CN106710768A - Method for improving neodymium, cerium, iron and boron sintered magnet coercivity by adding neodymium hydride - Google Patents

Method for improving neodymium, cerium, iron and boron sintered magnet coercivity by adding neodymium hydride Download PDF

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CN106710768A
CN106710768A CN201611228974.0A CN201611228974A CN106710768A CN 106710768 A CN106710768 A CN 106710768A CN 201611228974 A CN201611228974 A CN 201611228974A CN 106710768 A CN106710768 A CN 106710768A
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neodymium
powder
phase
boron
magnet
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吴凯云
马天宇
严密
金佳莹
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Zhejiang University ZJU
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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
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    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling

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Abstract

The invention discloses a method for improving neodymium, cerium, iron and boron sintered magnet coercivity by adding neodymium hydride. The method comprises the steps that on the basis of the dual-main-phase alloy technology and the crystal boundary technology, two-main-phase alloy and crystal boundary auxiliary alloy are separately designed, prepared and powdered, magnetic field compression, sintering and thermal sintering are performed after powder is mixed proportionally to obtain a magnet. The coercivity of the obtained neodymium, cerium, iron and boron sintered magnet is high, preparation is easy and convenient, operation is easy, and the raw material cost of the magnet is effectively lowered.

Description

One kind addition neodymium hydride improves the neodymium coercitive method of ferrocerium boron sintered magnet
Technical field
The neodymium coercitive method of ferrocerium boron sintered magnet is improved the present invention relates to one kind addition neodymium hydride.
Background technology
Sintered NdFeB magnet is the permanent-magnet material that current magnetic is most strong, most widely used, consumption rare earth is most, extensive use It is the pass of most important Rare Earth Functional Materials and national economy in high-tech sectors such as information, the energy, medical treatment, traffic and national defence Key basic material.Neodymium iron boron rapid growth for many years cause Nd that height relies on Pr Tb the element transition such as Dy consume, and abundance Ce, La high etc. is rarely employed.At present, efficient, reasonable, balanced is the Major Strategic Demand of China using rare earth resources.Realize Applications of the Ce in neodymium iron boron, can not only significantly reduce the production cost of neodymium iron boron, and will effectively expand high abundance rare earth Range of application, improve the innovation ability of rare earth downstream industry, promote the efficient of China rare earth resources and balance to apply.
In order to Ce is applied in neodymium iron boron magnetic body, forefathers had done many researchs.First method is melted with direct Refining method prepares neodymium cerium iron boron magnet.But due to Ce2Fe14The intrinsic magnetic properties of B is weaker than Nd2Fe14B, DIRECT ALLOYING replacement amount has Limit and deterioration magnetic property.There are some researches show when the replacement amount of Ce brings up to 40wt.% from 5wt.%, magnetic property is from 40MGOe It is reduced to 27MGOe.For low magnetic property neodymium ferrocerium boron magnet magnet prepared by relatively direct smelting process, the problem such as teacher Li Wei Double principal phase techniques of group development can produce the sintering neodymium cerium iron boron magnet of superior performance.When Ce accounts for total rare earth content During 30wt.%, magnetic energy product remains to reach 43MGOe.But coercivity only has 9.26kOe, wanting for business magnet is not reached still Ask.
Show according to the study, coercivity is not only relevant with intrinsic magnetic properties, it is also closely related with microscopic structure.Added by crystal boundary Heavy rare earth or heavy rare earth grain boundary decision, the anisotropy field in enhancing principal phase boundary layer, can improve coercivity.In addition, passing through shape Into thicker Grain-Boundary Phase, the adjacent main phase grain of Magnetic isolation can also improve coercivity.In view of Nd2Fe14The remanent magnetism and magnetocrystalline of B are each Anisotropy field is all higher than Ce2Fe14B, if in Ce2Fe14The surface of B forms rich Nd layers, and the magnetocrystalline that can not only strengthen local is each Anisotropy, improves coercivity, can also improve remanent magnetism；Meanwhile, crystal boundary introduces more Nd can also strengthen Nd-rich phase Volume fraction, so as to improve the wetability of principal phase and Grain-Boundary Phase, optimize crystal boundary distributed mutually, keep apart adjacent main phase grain.And Benefit from hydride is that it is easily prepared, also has high activity after dehydrogenation, beneficial to solid-state diffusion.
