CN105575577A - Sintered cerium-rich rare earth permanent magnetic material and preparation method thereof - Google Patents

Sintered cerium-rich rare earth permanent magnetic material and preparation method thereof Download PDF

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Publication number
CN105575577A
CN105575577A CN201610122354.2A CN201610122354A CN105575577A CN 105575577 A CN105575577 A CN 105575577A CN 201610122354 A CN201610122354 A CN 201610122354A CN 105575577 A CN105575577 A CN 105575577A
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rare earth
intergranular
magnetic material
master alloying
earth permanent
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CN105575577B (en
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刘颖
李军
沈鑫
温荣源
徐天宝
吴文远
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SICHUAN WANKAIFENG RARE EARTH NEW ENERGY TECHNOLOGY Co Ltd
Sichuan University
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SICHUAN WANKAIFENG RARE EARTH NEW ENERGY TECHNOLOGY Co Ltd
Sichuan University
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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
    • H01F1/0572—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 with a protective layer
    • 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
    • B22F3/02—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
    • B22F3/1003—Use of special medium during sintering, e.g. sintering aid
    • B22F3/1007—Atmosphere
    • 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
    • B22F3/24—After-treatment of workpieces or articles
    • 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
    • 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
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/248—Thermal after-treatment

Abstract

The invention provides a sintered cerium-rich rare earth permanent magnetic material. The sintered cerium-rich rare earth permanent magnetic material is prepared from, by mass, RE1 20%-28%, RE2 4%-15%, Fe 60.5%-70.5%, B 0.8%-1.2% and Tm 0.1%-5%. A main phase is Nd2Fe14B or (Nd, Pr) 2Fe14B, and Ce or Ce and La are distributed around the main phase grains. The RE1 is Nd, Nd and Pr, a rare earth element dominated by Nd or a rare earth element dominated by Nd and Pr, the RE2 is Ce or Ce and La, and the Tm is at least one of Co, Cu, Al, Ga, Nb, Zr, Mo, Mn and Cr. The invention further provides a preparation method of the rare earth permanent magnetic material. The problem that the Ce and La are used for replacing the Nd and Pr in part to prepare the cerium-rich rare earth permanent magnetic material and the intrinsic magnetic properties of the material are influenced can be solved, and meanwhile the cost of the rare earth permanent magnetic material can be reduced.

Description

Sintering cerium-rich rare earth permanent magnetic material and preparation method thereof
Technical field
The invention belongs to rare earth permanent-magnetic material preparation field, particularly sinter cerium-rich rare earth permanent magnetic material and preparation method thereof.
Background technology
Nd-Fe-B system rare earth permanent-magnetic material can obtain a wide range of applications in multiple fields such as electronic product, medicine equipment, auto industrys with its superior comprehensive magnetic.In recent years, along with Global Rare-earth Permanent Magnet material yield continues to increase, rare earth Nd, Pr resource are constantly consumed minimizing, and cost of material constantly rises, and greatly constrain the development of Rare-earth Permanent Magnet Industry.And high abundance Elements C e in China's Rare Earth Mine, the large utilance of La reserves are lower, deep processing is inadequate, and low value-added primary product are accumulated in a large number, and the overall balance having had a strong impact on rare earth resources utilizes.The elements such as Ce, La and Pr, Nd belong to lanthanide series metal together, have similar 4f electron structure, and replacing Pr, Nd with Ce, La and prepare the cost that cerium-rich rare earth permanent magnetic material can reduce permanent magnetic material, is also the effective way realizing Rare-Earth Ce, La resource value.
Some are disclosed about the research report preparing cerium-rich rare earth permanent magnetic material with Ce, La replacement Pr, Nd in prior art.But due to the restriction of light rare earth element intrinsic magnetic properties energy, obtained magnet performance relative Nd-Fe-B magnet degradation.Existing control Ce, La light rare earth element to magnet intrinsic magnetic properties can the method for restriction main again three kinds: one be by limit Ce to the substitution amount of Nd, Pr element in lower proportion to control the deterioration of magnet performance; Two by obtaining the Nd-Fe-B alloy casting piece mixed sintering of (Nd, Ce)-Fe-B alloy and high magnetic characteristics to improve the performance containing Ce magnet by melting; Three be by adulterate in magnet other improvement element with ensure there is certain magnetic property.But these methods do not tackle the problem at its root.The main cause causing magnet performance to decline is, in the preparation method of existing cerium-rich rare earth permanent magnetic material, Rare-Earth Ce, mostly the incorporation way of La or mixed rare earth alloy MM is its molten alloy together with Nd or Pr-Nd alloy etc., in rare earth permanent-magnetic material obtained like this, a large amount of Ce substitutes Nd, Pr element in principal phase, Ce element is mainly with (Nd, Ce) 2fe 14b or (Nd, Pr, Ce) 2fe 14b form exists, and along with the increase of alternative amount, causes principal phase saturated pole intensity J s, magnetocrystalline anisotropy field H a, Curie temperature T cetc. intrinsic magnetic parameter degradation, make magnet performance degradation.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, a kind of sintering cerium-rich rare earth permanent magnetic material and preparation method thereof is provided, so that effectively solutions Ce, La Some substitute Nd, Pr prepare cerium-rich rare earth permanent magnetic material affect problem to material intrinsic magnetic properties energy, reduce the cost of rare earth permanent-magnetic material simultaneously.
Sintering cerium-rich rare earth permanent magnetic material of the present invention, the mass percent of the component comprised and each component is as follows: RE1 is 20% ~ 28%, RE2 be 4% ~ 15%, Fe be 60.5% ~ 70.5%, B be 0.8% ~ 1.2%, Tm is 0.1% ~ 5%; The principal phase of this sintering cerium-rich rare earth permanent magnetic material is Nd 2fe 14b or (Nd, Pr) 2fe 14b, is distributed with Ce around main phase grain, or Ce and La; Described RE1 is Nd, Nd and Pr, rare earth element based on Nd or based on the rare earth element of Nd and Pr, described RE2 is Ce, or Ce and La, described T mfor at least one in Co, Cu, Al, Ga, Nb, Zr, Mo, Mn, Cr.
In above-mentioned sintering cerium-rich rare earth permanent magnetic material, described RE1 is that the rare earth element based on Nd refers to that the quality of Nd is more than or equal to 95% of RE1 quality, based on the rare earth element of Nd and Pr, described RE1 refers to that the quality of Nd and Pr is more than or equal to 95% of RE1 quality, when RE1 be the rare earth element based on Nd or the rare earth element based on Nd and Pr time, also comprise at least one rare earth element in Dy, Tb, Gd, Ho in RE1.
In above-mentioned sintering cerium-rich rare earth permanent magnetic material, also containing a small amount of Ce 2fe 14b phase or (Ce, La) 2fe 14b phase, when RE1 be the rare earth element based on Nd or the rare earth element based on Nd and Pr time, also comprise a small amount of Dy 2fe 14b, Tb 2fe 14b, Gd 2fe 14b, Ho 2fe 14at least one in B.
