specific embodiment will further illustrate the present invention in conjunction with above-mentioned accompanying drawing.
Embodiment
Below with reference to accompanying drawing, the preparation method to rare earth permanent-magnetic material provided by the invention is described further.
The invention provides a kind of preparation method of rare earth permanent-magnetic material, it comprises following step:
S1, provides Re-Fe-B quenched powder and Ce base quenched powder respectively, and wherein said Re-Fe-B quenched powder middle rare earth Re is one or more in Nd, Pr, Dy, Tb, and the chemical formula of described Ce base quenched powder is Ce
xfe
(100-x-y-z)b
ym
z, M be selected from Ga, Co, Al, Zn, Cu, Nb and Zr one or more, x, y and z are the mass percentage of corresponding element, and 28%≤x≤35%, 0.8%≤y≤1.5%, 0%≤z≤2%;
S2, mixed with described Re-Fe-B quenched powder by described Ce base quenched powder and obtain mixing magnetic, wherein, the mass percent described in described mixing magnetic shared by Ce base quenched powder is 10% ~ 50%; And
S3, carries out hot-forming, thermoforming and temper successively by described mixing magnetic, obtain the rare earth permanent-magnetic material primarily of nano-grade crystalline substance composition.
In step sl, the preparation method of described Ce base quenched powder is specific as follows:
S111, adopts the method melting Ce-Fe-of electric arc or induction melting
-b-M foundry alloy, described fusion process carries out under an inert atmosphere;
S112, in an inert atmosphere by molten state Ce-Fe-
-b-M foundry alloy is injected into water-cooled running roller and carries out fast quenching, obtains Ce base rapid tempering belt, and wherein roll surface speed is 10m/s ~ 50m/s, and fast quenching temperature is 1200 DEG C ~ 1500 DEG C, and expulsion pressure is 0.01MPa ~ 0.1MPa;
S113, carries out Mechanical Crushing by described Ce base rapid tempering belt, forms the Ce base quenched powder that particle diameter is 50 microns ~ 300 microns.
In step S111, first according to the proportioning preparation raw material of each element in Ce base quenched powder, then carry out melting and obtain molten state Ce-Fe-
-b-M foundry alloy.In the process of melting, can there is a series of chemical change in each atom in raw material, and formation has the principal phase of certain proportioning and rich Ce phase.Described inert atmosphere refers to the atmosphere such as nitrogen, argon gas, neon, Krypton.
In step S112, by fast quenching, obtain amorphous state or the nanocrystalline Ce base rapid tempering belt coexisted with amorphous, so that preparation has the rare earth material of high magnetic characteristics.
In step S113, described Ce base rapid tempering belt forms Ce base quenched powder by Mechanical Crushing so that follow-up hot-forming in form better contact with Re-Fe-B quenched powder.
The preparation method that described Re-Fe-B quenched powder can refer to above-mentioned Ce base quenched powder is prepared, and also directly can buy from market, not repeat them here.
In step s 2, by being mixed with described Re-Fe-B quenched powder by described Ce base quenched powder, described Ce base quenched powder is uniformly distributed in described Re-Fe-B quenched powder.Described mixing can be carried out in three-dimensional material mixer.Mass ratio described in described mixing magnetic shared by Ce base quenched powder is 10% ~ 50%.Mass ratio described in described mixing magnetic shared by Ce base quenched powder is preferably 10% ~ 20%, and the magnet magnetic energy product of the rare earth permanent-magnetic material now obtained is greater than 39MGOe, and HCJ is greater than 12kOe, and remanent magnetism is greater than 12.6kGs.
In step s3, many principal phases rare earth permanent-magnetic material of flake crystalline structure is prepared into by described hot-forming and thermoforming technique.Be specially: hot-formingly make alloy densification, obtain hot pressing blank; In thermal deformation process, hot pressing blank under high moderate pressure effect, (Nd, Ce)
2(Fe, Co)
14b phase crystal grain, by dissolving-mass transfer-recrystallization process, form the flake crystalline along the consistent orientation of easy magnetizing axis c-axis, therefore heat distortion magnet has higher remanent magnetism; Because forming temperature is low, temperature retention time is short, and therefore crystal grain is tiny, and coercive force is high.
Described hot-forming process is specially: mixing magnetic is put into the first mould, is heated to the first temperature, and applies the first pressure to the first mould, obtain hot pressing blank in vacuum environment to mixing magnetic.Wherein, described first temperature is 650 DEG C ~ 700 DEG C, and described first pressure is 150MPa ~ 200MPa, and the vacuum degree of described vacuum environment is not less than 5 × 10
-2pa.
