CN106816249B - A kind of preparation method of the nanocrystalline permanent magnet of cheap light rare earth lanthanum ferrocerium boron - Google Patents

A kind of preparation method of the nanocrystalline permanent magnet of cheap light rare earth lanthanum ferrocerium boron Download PDF

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CN106816249B
CN106816249B CN201710011250.9A CN201710011250A CN106816249B CN 106816249 B CN106816249 B CN 106816249B CN 201710011250 A CN201710011250 A CN 201710011250A CN 106816249 B CN106816249 B CN 106816249B
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rare earth
permanent magnet
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ingot casting
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CN106816249A (en
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路清梅
钮建
岳明
刘卫强
张东涛
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Beijing University of Technology
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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
    • H01F1/0576—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 pressed, e.g. hot working
    • 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
    • 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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  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Hard Magnetic Materials (AREA)
  • Manufacturing Cores, Coils, And Magnets (AREA)

Abstract

A kind of preparation method of the nanocrystalline permanent magnet of cheap light rare earth lanthanum ferrocerium boron, belongs to rare earth permanent magnet field.By (Lax/Ce1‑x)yFe14The elemental mole ratios example of B, x=0~1, y=2.0~4.0 is matched, and is put into suspension smelting furnace after completing ingredient, under argon atmosphere, is heated melting, is obtained uniform ingot casting；Surface oxides are polished off to ingot casting machinery, is crushed, is fitted into quartz ampoule；Quartz ampoule equipped with ingot casting is installed in fast melt-quenching equipment, is melted, aluminium alloy is allowed to be sprayed on high-speed rotating copper roller from nozzle, aluminium alloy contacts copper roller and is quickly cooled down, and obtains rapid tempering belt；By rapid tempering belt by screening removal impurity, it is crushed sieving, is fitted into mold, is put into discharge plasma sintering furnace later, carries out hot pressed sintering using suitable temperature, pressure.The present invention is easily achieved the Fast Sintering of material, to obtain fine and close Ultra-fine Grained or even nanocrystalline sintered body.

Description

A kind of preparation method of the nanocrystalline permanent magnet of cheap light rare earth lanthanum ferrocerium boron
Technical field
The present invention relates to a kind of preparation methods of the nanocrystalline permanent magnet of cheap light rare earth lanthanum ferrocerium boron, belong to rare earth permanent magnet neck Domain.
Background technique
In institute's magnetic material, the usage amount first of permanent-magnet material, and rare earth permanent magnet is the important composition of permanent-magnet material Part is widely used in the various fields such as machinery, information, the energy, traffic, it has also become the support of modern industry and science and technology One of material.
1984, Japan and U.S. scientific research personnel were prepared for using powder metallurgic method and quick quenching technique with tetragonal respectively Neodymium iron boron (2:14:1) permanent magnet, to declare the birth of third generation rare earth permanent-magnetic material.Even to this day, Nd-Fe-B permanent magnetic Body is still the best permanent magnet of performance, is known as " magnetic king ".With automatic technology, the development of information technology and new energy Technology fast development and it is universal, the usage amount of neodymium iron boron increasingly increases, and output also increases therewith, makes making for neodymium metal (Nd) Dosage is continuously improved.However in natural rare earth resources, rare earth element is symbiosis, by taking the baiyuneboite of packet header as an example, mixing In rare earth, La:26~29%, Ce:49~53%, Pr:4~6%, Nd:15~17%.Along with largely opening for Nd, Pr element It adopts, La, Ce element are also extract therewith, and the richer La element of reserves and Ce element are small by a large amount of spare time due to dosage It sets, causes the configuration of resource seriously uneven.
It is well known that neodymium metal accounts for the 90% of the cost of raw material in Nd-Fe-B permanent magnet material, and not with Nd element price Disconnected soaring, along with permanent magnet product price improves few, the investment of artificial, equipment and workshop can give Rare Earth Industry in China It brings and is faced with quite huge pressure.And the price of light rare earth metal lanthanum, cerium is only 1/10th of metal praseodymium neodymium, is utilized Lanthanum, cerium come substituted metal spectrum, neodymium, obtain the magnet with certain magnetic property, and great economic benefit and society's effect will be generated by having Benefit.