The preparation method of sintering cerium-rich rare earth permanent magnetic material of the present invention, processing step is as follows:
(1) preparation of master alloying slab, the auxiliary alloy casting piece of intergranular or block
1. prepare burden
Master alloying RE3-Fe-B-M athe mass percent of the component comprised and each component: RE3 is 27% ~ 30%, Fe is 65% ~ 72%, B is 0.9% ~ 1.1%, M abe 0.1% ~ 4%, described RE3 be Nd, Nd and Pr, rare earth element based on Nd or based on the rare earth element of Nd and Pr, described M afor at least one in Co, Cu, Al, Ga, Nb, Zr, Mo, Mn, Cr;
The auxiliary alloy RE4-Fe-B-M of intergranular bthe mass percent of the component comprised and each component: RE4 is 38% ~ 85%, Fe is 6% ~ 60%, B is 0.1% ~ 1.2%, M bbe 0.1% ~ 20%; Described RE4 is Ce, or based on the rare earth element of Ce and La, described M bfor at least one in Co, Cu, Al, Ga, Nb, Zr, Mo, Mn, Cr;
According to master alloying RE3-Fe-B-M a, the auxiliary alloy RE4-Fe-B-M of intergranular bsaid components and each component mass percent batching;
2. founding or founding and fragmentation
Master alloying raw material step 1. prepared, the auxiliary alloy raw material of intergranular carry out founding respectively and obtain master alloying slab and the auxiliary alloy casting piece of intergranular;
Or master alloying raw material step 1. to be prepared is prepared into slab by founding, pour into the auxiliary alloy cast ingot of intergranular after the melting of intergranular step 1. prepared auxiliary alloy raw material, after auxiliary for intergranular alloy cast ingot is carried out homogenizing annealing, be broken into the auxiliary alloy block of the intergranular being of a size of 10 ~ 30mm again;
(2) preparation of master alloying powder, the auxiliary alloy powder of intergranular or master alloying and the auxiliary mixed powder for alloy of intergranular
Master alloying slab step (1) obtained, the auxiliary alloy block of intergranular carry out suction hydrogen-Dehydroepiandrosterone derivative respectively, obtain the master alloying coarse crushing particle of particle diameter 10 ~ 300 μm and the intergranular auxiliary alloy coarse crushing particle of particle diameter 0.1 ~ 3mm, described master alloying coarse crushing particle is broken by airflow milling under nitrogen or inert gas shielding, obtain the master alloying powder of particle diameter 1 ~ 5 μm, auxiliary for described intergranular alloy coarse crushing particle is carried out ball milling, obtains the auxiliary alloy powder of intergranular of particle diameter 0.5 ~ 3 μm;
Or weigh according to the mass percent of the component of prepared rare earth permanent-magnetic material and each component the master alloying slab and the auxiliary alloy casting piece of intergranular that step (2) obtains, suction hydrogen-Dehydroepiandrosterone derivative is carried out after they being mixed, obtain the hybrid alloys coarse crushing particle that particle diameter is 10 ~ 300 μm, gained hybrid alloys coarse crushing particle is carried out airflow milling fragmentation under nitrogen or inert gas shielding, obtains the hybrid alloys powder that particle diameter is 1 ~ 5 μm;
(3) preparation of green compact
In step (2) gained hybrid alloys powder, add antioxidant and lubricant and mix formation blank, then blank being loaded die cavity juxtaposition in magnetic field, obtain green compact in room temperature is compressing under nitrogen protection;
Or weigh step (2) gained master alloying powder, the auxiliary alloy powder of intergranular they mixed and form hybrid alloys powder according to the mass percent of the component of prepared rare earth permanent-magnetic material and each component, formation blank is mixed after adding antioxidant and lubricant again, then blank is loaded die cavity juxtaposition in magnetic field, compressingly under nitrogen protection obtain green compact;
(4) isostatic cool pressing of green compact
The green compact that step (3) obtains are carried out the isostatic cool pressing green compact that isostatic cool pressing obtains;
(5) sinter
The isostatic cool pressing green compact that step (4) obtains are put into vacuum sintering furnace, under vacuum in 990 ~ 1070 DEG C of sintering 1 ~ 6h, passes into inert gas after terminating or nitrogen is cooled to room temperature, obtain sintered magnet;
(6) heat treatment
Step (5) gained sintered magnet is heated to 800 ~ 950 DEG C of insulation 0.5 ~ 4h, 100 ~ 40 DEG C are cooled to after insulation terminates, be heated to 460 ~ 600 DEG C of insulation 1 ~ 6h again, after insulation terminates, pass into inert gas or nitrogen is cooled to room temperature, namely obtain sintering cerium-rich rare earth permanent magnetic material.
The preparation method of above-mentioned sintering cerium-rich rare earth permanent magnetic material, in its step (1), the homogenizing annealing of the auxiliary alloy cast ingot of intergranular is incubated 1 ~ 20h in 600 ~ 1000 DEG C under inert gas shielding, then cools to room temperature with the furnace.
The preparation method of above-mentioned sintering cerium-rich rare earth permanent magnetic material, in its step (2), master alloying slab, the auxiliary alloy block of intergranular carries out suction hydrogen-Dehydroepiandrosterone derivative respectively, or when carrying out suction hydrogen-Dehydroepiandrosterone derivative after master alloying slab and the mixing of intergranular auxiliary alloy casting piece, the Hydrogen Vapor Pressure inhaling hydrogen process is 0.1 ~ 0.3MPa, hydrogen process (the dynamic hydrogen mended in hydrogen method supplementary furnace of employing is inhaled when namely completing after inhaling hydrogen and reaching capacity, when in stove in 10min, hydrogen pressure drop is less than or equal to 0.02MPa, be suction hydrogen to reach capacity), Dehydroepiandrosterone derivative vacuumizes dehydrogenation at 500 ~ 600 DEG C, when namely completing Dehydroepiandrosterone derivative after the slab of carrying out Dehydroepiandrosterone derivative or block hydrogen content≤250ppm.
The preparation method of above-mentioned sintering cerium-rich rare earth permanent magnetic material, in its step (3), the magnetic field intensity preparing green compact is 1.5 ~ 3T, and briquetting pressure is 40 ~ 100MPa, and the dwell time is 1 ~ 15s.
The preparation method of above-mentioned sintering cerium-rich rare earth permanent magnetic material, in its step (4), the pressure of green compact isostatic cool pressing is 120 ~ 320MPa, and the dwell time is 10 ~ 300s.
The preparation method of above-mentioned sintering cerium-rich rare earth permanent magnetic material, in its step (3), the quality sum of antioxidant and lubricant is 0.05% ~ 0.5% of hybrid alloys powder quality, and the mass ratio of antioxidant and lubricant is 1:1.Antioxidant is commercially available neodymium iron boron special antioxidant, and domestic You Duo company produces, and holy new material research institute is pleased in such as Tianjin, Yadong, Hangzhou new material Co., Ltd, Taiyuan Jia Ci Co., Ltd, Beijing Jun Cefeng development in science and technology Co., Ltd etc.; Lubricant can be oleic acid, stearic acid, zinc stearate etc., and the present invention selects zinc stearate.
The preparation method of above-mentioned sintering cerium-rich rare earth permanent magnetic material, in its step (1), described RE3 is that the rare earth element based on Nd refers to that the quality of Nd is more than or equal to 95% of RE3 quality, based on the rare earth element of Nd and Pr, described RE3 refers to that the quality of Nd and Pr is more than or equal to 95% of RE3 quality, when RE3 be the rare earth element based on Nd or the rare earth element based on Nd and Pr time, also comprise at least one rare earth element in Ce, La, Dy, Tb, Gd, Ho in RE3; Based on the rare earth element of Ce and La, described RE4 refers to that the quality of Ce and La is more than or equal to 75% of RE4 quality, when RE4 is the rare earth element based on Ce and La, also comprise at least one rare earth element in Nd, Pr, Dy, Tb, Gd, Ho in RE4.
Compared with prior art, the present invention has following beneficial effect:
1, sintering cerium-rich rare earth permanent magnetic material of the present invention, Ce containing mass fraction 4% ~ 15%, or Ce and La, namely instead of part Nd, Pr with Ce, La, thus can promote the comprehensive utilization of Rare-Earth Ce, La resource, effectively reduce the cost of rare earth permanent-magnetic material raw material simultaneously.
2, rare earth permanent-magnetic material prepared by the method for the invention, contained RE2 be mainly distributed in intergranular mutually in, the fusing point of intergranular phase can be reduced, in conjunction with a certain amount of Tm element (Cu, Ga, Al etc.), the fusing point (as CeCu fusing point is only 424 DEG C) of further reduction intergranular phase, play and sintering liquid phase is provided, reduce the object of sintering temperature, improve the wettability of intergranular phase simultaneously, the existence of a large amount of low melting point intergranular phase effectively can reduce sintering and the temperature of rare earth permanent-magnetic material, thus the uniform crystal particles of rare earth permanent-magnetic material is tiny and be evenly distributed, there is excellent magnetic property.
