CN108133797B - 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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- CN108133797B CN108133797B CN201711366476.7A CN201711366476A CN108133797B CN 108133797 B CN108133797 B CN 108133797B CN 201711366476 A CN201711366476 A CN 201711366476A CN 108133797 B CN108133797 B CN 108133797B
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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 preparation 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%, one of Pr:4-6%, Nd:15-17%, M Nb, Ti, V, Co, Cr, Mn, Ni, Zr, Ga, Ag, Ta, Al, Au, Pb, Cu, Si are several.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 technique
Sintered NdFeB is widely used in various fields because it is with excellent magnetic property, with people's life also close phase
It closes.Meanwhile sintered NdFeB is the ideal material of high-effect, small in size, the light-weight magnetic function device of manufacture, is expected to perhaps
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 balance benefit of the control and resource to cost
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%.Preparing Nd used in sintered NdFeB permanent magnet is obtained by mischmetal separating-purifying, in this process
In, a large amount of rare earth Las and Ce are idle, and it is dirty to generate serious environment due to needing to use soda acid for separating-purifying process
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 purify the dirt of Pr, Nd bring environment from Rare Earth Mine
Dye.But due to containing a large amount of Ce element 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 will affect the coercivity of magnet, lead to sintered magnet
To not be able to satisfy actual requirement, 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, to improve mischmetal iron boron
The magnetic property of magnet has and very big wishes that the substitution for low and middle-end magnet may be implemented.
Summary of the invention
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 inhibiting CeFe by La substitution2The 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 be Nb, Ti, V, Co, Cr, Mn, Ni, Zr, Ga,
One of Ag, Ta, Al, Au, Pb, Cu, Si are several, and x, y, z meets 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, to improve the magnetism of magnet
Energy.
One kind inhibiting CeFe by La substitution2The preparation method of the mischmetal iron boron magnet of phase, its step are as follows:
1) lanthanoid metal and mischmetal, iron, iron boron and other gold melting ingot casting and rapid-hardening flake: 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, is then poured above the water-cooled copper roller of rotation, copper roller revolving speed is 1-
5m/s is prepared with a thickness of the rapid hardening thicker strip of 0.2-0.5mm thickness；
2) hydrogen is quick-fried: carrying out the quick-fried processing of hydrogen to rapid casting using vacuum rotary hydrogen crushing furnace, obtains particle of uniform size；
3) airflow milling, be orientated die mould and wait static pressure: the quick-fried particle of hydrogen is placed in airflow mill, using high-pressure inert gas,
Airflow milling processing is carried out at 6-9 atm, the magnetic powder that average particle size is 2-5 μm is prepared, then under the magnetic field of 1.6-2T
Orientation die mould is carried out, and green compact are prepared in the cold isostatic press of 250kN pressure；
4) vacuum-sintering and tempering: being made magnet in 1000-1080 DEG C of sintering for green compact using sintering furnace, then into
The tempering of row level-one and two step tempering heat treatment of second annealing, level-one tempering temperature are 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 purification & isolation bring environmental pollution, reduce production cost.
2) present invention effectively inhibits the CeFe in magnet by the substitution that composition adjustment carries out La2Soft magnetic phase optimizes magnetic
The phase structure of body improves the performance of magnet.
Detailed description of the invention
Fig. 1 is La in embodiment and comparative examplexMMyFe100-x-y-z-1MzB1The XRD diagram of magnet.
Specific embodiment
Below 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.%), select mischmetal MM (MM ingredient is 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 on the copper roller that revolving speed is 3m/s, thickness is prepared
For 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, be orientated die mould and wait static pressure: the quick-fried particle of hydrogen is placed in airflow mill, using high-pressure inert gas,
Airflow milling processing is carried out at 6-9 atm, and the magnetic powder that average particle size is 5 μm is prepared, is then taken under the magnetic field of 2T
Green compact are prepared to die mould, and in the cold isostatic press of 250kN pressure.
4) using perseverance magnet is made in 1040 DEG C of sintering into sintering furnace in green compact by vacuum-sintering and tempering, then into
The tempering of row level-one and two step tempering heat treatment of second annealing, level-one tempering temperature are 950 DEG C, keep the temperature 3 hours, second annealing temperature
It is 525 DEG C, keeps the temperature 3 hours.