The process of described thermoforming is specially: described hot pressing blank is put into the second mould, in an inert atmosphere the second temperature is heated to described hot pressing blank, described hot pressing blank is made to carry out the distortion that degree of deformation is 30% ~ 95%, again the second pressure is applied to the hot pressing blank after distortion, obtain heat distortion magnet.Wherein said second temperature is 800 DEG C ~ 900 DEG C, and described second pressure is 30MPa ~ 100MPa.
The process of described temper is specially: in vacuum environment, described heat distortion magnet be heated to the 3rd temperature and be incubated, and terminating rear quenching chilling in insulation.Described 3rd temperature is 500 DEG C ~ 800 DEG C, and temperature retention time is 1 hour ~ 10 hours, during heating heating rate be 5 DEG C/min ~ 20 DEG C/min.It should be noted that, heat distortion magnet is through temper, and heat distortion magnet is through temper, and by atoms permeating, composition becomes branch's generation change to a certain degree mutually with crystal grain, but grain morphology and size do not change substantially.
The present invention also provides a kind of rare earth permanent-magnetic material, and described rare earth permanent-magnetic material is prepared by said method.Described rare earth permanent-magnetic material is many principal phases structure, and it is primarily of nano-grade crystalline substance composition.The chemical formula of described nano-grade crystalline substance is (Re
1-ace
a)
2(Fe
1-bco
b)
14b.Wherein, rare earth Re is one or more in Nd, Pr, Dy, Tb, a and b is the atomic ratio of corresponding element, 0≤a≤1,0≤b≤0.5.The length of described nano-grade crystalline substance is 200nm ~ 1000nm, and thickness is 50nm ~ 100nm.
In preparation method of the present invention, make alloy densification by hot press forming technology, obtain hot pressing blank; In thermal deformation process, hot pressing blank under high moderate pressure effect, (Nd, Ce)
2(Fe, Co)
14b phase crystal grain, by dissolving-mass transfer-recrystallization process, form the flake crystalline along the consistent orientation of easy magnetizing axis c-axis, therefore heat distortion magnet has higher remanent magnetism; Because forming temperature is low, temperature retention time is short, and therefore crystal grain is tiny, and coercive force is high, and the magnetic property of the described rare earth permanent-magnetic material obtained is excellent.Further, described rare earth permanent-magnetic material is many principal phases structure, and it is primarily of nano-grade crystalline substance composition, and corrosion resistance is strong, has good practicality.
And owing to adopting cheap Rare-Earth Ce part to replace the rare earth metals such as expensive Nd, Pr, Ce maximum level can reach 50% of total amount of rare earth, thus reduces production cost, and balance rare earth utilizes.
Further, also can regulate the mixed proportion of described Ce base quenched powder and described Re-Fe-B quenched powder as required, and then regulate the content of Ce in described rare earth material to adjust its magnetic characteristic, to meet the needs of magnetic property in different product.Described preparation method is easy to realize newly net forming, and material recovery rate is high, and technique is simple, is applicable to suitability for industrialized production.
Below, will further illustrate in conjunction with specific embodiments.
Embodiment (1)
According to Ce base quenched powder (Ce
31fe
68b
1) in the batching accurate in scale of each element, be prepared into Ce through electric arc or induction furnace melting
31fe
68b
1foundry alloy, fusion process carries out under argon shield.By Ce in argon gas atmosphere
31fe
68b
1foundry alloy remelting, then be injected into water-cooled copper roller and carry out fast quenching, obtain Ce
31fe
68b
1rapid tempering belt, wherein roll surface speed is 35m/s, and fast quenching temperature is 1350 DEG C, and expulsion pressure is 0.02MPa.By Ce
31fe
68b
1rapid tempering belt is broken into the Ce that particle diameter is 50 microns ~ 300u micron
31fe
68b
1quenched powder.
After magnetic separation, by Ce
31fe
68b
1(composition is Nd for quenched powder and MQP-F powder
29.8pr
0.4fe
64.41co
4b
0.93ga
0.46) in three-dimensional material mixer mixing within 3 hours, obtain mix magnetic.Wherein Ce
31fe
68b
1quenched powder accounts for 10% of mixing magnetic gross mass.