3, the method for the invention adopts two alloyage, namely with RE3-Fe-B-M afor master alloying, be mainly sintering cerium-rich rare earth permanent magnetic material and the principal phase Nd with high intrinsic magnetic properties energy is provided 2fe 14b or (Nd, Pr) 2fe 14b, ensures that permanent magnetic material has high saturated pole intensity Js and magnetocrystalline anisotropy field H a, with RE4-Fe-B-M bfor the auxiliary alloy of intergranular, mainly make the densification of cerium-rich rare earth permanent magnetic material agglomeration and the rich Ce needed for the magnetostatic coupling of principal phase is provided, or rich Ce and La intergranular phase, realize, to the regulation and control of rare earth element distribution, avoiding the elements such as Ce, La to enter Nd in a large number 2fe 14b or (Nd, Pr) 2fe14 bcause the decline of its intrinsic magnetic properties energy mutually, therefore effectively can reduce Ce, La Some substitute Pr, Nd impact on cerium-rich rare earth permanent magnetic material intrinsic magnetic properties energy.
4, first the method for the invention prepares master alloying and the auxiliary alloy of intergranular, based on master alloying and the auxiliary alloy of intergranular, Composition Design is carried out again according to the composition of sintering cerium-rich rare earth permanent magnetic material, performance requirement, thus flexibility and the degree of freedom high, be conducive to Industry Promotion.
Embodiment
Below by embodiment, sintering cerium-rich rare earth permanent magnetic material of the present invention and preparation method thereof is described further.
In following examples, this component of the digitized representation in alloy formula before each component mass percent in the alloy.
Embodiment 1
Described in the present embodiment, the preparation method of rare earth permanent-magnetic material is as follows:
(1) preparation of master alloying slab, the auxiliary alloy casting piece of intergranular
1. prepare burden
Raw material adopt the neodymium metal of technical pure purity, metallic cerium, pure iron, fine aluminium, fine copper and Boron contents to be the ferro-boron of 20% quality;
According to the mass percentage batching of component each in master alloying 27.67Nd-70.59Fe-1.02B-0.72Al and each component, and the oxide on each raw material surface and being mingled with is removed clean;
Prepare burden according to the mass percentage of each component and each component in auxiliary alloy 59.2Ce-36.1Fe-4.1Cu-0.6B, and the oxide on each feed metal surface and being mingled with is removed clean;
2. founding
Master alloying raw material step 1. prepared and the auxiliary alloy raw material of intergranular put into vacuum induction melting furnace respectively, after melting, aluminium alloy is cast in respectively under argon shield on the water-cooled copper running roller that linear velocity is 3m/s and cools fast, obtain rapid hardening master alloying slab that average thickness is 0.25mm and the auxiliary alloy casting piece of intergranular;
(2) preparation of master alloying and the auxiliary mixed powder for alloy of intergranular
The component proportion of the rare earth permanent-magnetic material of required preparation is 24.90Nd-5.92Ce-67.14Fe-0.98B-1.06T m, be the master alloying slab and the auxiliary alloy casting piece of intergranular that 90:10 weighs that step (1) obtains according to said ratio according to the mass ratio of master alloying slab and the auxiliary alloy casting piece of intergranular, suction hydrogen-Dehydroepiandrosterone derivative is carried out by putting into rotation hydrogen crushing furnace after two kinds of alloy casting piece mixing, the Hydrogen Vapor Pressure inhaling hydrogen process is 0.2MPa, adopt the hydrogen dynamically mended in hydrogen method supplementary furnace, namely complete after suction hydrogen reaches capacity and inhale hydrogen process (when in stove in 10min, hydrogen pressure drop is less than or equal to 0.02MPa, be suction hydrogen to reach capacity), Dehydroepiandrosterone derivative vacuumizes dehydrogenation at 560 DEG C, when namely completing Dehydroepiandrosterone derivative after the mixing slab hydrogen content≤250ppm carrying out Dehydroepiandrosterone derivative, inhale after hydrogen-Dehydroepiandrosterone derivative completes and obtain the hybrid alloys coarse crushing particle that particle diameter is 10 ~ 300 μm, gained hybrid alloys coarse crushing particle is carried out airflow milling fragmentation under nitrogen protection, obtain the hybrid alloys powder that average grain diameter is 3.2 μm,
(3) preparation of green compact
In step (2) gained hybrid alloys powder, add antioxidant and lubricant and mix formation blank, the quality sum of described antioxidant and lubricant is 0.1% of hybrid alloys powder quality, the mass ratio of antioxidant and lubricant is 1:1, antioxidant for please purchased from Tianjin holy new material research neodymium iron boron special antioxidant, lubricant is zinc stearate; Blank being loaded die cavity juxtaposition is in the magnetic field of 2T in magnetic field intensity, and in room temperature, 80MPa briquetting pressure, 4s of lower dwell time is compressing under nitrogen protection, obtains green compact;
(4) isostatic cool pressing of green compact
The green compact that step (3) obtains being placed in cold isostatic press at pressure is 150MPa pressurize compacting 100s, obtains isostatic cool pressing green compact after release;
(5) sinter
The isostatic cool pressing green compact that step (4) obtains are put into vacuum sintering furnace, 10 -3~ 10 -2in 1065 DEG C of heat preservation sintering 4h under Pa vacuum condition, pass into argon gas after terminating and be cooled to room temperature, obtain sintered magnet;
(6) heat treatment
By step (5) gained sintered magnet at 930 DEG C of insulation 1.5h, after insulation terminates, be cooled to less than 100 DEG C, then be heated to 570 DEG C of insulation 4h, pass into argon gas after insulation terminates and be cooled to room temperature, namely obtain sintering cerium-rich rare earth permanent magnetic material.
Measure through AMT-4 characteristic of magnetization automatic measuring instrument, the magnetic property of gained sintering cerium-rich rare earth permanent magnetic material is: B r=1.32T, H cj=826.5kA/m, (BH) max=335.2kJ/m 3.
Embodiment 2
Described in the present embodiment, the preparation method of rare earth permanent-magnetic material is as follows:
(1) preparation of master alloying slab, the auxiliary alloy casting piece of intergranular
1. prepare burden
Raw material adopt the neodymium metal of technical pure purity, metallic cerium, pure iron, fine aluminium, fine copper and Boron contents to be the ferro-boron of 20% quality;
According to the mass percentage batching of component each in master alloying 27.67Nd-70.59Fe-1.02B-0.72Al and each component, and the oxide on each raw material surface and being mingled with is removed clean;
Prepare burden according to the mass percentage of each component and each component in auxiliary alloy 59.2Ce-36.1Fe-4.1Cu-0.6B, and the oxide on each feed metal surface and being mingled with is removed clean;
2. founding
Master alloying raw material step 1. prepared and the auxiliary alloy raw material of intergranular put into vacuum induction melting furnace respectively, after melting, aluminium alloy is cast in respectively under argon shield on the water-cooled copper running roller that linear velocity is 3m/s and cools fast, obtain rapid hardening master alloying slab that average thickness is 0.25mm and the auxiliary alloy casting piece of intergranular;
(2) preparation of master alloying and the auxiliary mixed powder for alloy of intergranular
The component proportion of the rare earth permanent-magnetic material of required preparation is 23.52Nd-8.88Ce-65.41Fe-0.96B-1.23T m, be the master alloying slab and the auxiliary alloy casting piece of intergranular that 85:15 weighs that step (1) obtains according to said ratio according to the mass ratio of master alloying slab and the auxiliary alloy casting piece of intergranular, suction hydrogen-Dehydroepiandrosterone derivative is carried out by putting into rotation hydrogen crushing furnace after two kinds of alloy casting piece mixing, the Hydrogen Vapor Pressure inhaling hydrogen process is 0.2MPa, adopt the hydrogen dynamically mended in hydrogen method supplementary furnace, namely complete after suction hydrogen reaches capacity and inhale hydrogen process (when in stove in 10min, hydrogen pressure drop is less than or equal to 0.02MPa, be suction hydrogen to reach capacity), Dehydroepiandrosterone derivative vacuumizes dehydrogenation at 560 DEG C, when namely completing Dehydroepiandrosterone derivative after the mixing slab hydrogen content≤250ppm carrying out Dehydroepiandrosterone derivative, inhale after hydrogen-Dehydroepiandrosterone derivative completes and obtain the hybrid alloys coarse crushing particle that particle diameter is 10 ~ 300 μm, gained hybrid alloys coarse crushing particle is carried out airflow milling fragmentation under nitrogen protection, obtain the hybrid alloys powder that average grain diameter is 3.6 μm,
(3) preparation of green compact
In step (2) gained hybrid alloys powder, add antioxidant and lubricant and mix formation blank, the quality sum of described antioxidant and lubricant is 0.1% of hybrid alloys powder quality, the mass ratio of antioxidant and lubricant is 1:1, antioxidant for please purchased from Tianjin holy new material research neodymium iron boron special antioxidant, lubricant is zinc stearate; Blank being loaded die cavity juxtaposition is in the magnetic field of 2T in magnetic field intensity, and in room temperature, 80MPa briquetting pressure, 4s of lower dwell time is compressing under nitrogen protection, obtains green compact;
(4) isostatic cool pressing of green compact
The green compact that step (3) obtains being placed in cold isostatic press at pressure is 150MPa pressurize compacting 100s, obtains isostatic cool pressing green compact after release;
(5) sinter
The isostatic cool pressing green compact that step (4) obtains are put into vacuum sintering furnace, 10 -3~ 10 -2in 1065 DEG C of heat preservation sintering 4h under Pa vacuum condition, pass into argon gas after terminating and be cooled to room temperature, obtain sintered magnet;
(6) heat treatment
By step (5) gained sintered magnet at 930 DEG C of insulation 1h, after insulation terminates, be cooled to less than 100 DEG C, then be heated to 550 DEG C of insulation 4h, pass into argon gas after insulation terminates and be cooled to room temperature, namely obtain sintering cerium-rich rare earth permanent magnetic material.
