CN108133797A - A kind of inhibition CeFe2The preparation method of the mischmetal iron boron magnet of phase - Google Patents
A kind of inhibition CeFe2The preparation method of the mischmetal iron boron magnet of phase Download PDFInfo
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- CN108133797A CN108133797A CN201711366476.7A CN201711366476A CN108133797A CN 108133797 A CN108133797 A CN 108133797A CN 201711366476 A CN201711366476 A CN 201711366476A CN 108133797 A CN108133797 A CN 108133797A
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- iron boron
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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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- 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
- H01F41/0266—Moulding; Pressing
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Abstract
A kind of inhibition CeFe2The preparation method of the mischmetal iron boron magnet of phase, belongs to rareearth magnetic material preparing technical field.So that magnet nominal composition is LaxMMyFe100‑x‑y‑z‑1MzB1(20≤x+y≤40,4≤x≤10,0.1≤z≤2, wt.%), MM is norium, wherein Ce:48 58%, La:20 30%, Pr:4 6%, Nd:15 17%, the one or several kinds in M Nb, Ti, V, Co, Cr, Mn, Ni, Zr, Ga, Ag, Ta, Al, Au, Pb, Cu, Si.The present invention replaces MM to prepare inexpensive magnet by La, while the CeFe in magnet can be eliminated when La substitutes onto a certain amount of2Soft magnetic phase reduces the cost of sintered magnet in the case where improving magnet magnetic property, meets market demands, realize the comprehensive utilization of rare earth resources.
Description
Technical field
The present invention provides a kind of inhibition CeFe2The preparation method of the mischmetal iron boron magnet of phase, belongs to rare-earth magnetic
Technical field of material.
Background technology
Sintered NdFeB is widely used in various fields, with people's life also close phase because it is with excellent magnetic property
It closes.Meanwhile sintered NdFeB is the ideal material of high-effect, small, the light-weight magnetic function device of manufacture, is expected to being permitted
More application fields generate revolutionary impact.However, also making the rapidly increase of its demand with advances in technology, make neodymium iron boron
The rare earth raw material reserves of series permanent magnetic material are seriously reduced, while price is surging therewith.Therefore it is badly in need of finding a kind of magnetic property energy
Meet market requirement, the lower permanent magnet of cost replaces neodymium iron boron, realizes the control to cost and the balance profit of resource
With.
Mischmetal (MM) is made of elements such as Ce, La, Nd, Pr, wherein Ce:50-60%, La:25-35%, Pr:1-
10%, Nd:10-30%.It is obtained by mischmetal separating-purifying, in this process to prepare the Nd used in sintered NdFeB permanent magnet
In, a large amount of rare earth Las and Ce are idle, and separating-purifying process uses soda acid due to needing, and it is dirty to generate serious environment
Dye.Therefore using mischmetal as raw material, the mischmetal iron boron permanent-magnet attractive attention of numerous researchers is developed.One side
The utilization rate of rare earth element is improved in face, reduces cost；On the other hand alleviate and the environment dirt that Pr, Nd are brought is purified from Rare Earth Mine
Dye.But due to containing a large amount of Ce elements in mischmetal, CeFe can be generated in mischmetal iron boron magnet2Soft magnetism
Phase.CeFe2Soft magnetic phase can not only reduce the intensity of magnetization of magnet, but also can affect the coercivity of magnet, lead to sintered magnet
So as to which practical requirement cannot be met, the development of mischmetal iron boron is constrained.
In order to prepare high performance mischmetal iron boron magnet, the present invention substitutes mischmetal using Rare Earth Lanthanum,
By composition adjustment, the CeFe in mischmetal iron boron magnet is effectively inhibited2Soft magnetic phase, so as to improve mischmetal iron boron
The magnetic property of magnet has and very big wishes to realize the replacement for low and middle-end magnet.
Invention content
The present invention provides a kind of inhibition CeFe2The preparation method of the mischmetal iron boron magnet of phase, it is therefore an objective to reduce magnetic
Body cost eliminates the CeFe in magnet2Soft magnetic phase improves the magnetic property of magnet.