In sum, adding neodymium hydrogen compound by the crystal boundary in double principal phase neodymium cerium iron boron magnets can prepare high-coercive force Sintering neodymium cerium iron boron magnet.
The content of the invention
The purpose of the present invention is to overcome the deficiencies in the prior art, there is provided one kind addition neodymium hydride improves neodymium ferrocerium boron sintering The coercitive method of magnet, its step is：
1. double main-phase alloy powder are prepared, and step is as follows：
1) dispensing：By percentage to the quality, its composition is (Pr to A principal phases Nd Fe B alloys1-x,Ndx)a1Fe100-a1-b1- c1Mb1Bc1；By percentage to the quality, its composition is (Pr to B principal phase neodymium ferroceriums boron alloy1-y,Ndy)a2Ceb2Fe100-a2-b2-c2- d2Mc2Bd2, wherein M is a kind of or several in Nb, V, Ti, Co, Cr, Mo, Mn, Ni, Ga, Zr, Ta, Ag, Au, Al, Pb, Cu, Si element Kind, Pr is praseodymium element, and Nd is neodymium element, and Ce is Ce elements, and B is boron element, x, y, a1, b1, c1, a2, b2, c2, d2 meet with Lower relation：0.7≤x≤1、0.7≤y≤1、28.5≤a1≤32.5、0≤b1≤1.5、0.9≤c1≤1.05、14.25≤a2 ≤16.25、14.25≤b2≤16.25、0≤c2≤1、0.9≤d2≤1.05。
2) melting and rapid hardening strip casting：Two main-phase alloys are respectively adopted vacuum intermediate-frequency induction melting and go forward side by side the solidifying scale of scanning frequency Ingot casting is made thicker strip；
3) hydrogen is quick-fried and airflow milling：Two main-phase alloys are respectively adopted that hydrogen is quick-fried to be made particle mean size using airflow milling by the quick-fried powder of hydrogen again It is 1~10 μm of magnetic.
2. neodymium hydrogen compound powder is prepared, and step is as follows：
1) hydrogen is quick-fried：Pure neodymium by metal purity more than 99.5% prepares the fine grained chippings of neodymium hydrogen compound using the quick-fried method of hydrogen；
2) airflow milling：Use the method for ball milling by neodymium hydrogen compound be broken into average particulate diameter for 0.1-3.0 μm Grain powder.
3. powder is mixed, and step is as follows：
1) the two main-phase alloy powder that will be prepared uniformly are mixed with mass percent in batch mixer；
2) neodymium hydrogen compound powder is added into double main-phase alloys in the form of mass percentage content is as 1%-10% to exist Uniformly mix in glove box.
4. magnetic field orientating shaping：The alloy powder for completing will be mixed carries out oriented moulding under the magnetic field of 1.5T-2.0T, and Green compact are made through the isostatic cool pressing of 17MPa.
5. vacuum-sintering and heat treatment, step is as follows：
1) green compact are sintered into 2~5h at 1020~1080 DEG C with high vacuum positive pressure sintering furnace and is made magnet；
2) carry out carrying out second annealing between one-level tempering and 410~470 DEG C between 860~920 DEG C again, final magnetic is obtained Body.