Measure through AMT-4 characteristic of magnetization automatic measuring instrument, gained sintering cerium-rich rare earth permanent magnetic material magnetic property is: B r=1.298T, H cj=904.5kA/m, (BH) max=324.7kJ/m 3.
Embodiment 3
Described in the present embodiment, the preparation method of rare earth permanent-magnetic material is as follows:
(1) preparation of master alloying slab, the auxiliary alloy casting piece of intergranular
1. prepare burden
Raw material adopt the neodymium metal of technical pure purity, metallic cerium, pure iron, fine aluminium, fine copper and Boron contents to be the ferro-boron of 20% quality;
According to the mass percentage batching of component each in master alloying 27.67Nd-70.59Fe-1.02B-0.72Al and each component, and the oxide on each feed metal surface and being mingled with is removed clean;
Prepare burden according to the mass percentage of each component and each component in auxiliary alloy 59.2Ce-36.1Fe-4.1Cu-0.6B, and the oxide on each feed metal surface and being mingled with is removed clean;
2. founding
Master alloying raw material step 1. prepared and the auxiliary alloy raw material of intergranular put into vacuum induction melting furnace respectively, after melting, aluminium alloy is cast in respectively under argon shield on the water-cooled copper running roller that linear velocity is 3m/s and cools fast, obtain rapid hardening master alloying slab that average thickness is 0.25mm and the auxiliary alloy casting piece of intergranular;
(2) preparation of master alloying and the auxiliary mixed powder for alloy of intergranular
The component proportion of the rare earth permanent-magnetic material of required preparation is 22.13Nd-11.84Ce-63.69Fe-0.94B-1.40T m, be the master alloying slab and the auxiliary alloy casting piece of intergranular that 80:20 weighs that step (1) obtains according to said ratio according to the mass ratio of master alloying slab and the auxiliary alloy casting piece of intergranular, suction hydrogen-Dehydroepiandrosterone derivative is carried out by putting into rotation hydrogen crushing furnace after two kinds of alloy casting piece mixing, the Hydrogen Vapor Pressure inhaling hydrogen process is 0.15MPa, adopt the hydrogen dynamically mended in hydrogen method supplementary furnace, namely complete after suction hydrogen reaches capacity and inhale hydrogen process (when in stove in 10min, hydrogen pressure drop is less than or equal to 0.02MPa, be suction hydrogen to reach capacity), Dehydroepiandrosterone derivative vacuumizes dehydrogenation at 560 DEG C, when namely completing Dehydroepiandrosterone derivative after the mixing slab hydrogen content≤250ppm carrying out Dehydroepiandrosterone derivative, inhale after hydrogen-Dehydroepiandrosterone derivative completes and obtain the hybrid alloys coarse crushing particle that particle diameter is 10 ~ 300 μm, gained hybrid alloys coarse crushing particle is carried out airflow milling fragmentation under nitrogen protection, obtain the hybrid alloys powder that average grain diameter is 4.1 μm,
(3) preparation of green compact
In step (2) gained hybrid alloys powder, add antioxidant and lubricant and mix formation blank, the quality sum of described antioxidant and lubricant is 0.25% of hybrid alloys powder quality, the mass ratio of antioxidant and lubricant is 1:1, antioxidant for please purchased from Tianjin holy new material research neodymium iron boron special antioxidant, lubricant is zinc stearate; Blank being loaded die cavity juxtaposition is in the magnetic field of 1.8T in magnetic field intensity, and in room temperature, 70MPa briquetting pressure, 4s of lower dwell time is compressing under nitrogen protection, obtains green compact;
(4) isostatic cool pressing of green compact
The green compact that step (3) obtains being placed in cold isostatic press at pressure is 200MPa pressurize compacting 150s, obtains isostatic cool pressing green compact after release;
(5) sinter
The isostatic cool pressing green compact that step (4) obtains are put into vacuum sintering furnace, 10 -3~ 10 -2in 1065 DEG C of heat preservation sintering 4h under Pa vacuum condition, pass into argon gas after terminating and be cooled to room temperature, obtain sintered magnet;
(6) heat treatment
By step (5) gained sintered magnet at 900 DEG C of insulation 1h, after insulation terminates, be cooled to less than 100 DEG C, then be heated to 530 DEG C of insulation 4h, pass into argon gas after insulation terminates and be cooled to room temperature, namely obtain sintering cerium-rich rare earth permanent magnetic material.
Measure through AMT-4 characteristic of magnetization automatic measuring instrument, the magnetic property obtaining sintering cerium-rich rare earth permanent magnetic material is: B r=1.24T, H cj=858.9kA/m, (BH) max=286.7kJ/m 3.