Mixing magnetic is put into the first mould, induction heating in vacuum environment, when temperature is upgraded to 200 DEG C, start to apply the first pressure to the first mould, and maximum temperature controls to be 670 DEG C, obtains hot pressing blank.The time being wherein raised to maximum temperature from room temperature is 5 minutes ~ 6 minutes, and the first pressure is 150MPa, and in hot pressing, vacuum degree is not less than 5 × 10
-2pa.
Hot pressing blank is put into the second mould that diameter is larger, in argon gas atmosphere, induction heating is carried out to hot pressing blank, make described hot pressing blank carry out the distortion that degree of deformation is 70%.After temperature reaches maximum temperature 840 DEG C, be incubated 1.5 minutes, then apply the second pressure, obtain heat distortion magnet.Wherein, the time being raised to maximum temperature from room temperature is 6 minutes ~ 7 minutes, and the second pressure is 50MPa.
By heat distortion magnet in vacuum environment, 700 DEG C of tempering 3.5 hours.The rare earth permanent-magnetic material being of a size of Φ 10 × 10 is machined to after cooling.
For better analyzing the composition of the rare earth permanent-magnetic material obtained, also XRD (see Fig. 1) being carried out to rare earth permanent-magnetic material and analyzing.
Obtained rare earth permanent-magnetic material is at room temperature carried out test magnetic property, and test result is in table 1.Wherein, B
rrepresent remanent magnetism, unit is kGs; H
cjrepresent coercive force, unit is kOe; (BH)
mrepresent magnetic energy product, unit is MGOe.
The magnetic property of the rare earth permanent-magnetic material that table 1 embodiment 1 and 2 is obtained
Embodiment (2)
The process that embodiment (2) prepares rare earth permanent-magnetic material is substantially identical with embodiment (1), and difference is, when preparing mixing magnetic, and wherein Ce
31fe
68b
1quenched powder accounts for 20% of mixing magnetic gross mass, and when carrying out temper to heat distortion magnet, tempering time is 2.5 hours.
Obtained rare earth permanent-magnetic material is at room temperature carried out test magnetic property, and test result is in table 1.
For better analyzing composition and the microscopic pattern of described rare earth permanent-magnetic material, also XRD (see Fig. 1), SEM (see Fig. 2) and X-ray energy spectrum (EDS) (see table 2) analysis are carried out to described rare earth permanent-magnetic material.
The EDS result of rare earth permanent-magnetic material prepared by table 2 embodiment 2
Embodiment (3)
The process that embodiment (3) prepares rare earth permanent-magnetic material is substantially identical with embodiment (1), and difference is, when preparing mixing magnetic, and wherein Ce
31fe
68b
1quenched powder accounts for 30% of mixing magnetic gross mass.
For better analyzing composition and the microscopic pattern of described rare earth permanent-magnetic material, also XRD (see Fig. 1), SEM (see Fig. 3) and X-ray energy spectrum (EDS) (see table 3) analysis are carried out to described rare earth permanent-magnetic material.
The EDS result of rare earth permanent-magnetic material prepared by table 3 embodiment 3
Embodiment (4)
The process that embodiment (4) prepares rare earth permanent-magnetic material is substantially identical with embodiment (1), and difference is, when preparing mixing magnetic, and wherein Ce
31fe
68b
1quenched powder accounts for 50% of mixing magnetic gross mass.
The rare earth permanent-magnetic material obtained is carried out XRD analysis (see Fig. 1).
Reference examples
The process that reference examples prepares rare earth permanent-magnetic material is substantially identical with embodiment (1), and difference is, only with MQP-F powder, (composition is for Nd
29.8pr
0.4fe
64.41co
4b
0.93ga
0.46) as raw material, and do not add Ce
31fe
68b
1quenched powder.
The rare earth permanent-magnetic material obtained is carried out XRD analysis (see Fig. 1).
As seen from Figure 1, the principal phase of described rare earth permanent-magnetic material is (Nd, Ce)
2(Fe, Co)
14b phase.For comparative example, add Ce
31fe
68b
1after quenched powder, the diffraction maximum of described rare earth permanent-magnetic material moves to right.As Ce in mixing magnetic
31fe
68b
1when mass fraction shared by quenched powder is equal to or greater than 30%, in rare earth permanent-magnetic material, form a little CeFe
2phase.
From Fig. 2, Fig. 3, table 2 and table 3, rare earth permanent-magnetic material is by (Nd
1-ace
a)
2(Fe
1-bco
b)
14the many principal phase compositions of B, main phase grain mostly is flake crystalline, the equiax crystal that yet existence part is not out of shape.Described flake crystalline is of a size of nanoscale, and its length and thickness are about 800nm, 100nm respectively.