The present invention has the advantage that compared with prior art：
1) reserves of high abundance Rare-Earth Ce are 2-5 times of Nd and Pr, and market price is the 1/3-1/5 of Nd and Pr, this application The rare-earth permanent magnet of Ce productions can not only effective reduces cost, moreover it is possible to promote the comprehensive utilization of rare earth resources；
2) using the rare-earth permanent magnet of double principal phase technique productions, magnetic property higher can be ensured；
3) add to form more rich Nd Hard Magnetics shell principal phases using neodymium hydrogen compound powder, optimize the microscopic structure knot of magnet Structure, improves crystal boundary distributed mutually, further lifting magnet coercivity；
4) neodymium hydrogen compound powder process is prepared simple, the powder being made is micron level, can uniformly be wrapped in master Around phase, the dehydrogenation of hydride can effectively suppress the oxidation of magnet in sintering process, reduce magnet oxygen content, whole preparation process Simplicity, low cost is especially suitable for the batch production in industry.
Specific embodiment
By percentage to the quality, its composition is (Pr to A principal phases Nd Fe B alloys1-x,Ndx)a1Fe100-a1-b1-c1Mb1Bc1；B master By percentage to the quality, its composition is (Pr to phase neodymium ferrocerium boron alloy1-y,Ndy)a2Ceb2Fe100-a2-b2-c2-d2Mc2Bd2, wherein M is In Nb, V, Ti, Co, Cr, Mo, Mn, Ni, Ga, Zr, Ta, Ag, Au, Al, Pb, Cu, Si element one or more, Pr be praseodymium element, Nd is neodymium element, and Ce is Ce elements, and B is boron element, and x, y, a1, b1, c1, a2, b2, c2, d2 meet following relation：0.7≤x≤ 1、0.7≤y≤1、28.5≤a1≤32.5、0≤b1≤1.5、0.9≤c1≤1.05、14.25≤a2≤16.25、14.25≤ b2≤16.25、0≤c2≤1、0.9≤d2≤1.05.Crystal boundary adds neodymium hydrogen compound with atomic percentage, and its composition is NdHx, H is protium, and x meets 2≤x≤3.
Addition neodymium hydride improves the neodymium coercitive method of ferrocerium boron sintered magnet and concretely comprises the following steps：
1) A principal phases neodymium iron boron and B principal phase neodymium ferrocerium boron alloys are respectively adopted rapid hardening belt-rejecting technology and are made rapid casting, crystal boundary Addition neodymium hydrogen compound prepares the fine grained chippings of neodymium hydrogen compound using the quick-fried method of hydrogen；
2) it is quick-fried by hydrogen that rapid casting is crushed the principal phase for being made that average particulate diameter is 1-10 μm with airflow milling method Particle powder, uses ball-milling method that Grain-Boundary Phase hydride is broken into the particle powder that average particulate diameter is for 0.1-3.0 μm；
3) the two main-phase alloy powder that will be prepared uniformly are mixed with mass percent, then by neodymium hydrogen compound powder with matter Amount degree uniformly mixes for the form of 1%-10% is added in pair main-phase alloys；
4) will mix the alloy powder for completing carries out oriented moulding under the magnetic field of 1.5T-2.0T, and through the cold etc. of 17MPa Static pressure is made green compact；
5) magnetic patch that die mould is completed is sintered into 2~5h under 1020~1080 DEG C of vacuum, then by 860~920 DEG C of one-levels Tempering and 410~470 DEG C of second annealings, are obtained final magnet.
With reference to specific embodiment, the present invention will be further described, but the present invention is not limited only to following implementation Example：
Embodiment 1：
1) two main-phase alloys are respectively adopted quick-fried and airflow milling the four kinds of alloy works of vacuum induction melting, rapid hardening slab, hydrogen Skill prepares master alloying powder, particle diameters substantially at 3.5 μm or so, the master alloying in terms of atomic percentage, its alloy Composition is respectively Nd32.5FebalB1And Nd16.25Ce16.25FebalB1；
2) by mass percentage 46 in the glove box by A principal phases and B main-phase alloys powder under high pure nitrogen protection：54 enter The uniform batch mixing of row, obtains mixed-powder；The alloy powder for completing will be mixed carries out oriented moulding under the magnetic field of 1.5T-2.0T, And the isostatic cool pressing through 17MPa is made green compact；
3) green compact are sintered by 3h at 1045 DEG C using high vacuum sintering furnace, one-level tempering 2h is carried out at 890 DEG C, Second annealing 4h is carried out at 465 DEG C and obtains neodymium cerium iron boron magnet；
4) the neodymium cerium iron boron magnet magnetic property for preparing is measured, it is as a result as follows:Br=12.7kGs, Hcj=8.1kOe, (BH)max=39.8MGOe.