Embodiment 4
Described in the present embodiment, the preparation method of rare earth permanent-magnetic material is as follows:
(1) preparation of master alloying slab, the auxiliary alloy casting piece of intergranular
1. prepare burden
Raw material adopt the ferro-boron that the praseodymium content of technical pure purity is the praseodymium neodymium alloy of 20% quality, metallic cerium, pure iron, fine aluminium, fine copper and Boron contents are 20% quality;
According to master alloying 27.57 (Nd 0.8pr 0.2) the mass percentage batching of each component and each component in-70.69Fe-1.02B-0.72Al, and the oxide on each feed metal surface and being mingled with is removed clean;
Prepare burden according to the mass percentage of each component and each component in intergranular auxiliary alloy 56.34Ce-40.80Fe-2.05Cu-0.81B, and the oxide on each feed metal surface and being mingled with is removed clean;
2. founding
Master alloying raw material step 1. prepared and the auxiliary alloy raw material of intergranular put into vacuum induction melting furnace respectively, after melting, aluminium alloy is cast in respectively under argon shield on the water-cooled copper running roller that linear velocity is 3m/s and cools fast, obtain rapid hardening master alloying slab that average thickness is 0.25mm and the auxiliary alloy casting piece of intergranular;
(2) preparation of master alloying and the auxiliary mixed powder for alloy of intergranular
The component proportion of the rare earth permanent-magnetic material of required preparation is 23.44 (Nd, Pr)-8.45Ce-66.21Fe-0.99B-0.91T m, be the master alloying slab and the auxiliary alloy casting piece of intergranular that 85:15 weighs that step (1) obtains according to said ratio according to the mass ratio of master alloying slab and the auxiliary alloy casting piece of intergranular, suction hydrogen-Dehydroepiandrosterone derivative is carried out by putting into rotation hydrogen crushing furnace after two kinds of alloy casting piece mixing, the Hydrogen Vapor Pressure inhaling hydrogen process is 0.15MPa, adopt the hydrogen dynamically mended in hydrogen method supplementary furnace, namely complete after suction hydrogen reaches capacity and inhale hydrogen process (when in stove in 10min, hydrogen pressure drop is less than or equal to 0.02MPa, be suction hydrogen to reach capacity), Dehydroepiandrosterone derivative vacuumizes dehydrogenation at 560 DEG C, when namely completing Dehydroepiandrosterone derivative after the mixing slab hydrogen content≤250ppm carrying out Dehydroepiandrosterone derivative, inhale after hydrogen-Dehydroepiandrosterone derivative completes and obtain the hybrid alloys coarse crushing particle that particle diameter is 10 ~ 300 μm, gained hybrid alloys coarse crushing particle is carried out airflow milling fragmentation under nitrogen protection, obtain the hybrid alloys powder that average grain diameter is 4.1 μm,
(3) preparation of green compact
In step (2) gained hybrid alloys powder, add antioxidant and lubricant and mix formation blank, the quality sum of described antioxidant and lubricant is 0.25% of hybrid alloys powder quality, the mass ratio of antioxidant and lubricant is 1:1, antioxidant is the neodymium iron boron special antioxidant purchased from Yadong, Hangzhou new material Co., Ltd, and lubricant is zinc stearate; Blank being loaded die cavity juxtaposition is in the magnetic field of 1.8T in magnetic field intensity, and in room temperature, 70MPa briquetting pressure, 4s of lower dwell time is compressing under nitrogen protection, obtains green compact;
(4) isostatic cool pressing of green compact
The green compact that step (3) obtains being placed in cold isostatic press at pressure is 200MPa pressurize compacting 150s, obtains isostatic cool pressing green compact after release;
(5) sinter
The isostatic cool pressing green compact that step (4) obtains are put into vacuum sintering furnace, 10 -3~ 10 -2in 1035 DEG C of heat preservation sintering 6h under Pa vacuum condition, pass into argon gas after terminating and be cooled to room temperature, obtain sintered magnet;
(6) heat treatment
By step (5) gained sintered magnet at 910 DEG C of insulation 1.5h, after insulation terminates, be cooled to less than 100 DEG C, then be heated to 520 DEG C of insulation 4h, pass into argon gas after insulation terminates and be cooled to room temperature, namely obtain sintering cerium-rich rare earth permanent magnetic material.
Measure through AMT-4 characteristic of magnetization automatic measuring instrument, gained sintering cerium-rich rare earth permanent magnetic material magnetic property is: B r=1.30T, H cj=873.3kA/m, (BH) max=326.4kJ/m 3.
Embodiment 5
Described in the present embodiment, the preparation method of rare earth permanent-magnetic material is as follows:
(1) preparation of master alloying slab, the auxiliary alloy casting piece of intergranular
1. prepare burden
Raw material adopt the ferro-boron that the praseodymium content of technical pure purity is the praseodymium neodymium alloy of 20% quality, metallic cerium, pure iron, fine aluminium, fine copper and Boron contents are 20% quality;
According to master alloying 27.57 (Nd 0.8pr 0.2) the mass percentage batching of each component and each component in-70.69Fe-1.02B-0.72Al, and the oxide on each feed metal surface and being mingled with is removed clean;
Prepare burden according to the mass percentage of each component and each component in auxiliary alloy 56.34Ce-40.80Fe-2.05Cu-0.81B, and the oxide on each feed metal surface and being mingled with is removed clean;
2. founding
Master alloying raw material step 1. prepared and the auxiliary alloy raw material of intergranular put into vacuum induction melting furnace respectively, after melting, aluminium alloy is cast in respectively under argon shield on the water-cooled copper running roller that linear velocity is 3m/s and cools fast, obtain rapid hardening master alloying slab that average thickness is 0.25mm and the auxiliary alloy casting piece of intergranular;
(2) preparation of master alloying and the auxiliary mixed powder for alloy of intergranular
The component proportion of the rare earth permanent-magnetic material of required preparation is 20.68 (Nd, Pr)-14.08Ce-63.22Fe-0.97B-1.05T m, be the master alloying slab and the auxiliary alloy casting piece of intergranular that 75:25 weighs that step (1) obtains according to said ratio according to the mass ratio of master alloying slab and the auxiliary alloy casting piece of intergranular, suction hydrogen-Dehydroepiandrosterone derivative is carried out by putting into rotation hydrogen crushing furnace after two kinds of alloy casting piece mixing, the Hydrogen Vapor Pressure inhaling hydrogen process is 0.15MPa, adopt the hydrogen dynamically mended in hydrogen method supplementary furnace, namely complete after suction hydrogen reaches capacity and inhale hydrogen process (when in stove in 10min, hydrogen pressure drop is less than or equal to 0.02MPa, be suction hydrogen to reach capacity), Dehydroepiandrosterone derivative vacuumizes dehydrogenation at 560 DEG C, when namely completing Dehydroepiandrosterone derivative after the mixing slab hydrogen content≤250ppm carrying out Dehydroepiandrosterone derivative, inhale after hydrogen-Dehydroepiandrosterone derivative completes and obtain the hybrid alloys coarse crushing particle that particle diameter is 10 ~ 300 μm, gained hybrid alloys coarse crushing particle is carried out airflow milling fragmentation under nitrogen protection, obtain the hybrid alloys powder that average grain diameter is 4.5 μm,
(3) preparation of green compact
In step (2) gained hybrid alloys powder, add antioxidant and lubricant and mix formation blank, the quality sum of described antioxidant and lubricant is 0.4% of hybrid alloys powder quality, the mass ratio of antioxidant and lubricant is 1:1, antioxidant is the neodymium iron boron special antioxidant purchased from Yadong, Hangzhou new material Co., Ltd, and lubricant is zinc stearate; Blank being loaded die cavity juxtaposition is in the magnetic field of 2T in magnetic field intensity, and in room temperature, 60MPa briquetting pressure, 4s of lower dwell time is compressing under nitrogen protection, obtains green compact;
(4) isostatic cool pressing of green compact
The green compact that step (3) obtains being placed in cold isostatic press at pressure is 200MPa pressurize compacting 150s, obtains isostatic cool pressing green compact after release;
(5) sinter
The isostatic cool pressing green compact that step (4) obtains are put into vacuum sintering furnace, 10 -3~ 10 -2in 1025 DEG C of heat preservation sintering 6h under Pa vacuum condition, pass into argon gas after terminating and be cooled to room temperature, obtain sintered magnet;
(6) heat treatment
By step (5) gained sintered magnet at 870 DEG C of insulation 1.5h, after insulation terminates, be cooled to less than 100 DEG C, then be heated to 480 DEG C of insulation 5h, pass into argon gas after insulation terminates and be cooled to room temperature, namely obtain sintering cerium-rich rare earth permanent magnetic material.
Measure through AMT-4 characteristic of magnetization automatic measuring instrument, gained sintering cerium-rich rare earth permanent magnetic material magnetic property is: B r=1.19T, H cj=765.5kA/m, (BH) max=244.3kJ/m 3.