One kind inhibits CeFe by La substitutions2The preparation method of the mischmetal iron boron magnet of phase, makes final magnet name
Adopted ingredient is LaxMMyFe100-x-y-z-1MzB1(wt.%), MM is norium, wherein the mass percent of each ingredient is such as
Under：Ce:48-58%, La:20-30%, Pr:4-6%, Nd:15-17%；M for Nb, Ti, V, Co, Cr, Mn, Ni, Zr, Ga, Ag,
One or several kinds in Ta, Al, Au, Pb, Cu, Si, x, y, z meet following relationship：20≤x+y≤40,4≤x≤10,0.1
≤z≤2；When the substitution amount of La is 4%-10%, the CeFe in magnet can be eliminated2Phase, so as to improve the magnetic property of magnet.
One kind inhibits CeFe by La substitutions2The preparation method of the mischmetal iron boron magnet of phase, its step are as follows：
1) melting ingot casting and rapid-hardening flake：Lanthanoid metal and mischmetal, iron, iron boron and other gold are selected according to composition proportion
Belong to or element M is placed in crucible and is filled with argon gas and carries out melting, be then poured onto above the water-cooled copper roller of rotation, copper roller rotating speed is 1-
The rapid hardening thicker strip that thickness is 0.2-0.5mm thickness is prepared in 5m/s；
2) hydrogen is quick-fried：The quick-fried processing of hydrogen is carried out to rapid casting using vacuum rotary hydrogen crushing furnace, obtains particle of uniform size；
3) airflow milling, orientation die mould and isostatic pressed：The quick-fried particle of hydrogen is placed in airflow mill, using high-pressure inert gas,
Airflow milling processing is carried out under 6-9atm, it is 2-5 μm of magnetic powder that average particle size, which is prepared, then under the magnetic field of 1.6-2T into
Row orientation die mould, and green compact are prepared in the cold isostatic press of 250kN pressure；
4) vacuum-sintering and temper：Green compact are made by magnet, Ran Houjin in 1000-1080 DEG C of sintering using sintering furnace
Row level-one is tempered and two step tempering heat treatment of second annealing, and level-one temperature is 850-950 DEG C, and second annealing temperature is 450-
600℃。
The present invention has the advantage that compared with prior art：
1) present invention prepares sintered magnet using mischmetal (MM) and light rare earth metal lanthanum (La), realizes rare earth resources
Make full use of, alleviate the environmental pollution that purification ＆ isolation is brought, reduce production cost.
2) present invention carries out the effective CeFe inhibited in magnet of replacement of La by composition adjustment2Soft magnetic phase optimizes magnetic
The phase structure of body improves the performance of magnet.
Description of the drawings
Fig. 1 is La in embodiment and comparative examplexMMyFe100-x-y-z-1MzB1The XRD diagram of magnet.
Specific embodiment
With reference to embodiment and comparative example, the invention will be further described, but the present invention is not limited to following implementations
Example.
Comparative example 1：
1) melting ingot casting and rapid-hardening flake：According to nominal composition MM31.5Fe66.3M(Al0.2Cu0.2Co0.2Ga0.4Zr0.2)B1
(wt.%), selecting mischmetal MM, (MM ingredients are Ce:50%, La:30%, Pr:4%, Nd:16%), iron, iron boron and its
Its metal M, which is placed in crucible and is filled with argon gas, carries out melting, is then poured onto on the copper roller that rotating speed is 3m/s, thickness, which is prepared, is
The rapid casting of 0.2-0.5mm thickness.
2) hydrogen is quick-fried, carries out the quick-fried processing of hydrogen to rapid casting using vacuum rotary hydrogen crushing furnace, obtains particle of uniform size.
3) airflow milling, orientation die mould and isostatic pressed：The quick-fried particle of hydrogen is placed in airflow mill, using high-pressure inert gas,
Airflow milling processing is carried out under 6-9atm, the magnetic powder that average particle size is 5 μm is prepared, is then orientated under the magnetic field of 2T
Die mould, and green compact are prepared in the cold isostatic press of 250kN pressure.
4) using perseverance magnet, Ran Houjin is made in 1040 DEG C of sintering into sintering furnace in green compact by vacuum-sintering and temper
Row level-one is tempered and two step tempering heat treatment of second annealing, and level-one temperature is 950 DEG C, keeps the temperature 3 hours, second annealing temperature
It is 525 DEG C, keeps the temperature 3 hours.