Light rare earth lanthanum, there are the following problems for the preparation of cerium iron boron magnet: 1) intrinsic magnetic properties are relatively low.La2Fe14B and Ce2Fe14The saturation magnetization of B is respectively 13.8kGs and 11.7kGs, anisotropy field 20kOe and 26kOe, and Curie temperature is 257 DEG C and 149 DEG C, it is far below Nd2Fe14The saturation magnetization 16.1kGs of B, anisotropy field 73kOe and Curie temperature are 313℃；Therefore magnetic hardening is difficult using the sintering La/Ce-Fe-B magnet of prior powder metallurgy method preparation, obtains coercive Power, this is also one of the reason of it is not used widely.2) it is difficult to form stable single-phase 2:14:1 compound.On the one hand Lanthanum ion radius itself is excessive, on the other hand it is that tetravalence Ce is more readily formed in Ce elements when at phase that lanthanum iron boron is mutually very unstable Ion, while easily generating non magnetic second phase CeFe2；3) during the sintering process, rich La, Ce phase of low melting point is readily volatilized, The missing of Nd-rich phase leads to that enough magnetic isolation phases can not be formed between Ce-Fe-B magnet crystal grain, can not block (La/Ce)2Fe14The intercrystalline exchange-coupling interaction of B, and Rare Earth Lanthanum and cerium are easier to aoxidize, and so as to cause the decline of magnet coercivity, obtain The La/Ce-Fe-B magnet coercivity arrived is extremely low, is unable to satisfy market needs.
In fact, cheap light rare earth ferroboron research is main at present concentrates two aspects: first is that concentrating on lanthanum cerium dopping Aspect substitutes part praseodymium neodymium with Cheap rare-earth lanthanum cerium, reduces cost with this, this respect research is very more, in terms of rapid tempering belt There are patent CN105513732A, patent CN105280319A etc.；There is patent in terms of mischmetal sintered permanent magnet CN103035350A, patent CN104715876A etc..Second is that in terms of lanthanum ferrocerium boron powder and rapid tempering belt, patent CN105304250A prepares the lanthanum cerium rapid tempering belt that magnetic energy product is more than 8MGOe using fast melt-quenching method.Have but without seeing There is the relevant report of the pure lanthanum cerium block shaped magnet of higher coercivity, and the research of block shaped magnet has great meaning for practical application Justice.
Summary of the invention
It is considered herein that pure light rare earth La, Ce rare earth element can form Nd2Fe14The rare-earth-iron-boron crystal structure of Type B, But the composite light-weight rare earth La of a certain amount of La element doping/Ce iron boron is easier to obtain single-phase 2:14:1 structure, to be had more There is excellent magnetic property.The present invention obtains (La by melting firstx/Ce1-x)yFe14B (x=0~1, y=2.0~4.0) casting Ingot, obtaining by melt spun has Nd2Fe14The La of B structure2Fe14B and Ce2Fe14The rapid tempering belt of B nanometer crystal microstructure, by fast quenching Band is packed into sintered-carbide die by grinding is broken, and being obtained using discharge plasma sintering has the isotropism of superior performance dilute Native permanent magnet.
In order to achieve the above object, (La is obtainedx/Ce1-x)yFe14B (x=0~1, y=2.0~4.0) rare-earth permanent magnet side The specific method is as follows for method:
The first step presses (Lax/Ce1-x)yFe14B (x=0~1, y=2.0~4.0) elemental mole ratios example is matched, complete At being put into suspension smelting furnace after ingredient, under argon atmosphere, heating makes its thawing, naturally cools to room temperature after mixing, Melting is multiple repeatedly, to obtain uniform ingot casting；
Second step, the ingot casting that the first step is obtained take out, and mechanical grinding falls surface oxides, carry out Mechanical Crushing, ingot casting Fragment is uniform as far as possible, is then charged into quartz ampoule；
Quartz ampoule equipped with ingot casting is installed in fast melt-quenching equipment by third step, and opening heating system melts ingot casting block Change, aluminium alloy is allowed to be sprayed on high-speed rotating copper roller from nozzle, aluminium alloy contacts copper roller and is quickly cooled down, and is thrown in collecting bin；
4th step, the rapid tempering belt that step 3 is obtained remove impurity by screening, are crushed sieving, are fitted into mold, later It is put into discharge plasma sintering furnace, carries out hot pressed sintering using suitable temperature, pressure.