Embodiment 2：
1) two main-phase alloys are respectively adopted quick-fried and airflow milling the four kinds of alloy works of vacuum induction melting, rapid hardening slab, hydrogen Skill prepares master alloying powder, particle diameters substantially at 3.5 μm or so, the master alloying in terms of atomic percentage, its alloy Composition is respectively Nd32.5FebalB1And Nd16.25Ce16.25FebalB1；
2) it is neodymium metal hydrogen is quick-fried, and worn into particle diameter substantially 0.5-1.0 μm of powder, institute with mechanical attrition method Alloy is stated in terms of atomic percentage, its composition is NdHx；
3) carried out by matter in the glove box by two main-phase alloy powder with neodymium hydrogen compound powder under high pure nitrogen protection Uniform batch mixing, obtains mixed-powder, wherein A principal phases and B principal phases mass percent are 46 in two main-phase alloy powder：54, neodymium hydrogen Compound powder weight accounts for the 1% of total powder weight；
4) will mix the alloy powder for completing carries out oriented moulding under the magnetic field of 1.5T-2.0T, and through the cold etc. of 17MPa Static pressure is made green compact；
5) green compact are sintered by 3h at 1045 DEG C using high vacuum sintering furnace, one-level tempering 2h is carried out at 890 DEG C, Second annealing 4h is carried out at 465 DEG C and obtains neodymium cerium iron boron magnet；
6) the neodymium cerium iron boron magnet magnetic property for preparing is measured, it is as a result as follows:Br=12.6kGs, Hcj=9.9kOe, (BH)max=39.7MGOe.Compared to the neodymium cerium iron boron magnet without addition neodymium hydrogen compound, coercivity improves 22.2%.
Embodiment 3：
1) two main-phase alloys are respectively adopted quick-fried and airflow milling the four kinds of alloy works of vacuum induction melting, rapid hardening slab, hydrogen Skill prepares master alloying powder, particle diameters substantially at 3.5 μm or so, the master alloying in terms of atomic percentage, its alloy Composition is respectively Nd32.5FebalB1And Nd16.25Ce16.25FebalB1；
2) it is neodymium metal hydrogen is quick-fried, and worn into particle diameter substantially 0.5-1.0 μm of powder, institute with mechanical attrition method Alloy is stated in terms of atomic percentage, its composition is NdHx；
3) carried out by matter in the glove box by two main-phase alloy powder with neodymium hydrogen compound powder under high pure nitrogen protection Uniform batch mixing, obtains mixed-powder, wherein A principal phases and B principal phases mass percent are 46 in two main-phase alloy powder：54, neodymium hydrogen Compound powder weight accounts for the 2% of total powder weight；
4) will mix the alloy powder for completing carries out oriented moulding under the magnetic field of 1.5T-2.0T, and through the cold etc. of 17MPa Static pressure is made green compact；
5) green compact are sintered by 3h at 1045 DEG C using high vacuum sintering furnace, one-level tempering 2h is carried out at 890 DEG C, Second annealing 4h is carried out at 465 DEG C and obtains neodymium cerium iron boron magnet；
6) the neodymium cerium iron boron magnet magnetic property for preparing is measured, it is as a result as follows:Br=12.6kGs, Hcj=10.9kOe, (BH)max=39.5MGOe.