5) magnet prepared is put into BH testers and tests magnetic property, it is as a result as follows：
Br=12.14kG, Hcj=4.12kOe, (BH)max=14.58MGOe.
Comparative example 2：
1) melting ingot casting and rapid-hardening flake：According to nominal composition La3MM28.5Fe66.3M(Al0.2Cu0.2Co0.2Ga0.4Zr0.2)B1
(wt.%), selecting lanthanoid metal, mischmetal MM, (MM ingredients are Ce:50%, La:30%, Pr:4%, Nd:16%), iron, iron boron
And other metals are placed in crucible and are filled with argon gas and carry out melting, are then poured onto on the copper roller that rotating speed is 1m/s, are prepared
Thickness is the rapid casting of 0.2-0.5mm thickness.
2) hydrogen is quick-fried, carries out the quick-fried processing of hydrogen to rapid casting using vacuum rotary hydrogen crushing furnace, obtains particle of uniform size.
3) airflow milling, orientation die mould and isostatic pressed：The quick-fried particle of hydrogen is placed in airflow mill, using high-pressure inert gas,
Airflow milling processing is carried out under 6-9atm, the magnetic powder that average particle size is 2 μm is prepared, is then taken under the magnetic field of 1.6T
To die mould, and green compact are prepared in the cold isostatic press of 250kN pressure.
4) using perseverance magnet, Ran Houjin is made in 1000 DEG C of sintering into sintering furnace in green compact by vacuum-sintering and temper
Row level-one is tempered and two step tempering heat treatment of second annealing, and level-one temperature is 850 DEG C, keeps the temperature 3 hours, second annealing temperature
It is 450 DEG C, keeps the temperature 3 hours.
5) magnet prepared is put into BH testers and tests magnetic property, it is as a result as follows：
Br=12.32kG, Hcj=4.35kOe, (BH)max=15.28MGOe.
Embodiment 1：
1) melting ingot casting and rapid-hardening flake：According to nominal composition La7MM24.5Fe66M(Al0.3Cu0.3Co0.2Ga0.4Zr0.3)B1
(wt.%), selecting lanthanoid metal and mischmetal MM, (MM ingredients are Ce:50%, La:30%, Pr:4%, Nd:16%), iron, iron
Boron and other metals, which are placed in crucible and are filled with argon gas, carries out melting, is then poured onto on the copper roller that rotating speed is 3m/s, is prepared into
To the rapid casting that thickness is 0.2-0.5mm thickness.
2) hydrogen is quick-fried, carries out the quick-fried processing of hydrogen to rapid casting using vacuum rotary hydrogen crushing furnace, obtains particle of uniform size.
3) airflow milling, orientation die mould and isostatic pressed：The quick-fried particle of hydrogen is placed in airflow mill, using high-pressure inert gas,
Airflow milling processing is carried out under 6-9atm, the magnetic powder that average particle size is 3 μm is prepared, is then taken under the magnetic field of 1.8T
To die mould, and green compact are prepared in the cold isostatic press of 250kN pressure.
4) using perseverance magnet, Ran Houjin is made in 1040 DEG C of sintering into sintering furnace in green compact by vacuum-sintering and temper
Row level-one is tempered and two step tempering heat treatment of second annealing, and level-one temperature is 900 DEG C, keeps the temperature 3 hours, second annealing temperature
It is 525 DEG C, keeps the temperature 3 hours.
5) magnet prepared is put into BH testers and tests magnetic property, it is as a result as follows：
Br=12.57kG, Hcj=4.58kOe, (BH)max=20.05MGOe.
Embodiment 2：
1) melting ingot casting and rapid-hardening flake：According to nominal composition La10MM21.5Fe66.1M(Al0.3Cu0.2Co0.2Ga0.5Zr0.2)B1
(wt.%), selecting lanthanoid metal and mischmetal MM, (MM ingredients are Ce:50%, La:30%, Pr:4%, Nd:
16%), iron, iron boron and other metals, which are placed in crucible and are filled with argon gas, carries out melting, is then poured onto the copper that rotating speed is 5m/s
On roller, the rapid casting that thickness is 0.2-0.5mm thickness is prepared.
2) hydrogen is quick-fried, carries out the quick-fried processing of hydrogen to rapid casting using vacuum rotary hydrogen crushing furnace, obtains particle of uniform size.