In above-mentioned steps one, to avoid introducing excessive impurity using material purity 99% or more, rare earth is preferably 99.8% pure Ce, 99.9% pure La or commercially available mixed rare earth of lanthanum and cerium；99.8% Fe and pure B or ferroboron are dilute Native scaling loss amount is depending on equipment situation, generally the 0~10% of rare earth quality.
Above-mentioned steps three, during fast melt-quenching, the linear resonance surface velocity of the copper roller is 10~60m/s, nozzle diameter 0.4 ~1mm, nozzle are 0.2~0.6mm away from roller height.
In above-mentioned steps four, it is sieved after obtained rapid tempering belt is broken, suitable sintered bar is then selected according to alloying component Part, sintering temperature are generally 550~800 DEG C, and heating rate is 30~150 DEG C/min, and sintering pressure is 10~500MPa, protect The warm time is 1~10min.
It is preferred that x=0.2~0.8, further preferred x=0.3, y=3.0.
Sintering pressure uses graphite jig in 100MPa or less, and sintered-carbide die is used when more than 100MPa.Pressurization Mode is first to be pre-stressed to certain pressure, is then gradually added to setting pressure during the sintering process.Sintering terminates, and temperature drops 100 DEG C Gradually release afterwards.Release mode are as follows: terminate, gradually release after temperature drops 100 DEG C.
Material phase analysis and magnetism testing are carried out after the magnet surface polishing of acquisition.Material phase analysis is using X-ray diffraction point Analyzer carries out object and mutually tests, and magnetism testing is carried out using VersaLab system type vibrating specimen magnetometer (VSM).
The present invention studies have shown that a certain amount of earth La addition, can effectively inhibit non magnetic second phase CeFe2's It generates.As shown in Figure 1, there is no CeFe in addition La hot-pressed magnets XRD2Phase, the second phase CeFe2It is unfavorable to the magnetic property of magnet, disappear Except CeFe2The magnetic property of Ce-Fe-B can mutually be improved.Therefore, using the compound light rare earth of a certain proportion of La/Ce, by controlling La/ Ce ratio and m elt-spun overqu- enching, especially quenching speed obtain coercivity greater than 5kOe, and magnetic energy product can exceed that 7MGOe's Rapid tempering belt with single-phase 2:14:1 structure.Then in conjunction with discharge plasma sintering technique, put using its unique plasma A series of very fast etc. features of electric heating, pressurization, heating-cooling speed, it is easy to the Fast Sintering of material is realized, to be caused Close Ultra-fine Grained or even nanocrystalline sintered body.The present invention be using the technology, by high-performance rapid tempering belt it is screened and grinding after It is put into discharging plasma sintering equipment, under certain temperature and pressure, by controlling sintering condition, innovative obtains a system Column have coercitive ferrocerium boron sintered magnet.Preparation and subsequent magnet performance of this method for light rare earth iron boron sintered body Optimization provides possibility.
Detailed description of the invention
Fig. 1 is (La prepared by embodiment 2 and 40.3Ce0.7)3Fe14B and Ce3Fe14B hot-pressed magnets XRD spectrum.
Fig. 2 is (La prepared by embodiment 20.3Ce0.7)3Fe14B hot-pressed magnets hysteresis loop.
Specific embodiment
Hereinafter, carrying out the embodiment that the present invention will be described in detail in conjunction with attached drawing, but the present invention is not limited to following embodiments.
Using there are two types of rare earths materials, one is commercially available mixed rare earth of lanthanum and cerium, (typical case obtained after raw ore simple separation is mixed Close rare earth), total amount of rare earth >=99%, general ingredient are as follows: La=30~40wt.%, Ce=60~70wt.%, other are can not Avoid impurity；Another kind is the pure La that raw material is 99.9% pure Ce, 99.9%；Rare earth scaling loss amount is the 0~10% of rare earth quality. Sintering pressure uses graphite jig in 100MPa or less, and sintered-carbide die is used when more than 100MPa.Pressuring method is first It is pre-stressed to certain pressure, is then gradually added to setting pressure during the sintering process.Sintering terminates, and temperature is gradually unloaded after dropping 100 DEG C Pressure.