Embodiment 6
Described in the present embodiment, the preparation method of rare earth permanent-magnetic material is as follows:
(1) preparation of master alloying slab, the auxiliary alloy casting piece of intergranular
1. prepare burden
Raw material adopt the ferro-boron that the praseodymium content of technical pure purity is the praseodymium neodymium alloy of 20% quality, dysprosium content is 80% quality Dy-Fe alloy, pure iron, fine aluminium, fine copper, content of niobium are the ferrocolumbium of 70% quality, metallic cobalt, gallium and Boron contents are 20% quality;
According to master alloying 28.25 (Nd 0.8pr 0.15dy 0.05) the mass percentage batching of each component and each component in-68.01Fe-1.02B-0.42Al-1.9Co-0.4Nb, and the oxide on each feed metal surface and being mingled with is removed clean;
Prepare burden according to the mass percentage of each component and each component in auxiliary alloy 64.6Ce-26.9Fe-4.5Co-1.0Ga-2.5Cu-0.5B, and the oxide on each feed metal surface and being mingled with is removed clean;
2. founding
Master alloying raw material step 1. prepared and the auxiliary alloy raw material of intergranular put into vacuum induction melting furnace respectively, after melting, aluminium alloy is cast in respectively under argon shield on the water-cooled copper running roller that linear velocity is 3m/s and cools fast, obtain rapid hardening master alloying slab that average thickness is 0.25mm and the auxiliary alloy casting piece of intergranular;
(2) preparation of master alloying and the auxiliary mixed powder for alloy of intergranular
The component proportion of the rare earth permanent-magnetic material of required preparation is 24.86 (Nd, Pr, Dy)-7.75Ce-63.08Fe-0.96B-3.35T m, be the master alloying slab and the auxiliary alloy casting piece of intergranular that 88:12 weighs that step (1) obtains according to said ratio according to the mass ratio of master alloying slab and the auxiliary alloy casting piece of intergranular, suction hydrogen-Dehydroepiandrosterone derivative is carried out by putting into rotation hydrogen crushing furnace after two kinds of alloy casting piece mixing, the Hydrogen Vapor Pressure inhaling hydrogen process is 0.24MPa, adopt the hydrogen dynamically mended in hydrogen method supplementary furnace, namely complete after suction hydrogen reaches capacity and inhale hydrogen process (when in stove in 10min, hydrogen pressure drop is less than or equal to 0.02MPa, be suction hydrogen to reach capacity), Dehydroepiandrosterone derivative vacuumizes dehydrogenation at 560 DEG C, when namely completing Dehydroepiandrosterone derivative after the mixing slab hydrogen content≤250ppm carrying out Dehydroepiandrosterone derivative, inhale after hydrogen-Dehydroepiandrosterone derivative completes and obtain the hybrid alloys coarse crushing particle that particle diameter is 10 ~ 300 μm, gained hybrid alloys coarse crushing particle is carried out airflow milling fragmentation under argon shield, obtain the hybrid alloys powder that average grain diameter is 2.7 μm,
(3) preparation of green compact
In step (2) gained hybrid alloys powder, add antioxidant and lubricant and mix formation blank, the quality sum of described antioxidant and lubricant is 0.3% of hybrid alloys powder quality, the mass ratio of antioxidant and lubricant is 1:1, antioxidant is the neodymium iron boron special antioxidant purchased from Yadong, Hangzhou new material Co., Ltd, and lubricant is zinc stearate; Blank being loaded die cavity juxtaposition is in the magnetic field of 2.5T in magnetic field intensity, and in room temperature, 70MPa briquetting pressure, 4s of lower dwell time is compressing under nitrogen protection, obtains green compact;
(4) isostatic cool pressing of green compact
The green compact that step (3) obtains being placed in cold isostatic press at pressure is 200MPa pressurize compacting 150s, obtains isostatic cool pressing green compact after release;
(5) sinter
The isostatic cool pressing green compact that step (4) obtains are put into vacuum sintering furnace, 10 -3~ 10 -2in 1045 DEG C of heat preservation sintering 4h under Pa vacuum condition, pass into argon gas after terminating and be cooled to room temperature, obtain sintered magnet;
(6) heat treatment
By step (5) gained sintered magnet at 905 DEG C of insulation 1h, after insulation terminates, be cooled to less than 100 DEG C, then be heated to 510 DEG C of insulation 4h, pass into argon gas after insulation terminates and be cooled to room temperature, namely obtain sintering cerium-rich rare earth permanent magnetic material.
Measure through AMT-4 characteristic of magnetization automatic measuring instrument, gained sintering cerium-rich rare earth permanent magnetic material magnetic property is: B r=1.32T, H cj=1089.3kA/m, (BH) max=343.1kJ/m 3.
Embodiment 7
Described in the present embodiment, the preparation method of rare earth permanent-magnetic material is as follows:
(1) preparation of master alloying slab, the auxiliary alloy casting piece of intergranular
1. prepare burden
Raw material adopt the ferro-boron that the praseodymium content of technical pure purity is the praseodymium neodymium alloy of 20% quality, metallic cerium, pure iron, fine aluminium, fine copper and Boron contents are 20% quality;
According to master alloying 27.56 (Nd 0.8pr 0.15ce 0.05) the mass percentage batching of each component and each component in-70.70Fe-1.02B-0.72Al, and the oxide on each feed metal surface and being mingled with is removed clean;
Prepare burden according to the mass percentage of each component and each component in auxiliary alloy 59.2Ce-36.1Fe-4.1Cu-0.6B, and the oxide on each feed metal surface and being mingled with is removed clean;
2. founding
Master alloying raw material step 1. prepared and the auxiliary alloy raw material of intergranular put into vacuum induction melting furnace respectively, after melting, aluminium alloy is cast in respectively under argon shield on the water-cooled copper running roller that linear velocity is 3m/s and cools fast, obtain rapid hardening master alloying slab that average thickness is 0.25mm and the auxiliary alloy casting piece of intergranular;
(2) preparation of master alloying and the auxiliary mixed powder for alloy of intergranular
The component proportion of the rare earth permanent-magnetic material of required preparation is 23.43 (Nd, Pr)-8.88Ce-65.51Fe-0.96B-1.23T m, be the master alloying slab and the auxiliary alloy casting piece of intergranular that 85:15 weighs that step (1) obtains according to said ratio according to the mass ratio of master alloying slab and the auxiliary alloy casting piece of intergranular, suction hydrogen-Dehydroepiandrosterone derivative is carried out by putting into rotation hydrogen crushing furnace after two kinds of alloy casting piece mixing, the Hydrogen Vapor Pressure inhaling hydrogen process is 0.2MPa, adopt the hydrogen dynamically mended in hydrogen method supplementary furnace, namely complete after suction hydrogen reaches capacity and inhale hydrogen process (when in stove in 10min, hydrogen pressure drop is less than or equal to 0.02MPa, be suction hydrogen to reach capacity), Dehydroepiandrosterone derivative vacuumizes dehydrogenation at 560 DEG C, when namely completing Dehydroepiandrosterone derivative after the mixing slab hydrogen content≤250ppm carrying out Dehydroepiandrosterone derivative, inhale after hydrogen-Dehydroepiandrosterone derivative completes and obtain the hybrid alloys coarse crushing particle that particle diameter is 10 ~ 300 μm, gained hybrid alloys coarse crushing particle is carried out airflow milling fragmentation under nitrogen protection, obtain the hybrid alloys powder that average grain diameter is 3.8 μm,
(3) preparation of green compact
In step (2) gained hybrid alloys powder, add antioxidant and lubricant and mix formation blank, the quality sum of described antioxidant and lubricant is 0.25% of hybrid alloys powder quality, the mass ratio of antioxidant and lubricant is 1:1, antioxidant is the neodymium iron boron special antioxidant purchased from Yadong, Hangzhou new material Co., Ltd, and lubricant is zinc stearate; Blank being loaded die cavity juxtaposition is in the magnetic field of 1.8T in magnetic field intensity, and in room temperature, 70MPa briquetting pressure, 4s of lower dwell time is compressing under nitrogen protection, obtains green compact;
(4) isostatic cool pressing of green compact
The green compact that step (3) obtains being placed in cold isostatic press at pressure is 200MPa pressurize compacting 150s, obtains isostatic cool pressing green compact after release;
(5) sinter
The isostatic cool pressing green compact that step (4) obtains are put into vacuum sintering furnace, 10 -3~ 10 -2in 1050 DEG C of heat preservation sintering 2.5h under Pa vacuum condition, pass into argon gas after terminating and be cooled to room temperature, obtain sintered magnet;
(6) heat treatment
Step (5) gained sintered magnet is incubated 1.5h at 905 DEG C, after insulation terminates, is cooled to less than 100 DEG C, then be heated to 540 DEG C of insulation 1h, pass into argon gas after insulation terminates and be cooled to room temperature, namely obtain sintering cerium-rich rare earth permanent magnetic material.
Measure through AMT-4 characteristic of magnetization automatic measuring instrument, gained sintering cerium-rich rare earth permanent magnetic material magnetic property is: B r=1.26T, H cj=810.3kA/m, (BH) max=292.6kJ/m 3.