3) airflow milling, orientation die mould and isostatic pressed：The quick-fried particle of hydrogen is placed in airflow mill, using high-pressure inert gas,
Airflow milling processing is carried out under 6-9atm, the magnetic powder that average particle size is 5 μm is prepared, is then orientated under the magnetic field of 2T
Die mould, and green compact are prepared in the cold isostatic press of 250kN pressure.
4) using perseverance magnet, Ran Houjin is made in 1080 DEG C of sintering into sintering furnace in green compact by vacuum-sintering and temper
Row level-one is tempered and two step tempering heat treatment of second annealing, and level-one temperature is 950 DEG C, keeps the temperature 3 hours, second annealing temperature
It is 600 DEG C, keeps the temperature 3 hours.
5) magnet prepared is put into BH testers and tests magnetic property, it is as a result as follows：
Br=12.62kG, Hcj=4.25kOe, (BH) max=16.55MGOe.
La in 1 embodiment of tablexMMyFe100-x-y-z-1MzB1The remanent magnetism of magnet, coercivity and magnetic energy product and CeFe2Content.
Claims (2)
1. one kind inhibits CeFe by La substitutions2The preparation method of the mischmetal iron boron magnet of phase, which is characterized in that make most
Whole magnet nominal composition is LaxMMyFe100-x-y-z-1MzB1(wt.%), MM is norium, wherein the quality hundred of each ingredient
Divide ratio as follows：Ce:48-58%, La:20-30%, Pr:4-6%, Nd:15-17%；M for Nb, Ti, V, Co, Cr, Mn, Ni, Zr,
One or several kinds in Ga, Ag, Ta, Al, Au, Pb, Cu, Si, x, y, z meet following relationship：20≤x+y≤40,4≤x≤
10,0.1≤z≤2.
2. one kind described in claim 1 inhibits CeFe by La substitutions2The preparation method of the mischmetal iron boron magnet of phase,
It is characterized in that, its step are as follows：
1) melting ingot casting and rapid-hardening flake：According to composition proportion select lanthanoid metal and mischmetal, iron, iron boron and other metals or
Element M, which is placed in crucible and is filled with argon gas, carries out melting, is then poured onto above the water-cooled copper roller of rotation, copper roller rotating speed is 1-5m/
The rapid hardening thicker strip that thickness is 0.2-0.5mm thickness is prepared in s；
2) hydrogen is quick-fried：The quick-fried processing of hydrogen is carried out to rapid casting using vacuum rotary hydrogen crushing furnace, obtains particle of uniform size；
3) airflow milling, orientation die mould and isostatic pressed：The quick-fried particle of hydrogen is placed in airflow mill, using high-pressure inert gas, in 6-
Airflow milling processing is carried out under 9atm, the magnetic powder that average particle size is 2-5 μm is prepared, is then taken under the magnetic field of 1.6-2T
To die mould, and green compact are prepared in the cold isostatic press of 250kN pressure；
4) vacuum-sintering and temper：Green compact are made in 1000-1080 DEG C of sintering by magnet using sintering furnace, then carry out one
Grade tempering and two step tempering heat treatment of second annealing, level-one temperature are 850-950 DEG C, and second annealing temperature is 450-600
℃。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0632471A2 (en) * | 1993-06-14 | 1995-01-04 | Santoku Metal Industry Co., Ltd. | Permanent magnet containing rare earth metal, boron and iron |
| CN101241789A (en) * | 2007-11-07 | 2008-08-13 | 绵阳西磁科技开发公司 | A lanthanon permanent magnetic powder and its making method |
| CN103035350A (en) * | 2013-01-10 | 2013-04-10 | 浙江大学 | Low-cost permanent magnet prepared from misch metal (MM) and preparation method thereof |
-
2017
- 2017-12-18 CN CN201711366476.7A patent/CN108133797B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0632471A2 (en) * | 1993-06-14 | 1995-01-04 | Santoku Metal Industry Co., Ltd. | Permanent magnet containing rare earth metal, boron and iron |
| CN101241789A (en) * | 2007-11-07 | 2008-08-13 | 绵阳西磁科技开发公司 | A lanthanon permanent magnetic powder and its making method |
| CN103035350A (en) * | 2013-01-10 | 2013-04-10 | 浙江大学 | Low-cost permanent magnet prepared from misch metal (MM) and preparation method thereof |
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