Embodiment 1:
One kind (La0.3Ce0.7)2Fe14The preparation of B hot-pressed magnets, implements according to the following steps:
The first step presses (La0.3Ce0.7)2Fe14B ratio is matched, and is put into suspension smelting furnace after completing ingredient, in argon Under atmosphere is enclosed, heating makes its thawing, naturally cools to room temperature after mixing, repeatedly melting 4 times, to obtain uniformly casting Ingot；
Second step, the ingot casting that the first step is obtained take out, and mechanical grinding falls surface oxides, carry out Mechanical Crushing, ingot casting Fragment is uniform as far as possible, is then charged into quartz ampoule；
Quartz ampoule equipped with ingot casting is installed in fast melt-quenching equipment by third step, and opening heating system melts ingot casting block Change, allows aluminium alloy to be sprayed on high-speed rotating copper roller from nozzle, then collect rapid tempering belt.The linear resonance surface velocity of roller is 25m/s, spray Outspoken diameter 0.6mm, nozzle are 0.3mm away from roller height.Rapid tempering belt is obtained with a thickness of 0.10~0.45mm；
4th step, the rapid tempering belt that step 3 is obtained remove impurity by screening, broken to sieve with 100 mesh sieve, and being packed into diameter is In the sintered-carbide die of 20mm, it is put into the sintering of discharge plasma sintering furnace later.Specific sintering process are as follows: heating rate 50~ 80 DEG C/min, 600 DEG C of sintering temperature simultaneously keeps the temperature 3 minutes, pressure 300MPa.
(the La obtained according to above-mentioned technique0.3Ce0.7)2Fe14B hot-pressed magnets density reaches 7.63g/cm3, VSM test knot Fruit shows its remanent magnetism 1.61kGs, coercivity 1.11kOe, magnetic energy product 0.51MGOe.
Embodiment 2:
One kind (La0.3Ce0.7)3Fe14The preparation of B hot-pressed magnets, implements according to the following steps:
The first step presses (La0.3Ce0.7)3Fe14B ratio is matched, and is put into suspension smelting furnace after completing ingredient, in argon Under atmosphere is enclosed, heating makes its thawing, naturally cools to room temperature after mixing, repeatedly melting 4 times, to obtain uniformly casting Ingot；
Second step, the ingot casting that the first step is obtained take out, and mechanical grinding falls surface oxides, carry out Mechanical Crushing, ingot casting Fragment is uniform as far as possible, is then charged into quartz ampoule；
Quartz ampoule equipped with ingot casting is installed in fast melt-quenching equipment by third step, and opening heating system melts ingot casting block Change, allows aluminium alloy to be sprayed on high-speed rotating copper roller from nozzle, then collect rapid tempering belt.The linear resonance surface velocity of roller is 25m/s, spray Outspoken diameter 0.6mm, nozzle are 0.3mm away from roller height.Rapid tempering belt is obtained with a thickness of 0.10~0.45mm；
4th step, the rapid tempering belt that step 3 is obtained remove impurity by screening, broken to sieve with 100 mesh sieve, and being packed into diameter is In the sintered-carbide die of 20mm, it is put into the sintering of discharge plasma sintering furnace later.Specific sintering process are as follows: heating rate 50~ 80 DEG C/min, 600 DEG C of sintering temperature simultaneously keeps the temperature 3 minutes, pressure 300MPa.
(the La obtained according to above-mentioned technique0.3Ce0.7)3Fe14B hot-pressed magnets density reaches 7.51g/cm3, crystal structure Single-phase 2:14:1 structure is shown as, as shown in Fig. 1 XRD spectrum；VSM test result shows its remanent magnetism 4.31kGs, coercivity 3.25kOe, magnetic energy product 2.39MGOe.