Embodiment 4：
1) two main-phase alloys are respectively adopted quick-fried and airflow milling the four kinds of alloy works of vacuum induction melting, rapid hardening slab, hydrogen Skill prepares master alloying powder, particle diameters substantially at 3.5 μm or so, the master alloying in terms of atomic percentage, its alloy Composition is respectively Nd32.5FebalB1And Nd16.25Ce16.25FebalB1；
2) it is neodymium metal hydrogen is quick-fried, and worn into particle diameter substantially 0.5-1.0 μm of powder, institute with mechanical attrition method Alloy is stated in terms of atomic percentage, its composition is NdHx；
3) carried out by matter in the glove box by two main-phase alloy powder with neodymium hydrogen compound powder under high pure nitrogen protection Uniform batch mixing, obtains mixed-powder, wherein A principal phases and B principal phases mass percent are 46 in two main-phase alloy powder：54, neodymium hydrogen Compound powder weight accounts for the 3% of total powder weight；
4) will mix the alloy powder for completing carries out oriented moulding under the magnetic field of 1.5T-2.0T, and through the cold etc. of 17MPa Static pressure is made green compact；
5) green compact are sintered by 3h at 1045 DEG C using high vacuum sintering furnace, one-level tempering 2h is carried out at 890 DEG C, Second annealing 4h is carried out at 465 DEG C and obtains neodymium cerium iron boron magnet；
6) the neodymium cerium iron boron magnet magnetic property for preparing is measured, it is as a result as follows:Br=12.0kGs, Hcj=12.2kOe, (BH)max=34.9MGOe.
Embodiment 5：
1) two main-phase alloys are respectively adopted quick-fried and airflow milling the four kinds of alloy works of vacuum induction melting, rapid hardening slab, hydrogen Skill prepares master alloying powder, particle diameters substantially at 3.5 μm or so, the master alloying in terms of atomic percentage, its alloy Composition is respectively Nd32.5FebalB1And Nd16.25Ce16.25FebalB1；
2) it is neodymium metal hydrogen is quick-fried, and worn into particle diameter substantially 0.5-1.0 μm of powder, institute with mechanical attrition method Alloy is stated in terms of atomic percentage, its composition is NdHx；
3) carried out by matter in the glove box by two main-phase alloy powder with neodymium hydrogen compound powder under high pure nitrogen protection Uniform batch mixing, obtains mixed-powder, wherein A principal phases and B principal phases mass percent are 46 in two main-phase alloy powder：54, neodymium hydrogen Compound powder weight accounts for the 4% of total powder weight；
4) will mix the alloy powder for completing carries out oriented moulding under the magnetic field of 1.5T-2.0T, and through the cold etc. of 17MPa Static pressure is made green compact；
5) green compact are sintered by 3h at 1045 DEG C using high vacuum sintering furnace, one-level tempering 2h is carried out at 890 DEG C, Second annealing 4h is carried out at 465 DEG C and obtains neodymium cerium iron boron magnet；
6) the neodymium cerium iron boron magnet magnetic property for preparing is measured, it is as a result as follows:Br=11.8kGs, Hcj=13.0kOe, (BH)max=33.7MGOe.

Claims (6)

1. a kind of addition neodymium hydride improves the neodymium coercitive method of ferrocerium boron sintered magnet, it is characterised in that including:
1) A principal phases neodymium iron boron and B principal phase neodymium ferrocerium boron alloys are respectively adopted rapid hardening belt-rejecting technology and are made rapid casting, metal purity Pure neodymium more than 99.5% prepares the fine grained chippings that crystal boundary adds neodymium hydrogen compound using the quick-fried method of hydrogen；
2) it is quick-fried by hydrogen that rapid casting is crushed the principal phase particle for being made that average particulate diameter is 1-10 μm with airflow milling method Powder, uses ball-milling method that crystal boundary addition neodymium hydrogen compound is broken into the particle powder that average particulate diameter is for 0.1-3.0 μm；
3) the two main-phase alloy powder that will be prepared uniformly mix, then neodymium hydrogen compound powder is added into double main-phase alloys in nothing Oxygen atmosphere uniformly mixes in being；Neodymium hydrogen compound powder is 1%-10% relative to the mass percent of two main-phase alloy powder；
4) will mix the alloy powder for completing carries out oriented moulding under the magnetic field of 1.5T-2.0T, and is made life through isostatic cool pressing Base；
5) magnetic patch that die mould is completed is sintered into 2~5h under 1020~1080 DEG C of vacuum, then carries out one-level between 860~920 DEG C It is tempered and second annealing is carried out between 410~470 DEG C, final magnet is obtained.