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection range of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (8)
1. a preparation method for rare earth permanent-magnetic material, it comprises the following steps:
(1) provide Re-Fe-B quenched powder and Ce base quenched powder respectively, wherein said Re-Fe-B quenched powder middle rare earth Re is one or more in Nd, Pr, Dy, Tb, and the chemical formula of described Ce base quenched powder is Ce
xfe
(100-x-y-z)b
ym
z, M be selected from Ga, Co, Al, Zn, Cu, Nb and Zr one or more, x, y and z are the mass percentage of corresponding element, and 28%≤x≤35%, 0.8%≤y≤1.5%, 0%≤z≤2%;
(2) mixed with described Re-Fe-B quenched powder by described Ce base quenched powder and obtain mixing magnetic, wherein, the mass percent described in described mixing magnetic shared by Ce base quenched powder is 10% ~ 50%;
(3) described mixing magnetic is carried out successively hot-forming, thermoforming and temper, obtain rare earth permanent-magnetic material, described rare earth permanent-magnetic material is many principal phases structure, and described rare earth permanent-magnetic material is primarily of nano-grade crystalline substance composition.
2. the preparation method of rare earth permanent-magnetic material as claimed in claim 1, it is characterized in that, the mass percent described in described mixing magnetic shared by Ce base quenched powder is 10% ~ 20%.
3. the preparation method of rare earth permanent-magnetic material as claimed in claim 1, is characterized in that, step (1) described in the preparation method of Ce base quenched powder as follows:
First, the method melting Ce-Fe-of electric arc or induction melting is adopted
-b-M foundry alloy, described fusion process carries out under an inert atmosphere;
Then, in an inert atmosphere by molten state Ce-Fe-
-b-M foundry alloy is injected into water-cooled running roller and carries out fast quenching, obtains Ce base rapid tempering belt, and wherein roll surface speed is 10m/s ~ 50m/s, and fast quenching temperature is 1200 DEG C ~ 1500 DEG C, and expulsion pressure is 0.01MPa ~ 0.1MPa;
Finally, described Ce base rapid tempering belt is carried out Mechanical Crushing, form the Ce base quenched powder that particle diameter is 50 microns ~ 300 microns.
4. the preparation method of rare earth permanent-magnetic material as claimed in claim 1, it is characterized in that, step (3) described in hot-forming process be specially: mixing magnetic is put into the first mould, in vacuum environment, the first temperature is heated to mixing magnetic, and the first pressure is applied to the first mould, obtain hot pressing blank, wherein, described first temperature is 650 DEG C ~ 700 DEG C, and described first pressure is 150MPa ~ 200MPa, and the vacuum degree of described vacuum environment is not less than 5 × 10
-2pa.
5. the preparation method of rare earth permanent-magnetic material as claimed in claim 4, it is characterized in that, step (3) described in the process of thermoforming be specially: described hot pressing blank is put into the second mould, in an inert atmosphere the second temperature is heated to described hot pressing blank, described hot pressing blank is made to carry out the distortion that degree of deformation is 30% ~ 95%, again the second pressure is applied to the hot pressing blank after distortion, obtain heat distortion magnet, wherein said second temperature is 800 DEG C ~ 900 DEG C, and described second pressure is 30MPa ~ 100MPa.
6. the preparation method of rare earth permanent-magnetic material as claimed in claim 5, it is characterized in that, step (3) described in the process of temper be specially: in vacuum environment, described heat distortion magnet be heated to the 3rd temperature and be incubated, and terminate rear quenching chilling in insulation, wherein the 3rd temperature is 500 DEG C ~ 800 DEG C, temperature retention time is 1 hour ~ 10 hours, during heating heating rate be 5 DEG C/min ~ 20 DEG C/min.
7. one kind adopts the rare earth permanent-magnetic material that preparation method obtains as described in claim 1 to 6, it is characterized in that, described rare earth permanent-magnetic material is many principal phases structure, and described rare earth permanent-magnetic material is primarily of nano-grade crystalline substance composition, and the chemical formula of described nano-grade crystalline substance is (Re
1-ace
a)
2(Fe
1-bco
b)
14b, wherein, rare earth Re is one or more in Nd, Pr, Dy, Tb, a and b is the atomic ratio of corresponding element, 0≤a≤1,0≤b≤0.5.
8. rare earth permanent-magnetic material as claimed in claim 7, it is characterized in that, the length of described nano-grade crystalline substance is 200nm ~ 1000nm, and thickness is 50nm ~ 100nm.
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