Embodiment 3:
One kind (La0.3Ce0.7)4Fe14The preparation of B hot-pressed magnets, implements according to the following steps:
The first step presses (La0.3Ce0.7)4Fe14B ratio is matched, and is put into suspension smelting furnace after completing ingredient, in argon Under atmosphere is enclosed, heating makes its thawing, naturally cools to room temperature after mixing, repeatedly melting 4 times, to obtain uniformly casting Ingot；
Second step, the ingot casting that the first step is obtained take out, and mechanical grinding falls surface oxides, carry out Mechanical Crushing, ingot casting Fragment is uniform as far as possible, is then charged into quartz ampoule；
Quartz ampoule equipped with ingot casting is installed in fast melt-quenching equipment by third step, and opening heating system melts ingot casting block Change, allows aluminium alloy to be sprayed on high-speed rotating copper roller from nozzle, then collect rapid tempering belt.The linear resonance surface velocity of roller is 25m/s, spray Outspoken diameter 0.6mm, nozzle are 0.3mm away from roller height.Rapid tempering belt is obtained with a thickness of 0.10~0.45mm；
4th step, the rapid tempering belt that step 3 is obtained remove impurity by screening, broken to sieve with 100 mesh sieve, and being packed into diameter is In the sintered-carbide die of 20mm, it is put into the sintering of discharge plasma sintering furnace later.Specific sintering process are as follows: heating rate 50~ 80 DEG C/min, 600 DEG C of sintering temperature simultaneously keeps the temperature 3 minutes, pressure 300MPa.
(the La obtained according to above-mentioned technique0.3Ce0.7)4Fe14B hot-pressed magnets density reaches 7.45g/cm3, VSM test knot Fruit shows its remanent magnetism 3.04kGs, coercivity 1.98kOe, magnetic energy product 1.07MGOe.
Embodiment 4:
A kind of Ce3Fe14The preparation of B hot-pressed magnets, implements according to the following steps:
The first step, by Ce3Fe14B ratio is matched, and is put into suspension smelting furnace after completing ingredient, under argon atmosphere, Heating makes its thawing, room temperature is naturally cooled to after mixing, repeatedly melting 4 times, to obtain uniform ingot casting；
Second step, the ingot casting that the first step is obtained take out, and mechanical grinding falls surface oxides, carry out Mechanical Crushing, ingot casting Fragment is uniform as far as possible, is then charged into quartz ampoule；
Quartz ampoule equipped with ingot casting is installed in fast melt-quenching equipment by third step, and opening heating system melts ingot casting block Change, allows aluminium alloy to be sprayed on high-speed rotating copper roller from nozzle, then collect rapid tempering belt.The linear resonance surface velocity of roller is 25m/s, spray Outspoken diameter 0.6mm, nozzle are 0.3mm away from roller height.Rapid tempering belt is obtained with a thickness of 0.10~0.45mm；
4th step, the rapid tempering belt that step 3 is obtained remove impurity by screening, broken to sieve with 100 mesh sieve, and being packed into diameter is In the sintered-carbide die of 20mm, it is put into the sintering of discharge plasma sintering furnace later.Specific sintering process are as follows: heating rate 50~ 80 DEG C/min, 600 DEG C of sintering temperature simultaneously keeps the temperature 3 minutes, pressure 300MPa.
The Ce obtained according to above-mentioned technique3Fe14B hot-pressed magnets density reaches 7.73g/cm3, crystal structure shows as list Phase 2:14:1 structure and miscellaneous phase CeFe2, as shown in Fig. 1 XRD spectrum；VSM test result shows its remanent magnetism 3.39kGs, coercivity 2.05kOe, magnetic energy product 1.53MGOe.
Embodiment 5:
One kind (La0.2Ce0.8)3Fe14The preparation of B hot-pressed magnets, implements according to the following steps:
The first step presses (La0.2Ce0.8)3Fe14B ratio is matched, and is put into suspension smelting furnace after completing ingredient, in argon Under atmosphere is enclosed, heating makes its thawing, naturally cools to room temperature after mixing, repeatedly melting 4 times, to obtain uniformly casting Ingot；
Second step, the ingot casting that the first step is obtained take out, and mechanical grinding falls surface oxides, carry out Mechanical Crushing, ingot casting Fragment is uniform as far as possible, is then charged into quartz ampoule；
Quartz ampoule equipped with ingot casting is installed in fast melt-quenching equipment by third step, and opening heating system melts ingot casting block Change, allows aluminium alloy to be sprayed on high-speed rotating copper roller from nozzle, then collect rapid tempering belt.The linear resonance surface velocity of roller is 25m/s, spray Outspoken diameter 0.6mm, nozzle are 0.3mm away from roller height.Rapid tempering belt is obtained with a thickness of 0.10~0.45mm；
4th step, the rapid tempering belt that step 3 is obtained remove impurity by screening, broken to sieve with 100 mesh sieve, and being packed into diameter is In the sintered-carbide die of 20mm, it is put into the sintering of discharge plasma sintering furnace later.Specific sintering process are as follows: heating rate 50~ 80 DEG C/min, 600 DEG C of sintering temperature simultaneously keeps the temperature 3 minutes, pressure 300MPa.