Embodiment 8
Described in the present embodiment, the preparation method of rare earth permanent-magnetic material is as follows:
(1) preparation of master alloying slab, the auxiliary alloy casting piece of intergranular
1. prepare burden
Raw material adopt the ferro-boron that the praseodymium content of technical pure purity is the praseodymium neodymium alloy of 20% quality, metallic cerium, pure iron, fine aluminium, fine copper and Boron contents are 20% quality;
According to master alloying 28.66 (Nd 0.8pr 0.2) the mass percentage batching of each component and each component in-69.60Fe-1.02B-0.72Al, and the oxide on each feed metal surface and being mingled with is removed clean;
Prepare burden according to the mass percentage of each component and each component in auxiliary alloy 59.2Ce-36.1Fe-4.1Cu-0.6B, and the oxide on each feed metal surface and being mingled with is removed clean;
2. founding
Master alloying raw material step 1. prepared and the auxiliary alloy raw material of intergranular put into vacuum induction melting furnace respectively, after melting, aluminium alloy is cast in respectively under argon shield on the water-cooled copper running roller that linear velocity is 3m/s and cools fast, obtain rapid hardening master alloying slab that average thickness is 0.25mm and the auxiliary alloy casting piece of intergranular;
(2) preparation of master alloying and the auxiliary mixed powder for alloy of intergranular
The component proportion of the rare earth permanent-magnetic material of required preparation is 24.36 (Nd, Pr)-8.88Ce-64.58Fe-0.96B-1.22T m, be the master alloying slab and the auxiliary alloy casting piece of intergranular that 85:15 weighs that step (1) obtains according to said ratio according to the mass ratio of master alloying slab and the auxiliary alloy casting piece of intergranular, suction hydrogen-Dehydroepiandrosterone derivative is carried out by putting into rotation hydrogen crushing furnace after two kinds of alloy casting piece mixing, the Hydrogen Vapor Pressure inhaling hydrogen process is 0.2MPa, adopt the hydrogen dynamically mended in hydrogen method supplementary furnace, namely complete after suction hydrogen reaches capacity and inhale hydrogen process (when in stove in 10min, hydrogen pressure drop is less than or equal to 0.02MPa, be suction hydrogen to reach capacity), Dehydroepiandrosterone derivative vacuumizes dehydrogenation at 560 DEG C, when namely completing Dehydroepiandrosterone derivative after the mixing slab hydrogen content≤250ppm carrying out Dehydroepiandrosterone derivative, inhale after hydrogen-Dehydroepiandrosterone derivative completes and obtain the hybrid alloys coarse crushing particle that particle diameter is 10 ~ 300 μm, gained hybrid alloys coarse crushing particle is carried out airflow milling fragmentation under nitrogen protection, obtain the hybrid alloys powder that average grain diameter is 3.8 μm,
(3) preparation of green compact
In step (2) gained hybrid alloys powder, add antioxidant and lubricant and mix formation blank, the quality sum of described antioxidant and lubricant is 0.25% of hybrid alloys powder quality, the mass ratio of antioxidant and lubricant is 1:1, antioxidant is the neodymium iron boron special antioxidant purchased from Taiyuan Jia Ci Co., Ltd, and lubricant is zinc stearate; Blank being loaded die cavity juxtaposition is in the magnetic field of 2T in magnetic field intensity, and in room temperature, 70MPa briquetting pressure, 4s of lower dwell time is compressing under nitrogen protection, obtains green compact;
(4) isostatic cool pressing of green compact
The green compact that step (3) obtains being placed in cold isostatic press at pressure is 200MPa pressurize compacting 150s, obtains isostatic cool pressing green compact after release;
(5) sinter
The isostatic cool pressing green compact that step (4) obtains are put into vacuum sintering furnace, 10 -3~ 10 -2in 1050 DEG C of heat preservation sintering 4h under Pa vacuum condition, pass into nitrogen after terminating and be cooled to room temperature, obtain sintered magnet;
(6) heat treatment
Step (5) gained sintered magnet is incubated 1.5h at 910 DEG C, after insulation terminates, is cooled to less than 100 DEG C, then be heated to 510 DEG C of insulation 4h, pass into nitrogen after insulation terminates and be cooled to room temperature, namely sintered cerium-rich rare earth permanent magnetic material.
Measure through AMT-4 characteristic of magnetization automatic measuring instrument, the magnetic property of gained sintering cerium-rich rare earth permanent magnetic material is: B r=1.286T, H cj=912.7kA/m, (BH) max=313.68kJ/m 3.
Embodiment 9
Described in the present embodiment, the preparation method of rare earth permanent-magnetic material is as follows:
(1) preparation of master alloying slab, the auxiliary alloy casting piece of intergranular
1. prepare burden
Raw material adopt the ferro-boron that the praseodymium content of technical pure purity is the praseodymium neodymium alloy of 20% quality, metallic cerium, pure iron, fine aluminium, fine copper and Boron contents are 20% quality;
According to master alloying 28.66 (Nd 0.8pr 0.2) the mass percentage batching of each component and each component in-69.60Fe-1.02B-0.72Al, and the oxide on each feed metal surface and being mingled with is removed clean;
Prepare burden according to the mass percentage of each component and each component in auxiliary alloy 69.3Ce-14.48Fe-16.01Cu-0.21B, and the oxide on each feed metal surface and being mingled with is removed clean;
2. founding
Master alloying raw material step 1. prepared and the auxiliary alloy raw material of intergranular put into vacuum induction melting furnace respectively, after melting, aluminium alloy is cast in respectively under argon shield on the water-cooled copper running roller that linear velocity is 3m/s and cools fast, obtain rapid hardening master alloying slab that average thickness is 0.25mm and the auxiliary alloy casting piece of intergranular;
(2) preparation of master alloying and the auxiliary mixed powder for alloy of intergranular
The component proportion of the rare earth permanent-magnetic material of required preparation is 25.22 (Nd, Pr)-8.32Ce-62.99Fe-0.92B-2.55T m, be the master alloying slab and the auxiliary alloy casting piece of intergranular that 88:12 weighs that step (1) obtains according to said ratio according to the mass ratio of master alloying slab and the auxiliary alloy casting piece of intergranular, suction hydrogen-Dehydroepiandrosterone derivative is carried out by putting into rotation hydrogen crushing furnace after two kinds of alloy casting piece mixing, the Hydrogen Vapor Pressure inhaling hydrogen process is 0.2MPa, adopt the hydrogen dynamically mended in hydrogen method supplementary furnace, namely complete after suction hydrogen reaches capacity and inhale hydrogen process (when in stove in 10min, hydrogen pressure drop is less than or equal to 0.02MPa, be suction hydrogen to reach capacity), Dehydroepiandrosterone derivative vacuumizes dehydrogenation at 560 DEG C, when namely completing Dehydroepiandrosterone derivative after the mixing slab hydrogen content≤250ppm carrying out Dehydroepiandrosterone derivative, inhale after hydrogen-Dehydroepiandrosterone derivative completes and obtain the hybrid alloys coarse crushing particle that particle diameter is 10 ~ 300 μm, gained hybrid alloys coarse crushing particle is carried out airflow milling fragmentation under nitrogen protection, obtain the hybrid alloys powder that average grain diameter is 3.8 μm,
(3) preparation of green compact
In step (2) gained hybrid alloys powder, add antioxidant and lubricant and mix formation blank, the quality sum of described antioxidant and lubricant is 0.25% of hybrid alloys powder quality, the mass ratio of antioxidant and lubricant is 1:1, antioxidant is the neodymium iron boron special antioxidant purchased from Taiyuan Jia Ci Co., Ltd, and lubricant is zinc stearate; Blank being loaded die cavity juxtaposition is in the magnetic field of 2T in magnetic field intensity, and in room temperature, 70MPa briquetting pressure, 6s of lower dwell time is compressing under nitrogen protection, obtains green compact;
(4) isostatic cool pressing of green compact
The green compact that step (3) obtains being placed in cold isostatic press at pressure is 200MPa pressurize compacting 150s, obtains isostatic cool pressing green compact after release;
(5) sinter
The isostatic cool pressing green compact that step (4) obtains are put into vacuum sintering furnace, 10 -3~ 10 -2in 1050 DEG C of heat preservation sintering 4h under Pa vacuum condition, pass into nitrogen after terminating and be cooled to room temperature, obtain sintered magnet;
(6) heat treatment
Step (5) gained sintered magnet is incubated 1.5h at 850 DEG C, after insulation terminates, is cooled to less than 100 DEG C, then be heated to 520 DEG C of insulation 4h, pass into nitrogen after insulation terminates and be cooled to room temperature, namely obtain sintering cerium-rich rare earth permanent magnetic material.