2. a kind of addition neodymium hydride according to claim 1 improves the neodymium coercitive method of ferrocerium boron sintered magnet, and it is special Levy and be, in step (1), by percentage to the quality, its composition is (Pr to the A principal phases Nd Fe B alloys1-x,Ndx)a1Fe100-a1-b1-c1Mb1Bc1, by percentage to the quality, its composition is (Pr to B principal phase neodymium ferroceriums boron alloy1-y,Ndy)a2Ceb2Fe100-a2-b2-c2-d2Mc2Bd2, wherein M be Nb, V, Ti, Co, Cr, Mo, Mn, Ni, Ga, Zr, Ta, Ag, Au, Al, Pb, Cu, In Si elements one or more, Pr is praseodymium element, and Nd is neodymium element, and Ce is Ce elements, and B is boron element, x, y, a1, b1, c1, A2, b2, c2, d2 meet following relation：0.7≤x≤1、0.7≤y≤1、28.5≤a1≤32.5、0≤b1≤1.5、0.9≤c1 ≤1.05、14.25≤a2≤16.25、14.25≤b2≤16.25、0≤c2≤1、0.9≤d2≤1.05。
3. a kind of addition neodymium hydride according to claim 2 improves the neodymium coercitive method of ferrocerium boron sintered magnet, and it is special Levy and be, crystal boundary adds neodymium hydrogen compound with atomic percentage, its composition is NdHx, H is protium, and x meets 2≤x≤3.
4. a kind of addition neodymium hydride according to claim 1 improves the neodymium coercitive method of ferrocerium boron sintered magnet, and it is special Levy be the isostatic cool pressing pressure be 17MPa.
5. a kind of addition neodymium hydride according to claim 1 improves the neodymium coercitive method of ferrocerium boron sintered magnet,
It is characterized in that the step 3) in two main-phase alloy powder the mass ratio of A principal phases and B principal phases be：0.1-0.9.
6. many principal phase neodymium ferrocerium boron sintered magnets that a kind of method as claimed in claim 1 is prepared.
CN201611228974.0A 2016-12-27 2016-12-27 Method for improving neodymium, cerium, iron and boron sintered magnet coercivity by adding neodymium hydride Pending CN106710768A (en)

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US11721460B2 (en) 2016-11-08 2023-08-08 Lg Chem, Ltd. Method for preparing metal powder, and metal powder
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CN110911077A (en) * 2019-11-18 2020-03-24 江苏大学 Preparation method of high-coercivity neodymium cerium iron boron magnet
CN110911077B (en) * 2019-11-18 2021-02-12 江苏大学 Preparation method of high-coercivity neodymium cerium iron boron magnet
CN112086255A (en) * 2020-09-18 2020-12-15 湖南奔朗新材料科技有限公司 High-coercivity and high-temperature-resistant sintered neodymium-iron-boron magnet and preparation method thereof
EP4152349A1 (en) 2021-09-16 2023-03-22 Yantai Dongxing Magnetic Materials Inc. Method for preparing ndfeb magnets including lanthanum or cerium
CN114823113A (en) * 2022-04-14 2022-07-29 浙江大学 Preparation method of high-coercivity cerium-rich rare earth permanent magnet material

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