(the La obtained according to above-mentioned technique0.2Ce0.8)3Fe14B hot-pressed magnets density reaches 7.58g/cm3, VSM test knot Fruit shows its remanent magnetism 4.11kGs, coercivity 3.07kOe, magnetic energy product 1.95MGOe.
Embodiment 6:
One kind (La0.4Ce0.6)3Fe14The preparation of B hot-pressed magnets, implements according to the following steps:
The first step presses (La0.4Ce0.6)3Fe14B ratio is matched, and is put into suspension smelting furnace after completing ingredient, in argon Under atmosphere is enclosed, heating makes its thawing, naturally cools to room temperature after mixing, repeatedly melting 4 times, to obtain uniformly casting Ingot；
Second step, the ingot casting that the first step is obtained take out, and mechanical grinding falls surface oxides, carry out Mechanical Crushing, ingot casting Fragment is uniform as far as possible, is then charged into quartz ampoule；
Quartz ampoule equipped with ingot casting is installed in fast melt-quenching equipment by third step, and opening heating system melts ingot casting block Change, allows aluminium alloy to be sprayed on high-speed rotating copper roller from nozzle, then collect rapid tempering belt.The linear resonance surface velocity of roller is 25m/s, spray Outspoken diameter 0.6mm, nozzle are 0.3mm away from roller height.Rapid tempering belt is obtained with a thickness of 0.10~0.45mm；
4th step, the rapid tempering belt that step 3 is obtained remove impurity by screening, broken to sieve with 100 mesh sieve, and being packed into diameter is In the sintered-carbide die of 20mm, it is put into the sintering of discharge plasma sintering furnace later.Specific sintering process are as follows: heating rate 50~ 80 DEG C/min, 600 DEG C of sintering temperature simultaneously keeps the temperature 3 minutes, pressure 300MPa.
(the La obtained according to above-mentioned technique0.4Ce0.6)3Fe14B hot-pressed magnets density reaches 7.43g/cm3, VSM test knot Fruit shows its remanent magnetism 3.72kGs, coercivity 2.64kOe, magnetic energy product 1.51MGOe.
Embodiment 7:
One kind (La0.6Ce0.4)3Fe14The preparation of B hot-pressed magnets, implements according to the following steps:
The first step presses (La0.6Ce0.4)3Fe14B ratio is matched, and is put into suspension smelting furnace after completing ingredient, in argon Under atmosphere is enclosed, heating makes its thawing, naturally cools to room temperature after mixing, repeatedly melting 4 times, to obtain uniformly casting Ingot；
Second step, the ingot casting that the first step is obtained take out, and mechanical grinding falls surface oxides, carry out Mechanical Crushing, ingot casting Fragment is uniform as far as possible, is then charged into quartz ampoule；
Quartz ampoule equipped with ingot casting is installed in fast melt-quenching equipment by third step, and opening heating system melts ingot casting block Change, allows aluminium alloy to be sprayed on high-speed rotating copper roller from nozzle, then collect rapid tempering belt.The linear resonance surface velocity of roller is 25m/s, spray Outspoken diameter 0.6mm, nozzle are 0.3mm away from roller height.Rapid tempering belt is obtained with a thickness of 0.10~0.45mm；
4th step, the rapid tempering belt that step 3 is obtained remove impurity by screening, broken to sieve with 100 mesh sieve, and being packed into diameter is In the sintered-carbide die of 20mm, it is put into the sintering of discharge plasma sintering furnace later.Specific sintering process are as follows: heating rate 50~ 80 DEG C/min, 600 DEG C of sintering temperature simultaneously keeps the temperature 3 minutes, pressure 300MPa.