5) magnet prepared is put into BH tester and tests magnetic property, 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.%), lanthanoid metal, mischmetal MM (MM ingredient is Ce:50%, La:30%, Pr:4%, Nd:16%), iron, iron boron are selected
And other metals are placed in crucible and are filled with argon gas and carry out melting, are then poured on the copper roller that revolving speed is 1m/s, are prepared
With a thickness of 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, be orientated die mould and wait static pressure: the quick-fried particle of hydrogen is placed in airflow mill, using high-pressure inert gas,
Airflow milling processing is carried out at 6-9atm, and the magnetic powder that average particle size is 2 μm is prepared, then carries out under the magnetic field of 1.6T
It is orientated die mould, and green compact are prepared in the cold isostatic press of 250kN pressure.
4) using perseverance magnet is made in 1000 DEG C of sintering into sintering furnace in green compact by vacuum-sintering and tempering, then into
The tempering of row level-one and two step tempering heat treatment of second annealing, level-one tempering temperature are 850 DEG C, keep the temperature 3 hours, second annealing temperature
It is 450 DEG C, keeps the temperature 3 hours.
5) magnet prepared is put into BH tester and tests magnetic property, 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.%), lanthanoid metal and mischmetal MM (MM ingredient is Ce:50%, La:30%, Pr:4%, Nd:16%), iron, iron are selected
Boron and other metals, which are placed in crucible and are filled with argon gas, carries out melting, is then poured on the copper roller that revolving speed is 3m/s, is prepared into
To the rapid casting with a thickness 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, be orientated die mould and wait static pressure: the quick-fried particle of hydrogen is placed in airflow mill, using high-pressure inert gas,
Airflow milling processing is carried out at 6-9atm, and the magnetic powder that average particle size is 3 μm is prepared, then carries out under the magnetic field of 1.8T
It is orientated die mould, and green compact are prepared in the cold isostatic press of 250kN pressure.
4) using perseverance magnet is made in 1040 DEG C of sintering into sintering furnace in green compact by vacuum-sintering and tempering, then into
The tempering of row level-one and two step tempering heat treatment of second annealing, level-one tempering temperature are 900 DEG C, keep the temperature 3 hours, second annealing temperature
It is 525 DEG C, keeps the temperature 3 hours.
5) magnet prepared is put into BH tester and tests magnetic property, 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.%), select lanthanoid metal and mischmetal MM (MM ingredient is 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 revolving speed is 5m/s
On roller, it is prepared with a thickness of 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, be orientated die mould and wait static pressure: the quick-fried particle of hydrogen is placed in airflow mill, using high-pressure inert gas,
Airflow milling processing is carried out at 6-9atm, and the magnetic powder that average particle size is 5 μm is prepared, is then taken under the magnetic field of 2T
Green compact are prepared to die mould, and in the cold isostatic press of 250kN pressure.
4) using perseverance magnet is made in 1080 DEG C of sintering into sintering furnace in green compact by vacuum-sintering and tempering, then into
The tempering of row level-one and two step tempering heat treatment of second annealing, level-one tempering temperature are 950 DEG C, keep the temperature 3 hours, second annealing temperature
It is 600 DEG C, keeps the temperature 3 hours.
5) magnet prepared is put into BH tester and tests magnetic property, 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 (1)
1. one kind inhibits CeFe by La substitution2The preparation method of the mischmetal iron boron magnet of phase, which is characterized in that make most
Whole magnet meets nominal mass percent ingredient LaxMMyFe100-x-y-z-1MzB1, MM is norium, wherein respectively at
The mass percent divided is as follows: Ce:48-58%, La:20-30%, Pr:4-6%, Nd:15-17%；M be Nb, Ti, V, Co,
One of Cr, Mn, Ni, Zr, Ga, Ag, Ta, Al, Au, Pb, Cu, Si are several, and x, y, z meets following relationship: 20≤x+y
≤ 40,4≤x≤10,0.1≤z≤2；
Specific step is as follows for preparation method:
1) melting ingot casting and rapid-hardening flake: lanthanoid metal and mischmetal, iron, iron boron and element M is selected to be placed according to composition proportion
In crucible and it is filled with argon gas progress melting, is then poured above the water-cooled copper roller of rotation, copper roller revolving speed is 1-5m/s, is prepared
With a thickness of the rapid hardening thicker strip of 0.2-0.5mm thickness；
2) hydrogen is quick-fried: carrying out the quick-fried processing of hydrogen to rapid casting using vacuum rotary hydrogen crushing furnace, obtains particle of uniform size；
3) airflow milling, be orientated die mould and wait static pressure: 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, and the magnetic powder that average particle size is 2-5 μm is prepared, is then taken under the magnetic field of 1.6-2T
Green compact are prepared to die mould, and in the cold isostatic press of 250kN pressure；
4) vacuum-sintering and tempering: 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 tempering temperature are 850-950 DEG C, and second annealing temperature is 450-600
℃。
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