(the La obtained according to above-mentioned technique0.6Ce0.4)3Fe14B hot-pressed magnets density reaches 7.31g/cm3, VSM test knot Fruit shows its remanent magnetism 2.75kGs, coercivity 1.87kOe, magnetic energy product 0.98MGOe.
Embodiment 8:
One kind (La0.8Ce0.2)3Fe14The preparation of B hot-pressed magnets, implements according to the following steps:
The first step presses (La0.8Ce0.2)3Fe14B ratio is matched, and is put into suspension smelting furnace after completing ingredient, in argon Under atmosphere is enclosed, heating makes its thawing, naturally cools to room temperature after mixing, repeatedly melting 4 times, to obtain uniformly casting Ingot；
Second step, the ingot casting that the first step is obtained take out, and mechanical grinding falls surface oxides, carry out Mechanical Crushing, ingot casting Fragment is uniform as far as possible, is then charged into quartz ampoule；
Quartz ampoule equipped with ingot casting is installed in fast melt-quenching equipment by third step, and opening heating system melts ingot casting block Change, allows aluminium alloy to be sprayed on high-speed rotating copper roller from nozzle, then collect rapid tempering belt.The linear resonance surface velocity of roller is 25m/s, spray Outspoken diameter 0.6mm, nozzle are 0.3mm away from roller height.Rapid tempering belt is obtained with a thickness of 0.10~0.45mm；
4th step, the rapid tempering belt that step 3 is obtained remove impurity by screening, broken to sieve with 100 mesh sieve, and being packed into diameter is In the sintered-carbide die of 20mm, it is put into the sintering of discharge plasma sintering furnace later.Specific sintering process are as follows: heating rate 50~ 80 DEG C/min, 600 DEG C of sintering temperature simultaneously keeps the temperature 3 minutes, pressure 300MPa.
(the La obtained according to above-mentioned technique0.8Ce0.2)3Fe14B hot-pressed magnets density reaches 7.19g/cm3, VSM test knot Fruit shows its remanent magnetism 1.05kGs, coercivity 0.63kOe, magnetic energy product 0.09MGOe.
Embodiment 9:
A kind of La3Fe14The preparation of B hot-pressed magnets, implements according to the following steps:
The first step, by La3Fe14B ratio is matched, and is put into suspension smelting furnace after completing ingredient, under argon atmosphere, Heating makes its thawing, room temperature is naturally cooled to after mixing, repeatedly melting 4 times, to obtain uniform ingot casting；
Second step, the ingot casting that the first step is obtained take out, and mechanical grinding falls surface oxides, carry out Mechanical Crushing, ingot casting Fragment is uniform as far as possible, is then charged into quartz ampoule；
Quartz ampoule equipped with ingot casting is installed in fast melt-quenching equipment by third step, and opening heating system melts ingot casting block Change, allows aluminium alloy to be sprayed on high-speed rotating copper roller from nozzle, then collect rapid tempering belt.The linear resonance surface velocity of roller is 25m/s, spray Outspoken diameter 0.6mm, nozzle are 0.3mm away from roller height.Rapid tempering belt is obtained with a thickness of 0.10~0.45mm；
4th step, the rapid tempering belt that step 3 is obtained remove impurity by screening, broken to sieve with 100 mesh sieve, and being packed into diameter is In the sintered-carbide die of 20mm, it is put into the sintering of discharge plasma sintering furnace later.Specific sintering process are as follows: heating rate 50~ 80 DEG C/min, 600 DEG C of sintering temperature simultaneously keeps the temperature 3 minutes, pressure 300MPa.
The La obtained according to above-mentioned technique3Fe14B hot-pressed magnets density reaches 7.30g/cm3, VSM test result shows it Remanent magnetism 0.92kGs, coercivity 0.51kOe, magnetic energy product 0.02MGOe.
Performance test
Test above embodiments are carried out using VersaLab system type vibrating specimen magnetometer (VSM), and sample, test is made Hysteresis loop at room temperature, hot-pressed magnets performance are as shown in table 1:
1 (La of tablex/Ce1-x)yFe14The magnetic property of B magnet
As known from Table 3, with the increase of content of rare earth, hot-pressed magnets performance is first increased and is reduced afterwards, when rare earth element reaches When 3:14:1, hot-pressed magnets performance highest, at this point, hot-pressed magnets remanent magnetism is 4.31kGs, coercivity 3.25kOe, maximum magnetic energy Product is 2.39MGOe.With being increasing for La content, performance is reduced after being first increased to reach to peak value, best La/Ce =3:7, hot-pressed magnets hysteresis loop is as shown in Figure 2 at this time.
Above example is only preferred embodiment of the invention, and basic principle of the invention, main spy has been shown and described Sign and advantages of the present invention, are not intended to restrict the invention.The technical staff and scientific research personnel of the industry are it should be appreciated that this hair It is bright to have various modifications and variations.It is all within the scope of the spirit and principles in the present invention, it is any modification be equal to replacement, improve Deng these variations are all within the scope of the present invention.

Claims (9)

1. a kind of preparation method of the nanocrystalline permanent magnet of cheap light rare earth lanthanum ferrocerium boron, which comprises the following steps:
The first step presses (Lax/Ce1-x)yFe14The elemental mole ratios example of B, x=0~1, y=2.0~4.0 is matched, and ingredient is completed After be put into suspension smelting furnace, under argon atmosphere, heating makes its thawing, naturally cools to room temperature after mixing, so anti- Remelt refining is multiple, to obtain uniform ingot casting；
Second step, the ingot casting that the first step is obtained take out, and mechanical grinding falls surface oxides, carry out Mechanical Crushing, ingot casting fragment As far as possible uniformly, it is then charged into quartz ampoule；
Quartz ampoule equipped with ingot casting is installed in fast melt-quenching equipment by third step, and opening heating system melts ingot casting block, is allowed Aluminium alloy is sprayed on high-speed rotating copper roller from nozzle, and aluminium alloy contacts copper roller and is quickly cooled down, and is obtained rapid tempering belt and is thrown to collecting bin In, during fast melt-quenching, the linear resonance surface velocity of copper roller is 10~60m/s, 0.4~1mm of nozzle diameter, and nozzle is away from roller height 0.2~0.6mm；
4th step, the rapid tempering belt that step 3 is obtained remove impurity by screening, are crushed sieving, are fitted into mold, are put into later In discharge plasma sintering furnace, hot pressed sintering is carried out using suitable temperature, pressure.
2. a kind of preparation method of the nanocrystalline permanent magnet of cheap light rare earth lanthanum ferrocerium boron according to claim 1, which is characterized in that The first step, to avoid introducing excessive impurity using material purity 99% or more, rare earth scaling loss amount is depending on equipment situation The 0~10% of rare earth quality.
3. a kind of preparation method of the nanocrystalline permanent magnet of cheap light rare earth lanthanum ferrocerium boron according to claim 1, which is characterized in that In 4th step, it is sieved after obtained rapid tempering belt is broken, suitable sintering condition is then selected according to alloying component, sintering temperature is 550~800 DEG C, heating rate is 30~150 DEG C/min, and pressure is 10~500MPa, and soaking time is 1~10min.
4. a kind of preparation method of the nanocrystalline permanent magnet of cheap light rare earth lanthanum ferrocerium boron according to claim 1, which is characterized in that X=0.2~0.8, y=3.0.
5. a kind of preparation method of the nanocrystalline permanent magnet of cheap light rare earth lanthanum ferrocerium boron according to claim 4, which is characterized in that X=0.3.
6. a kind of preparation method of the nanocrystalline permanent magnet of cheap light rare earth lanthanum ferrocerium boron according to claim 1, which is characterized in that Sintering pressure uses graphite jig in 100MPa or less, and sintered-carbide die is used when more than 100MPa.
7. a kind of preparation method of the nanocrystalline permanent magnet of cheap light rare earth lanthanum ferrocerium boron according to claim 1, which is characterized in that Pressuring method is first to be pre-stressed to certain pressure, is then gradually added to setting pressure during the sintering process.
8. a kind of preparation method of the nanocrystalline permanent magnet of cheap light rare earth lanthanum ferrocerium boron according to claim 1, which is characterized in that Sintering terminates, gradually release after temperature drops 100 DEG C.
9. the nanocrystalline permanent magnet of light rare earth lanthanum ferrocerium boron being prepared according to any one of claim 1-8 method.
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