Measure through AMT-4 characteristic of magnetization automatic measuring instrument, the magnetic property of gained sintering cerium-rich rare earth permanent magnetic material is: B r=1.293T, H cj=822.65kA/m, (BH) max=312.3kJ/m 3.
Embodiment 10
Described in the present embodiment, the preparation method of rare earth permanent-magnetic material is as follows:
(1) preparation of master alloying slab, the auxiliary alloy block of intergranular
1. prepare burden
Raw material adopt the praseodymium content of technical pure purity is the praseodymium neodymium alloy of 20% quality, pure iron, fine aluminium, fine copper, content of niobium are 70% quality ferrocolumbium, metallic cobalt and Boron contents to be the ferro-boron of 20% quality;
According to master alloying 29.71 (Nd 0.8pr 0.2) the mass percentage batching of each component and each component in-67.73Fe-1.01B-0.70Al-0.75Co-0.1Nb, and the oxide on each feed metal surface and being mingled with is removed clean;
Prepare burden according to the mass percentage of each component and each component in intergranular auxiliary alloy 81.13Ce-8.40Fe-10.33Cu-0.14B, and the oxide on each feed metal surface and being mingled with is removed clean;
2. founding is with broken
Vacuum induction melting furnace put into by master alloying raw material step 1. prepared, and is cast in by aluminium alloy on the water-cooled copper running roller that linear velocity is 3m/s and cools fast under argon shield after melting, obtains the rapid hardening master alloying slab that average thickness is 0.25mm; The auxiliary alloy raw material of intergranular step (1) prepared puts into vacuum induction melting furnace, melting under argon gas condition, and aluminium alloy melting obtained is cast on water cooled copper mould, obtain the auxiliary alloy cast ingot of rapid hardening intergranular that average thickness is 10mm, then auxiliary for intergranular alloying ingot is put into vacuum furnace, under argon shield, carry out homogenizing annealing in 650 DEG C of insulation 3h, after cooling to room temperature with the furnace, coarse crushing becomes the auxiliary alloy block of the intergranular of 10 ~ 30mm again;
(2) preparation of master alloying powder, the auxiliary alloy powder of intergranular
By the master alloying slab that step (1) obtains, the auxiliary alloy block of intergranular is put into rotation hydrogen crushing furnace respectively and is carried out suction hydrogen-Dehydroepiandrosterone derivative, the Hydrogen Vapor Pressure inhaling hydrogen process is 0.2MPa, adopt the hydrogen dynamically mended in hydrogen method supplementary furnace, namely complete after suction hydrogen reaches capacity and inhale hydrogen process (when in stove in 10min, hydrogen pressure drop is less than or equal to 0.02MPa, be suction hydrogen to reach capacity), Dehydroepiandrosterone derivative vacuumizes dehydrogenation at 560 DEG C, when namely completing Dehydroepiandrosterone derivative after the slab of carrying out Dehydroepiandrosterone derivative or block hydrogen content≤250ppm, after suction hydrogen-Dehydroepiandrosterone derivative completes, to obtain particle diameter be the master alloying coarse crushing particle of 10 ~ 300 μm and particle diameter is the intergranular auxiliary alloy coarse crushing particle of 0.1 ~ 3mm, gained master alloying coarse crushing particle is carried out airflow milling fragmentation under nitrogen protection, obtain the master alloying powder that average grain diameter is 3.5 μm, auxiliary for gained intergranular alloy coarse crushing particle is carried out ball milling in the oil, ratio of grinding media to material is 12:1, rotational speed of ball-mill is 450r/min, Ball-milling Time 60min, obtain the auxiliary alloy powder of intergranular that average grain diameter is 1 μm,
(3) preparation of green compact
The component proportion of the rare earth permanent-magnetic material of required preparation is 26.74 (Nd, Pr)-8.11Ce-61.79Fe-0.92B-2.44T m, be that 90:10 weighs step (2) gained master alloying powder and the auxiliary alloy powder of intergranular according to said ratio according to master alloying powder and intergranular auxiliary alloy powder mass ratio and just they mix and obtain hybrid alloys powder; In hybrid alloys powder, add antioxidant and lubricant and mix formation blank, the quality sum of described antioxidant and lubricant is 0.25% of hybrid alloys powder quality, the mass ratio of antioxidant and lubricant is 1:1, antioxidant is the neodymium iron boron special antioxidant purchased from Taiyuan Jia Ci Co., Ltd, and lubricant is zinc stearate; Blank being loaded die cavity juxtaposition is in the magnetic field of 2T in magnetic field intensity, and in room temperature, 90MPa briquetting pressure, 4s of lower dwell time is compressing under nitrogen protection, obtains green compact;
(4) isostatic cool pressing of green compact
The green compact that step (3) obtains being placed in cold isostatic press at pressure is 240MPa pressurize compacting 200s, obtains isostatic cool pressing green compact after release;
(5) sinter
The isostatic cool pressing green compact that step (4) obtains are put into vacuum sintering furnace, 10 -3~ 10 -2in 1045 DEG C of heat preservation sintering 4h under Pa vacuum condition, pass into argon gas after terminating and be cooled to room temperature, obtain sintered magnet;
(6) heat treatment
Step (5) gained sintered magnet is incubated 1.5h at 890 DEG C, after insulation terminates, is cooled to less than 100 DEG C, then be heated to 505 DEG C of insulation 4h, pass into argon gas after insulation terminates and be cooled to room temperature, namely obtain sintering cerium-rich rare earth permanent magnetic material.
Measure through AMT-4 characteristic of magnetization automatic measuring instrument, the magnetic property of gained sintering cerium-rich rare earth permanent magnetic material is: B r=1.261T, H cj=1093.1kA/m, (BH) max=300.7kJ/m 3.
Embodiment 11
Described in the present embodiment, the preparation method of rare earth permanent-magnetic material is as follows:
(1) preparation of master alloying slab, the auxiliary alloy casting piece of intergranular
1. prepare burden
Raw material adopt the praseodymium content of technical pure purity is the praseodymium neodymium alloy of 20% quality, pure iron, fine aluminium, fine copper, Boron contents are 20% quality ferro-boron and composition to be the mishmetal MM of 51.56%Ce, 25.31%La, 16.94%Nd, 6.19%Pr quality.
According to master alloying 27.57 (Nd 0.8pr 0.2) the mass percentage batching of each component and each component in-70.69Fe-1.02B-0.72Al, and the oxide on each feed metal surface and being mingled with is removed clean;
Prepare burden according to the mass percentage of each component and each component in auxiliary alloy 61.8MM-33.5Fe-4.1Cu-0.6B, and the oxide on each feed metal surface and being mingled with is removed clean;
2. founding
Master alloying raw material step 1. prepared and the auxiliary alloy raw material of intergranular put into vacuum induction melting furnace respectively, after melting, aluminium alloy is cast in respectively under argon shield on the water-cooled copper running roller that linear velocity is 3m/s and cools fast, obtain rapid hardening master alloying slab that average thickness is 0.25mm and the auxiliary alloy casting piece of intergranular;
(2) preparation of master alloying and the auxiliary mixed powder for alloy of intergranular
The component proportion of the rare earth permanent-magnetic material of required preparation is 25.57 (Nd, Pr)-7.13 (Ce, La)-65.11Fe-0.96B-1.23T m, be the master alloying slab and the auxiliary alloy casting piece of intergranular that 85:15 weighs that step (1) obtains according to said ratio according to the mass ratio of master alloying slab and the auxiliary alloy casting piece of intergranular, suction hydrogen-Dehydroepiandrosterone derivative is carried out by putting into rotation hydrogen crushing furnace after two kinds of alloy casting piece mixing, the Hydrogen Vapor Pressure inhaling hydrogen process is 0.18MPa, adopt the hydrogen dynamically mended in hydrogen method supplementary furnace, namely complete after suction hydrogen reaches capacity and inhale hydrogen process (when in stove in 10min, hydrogen pressure drop is less than or equal to 0.02MPa, be suction hydrogen to reach capacity), Dehydroepiandrosterone derivative vacuumizes dehydrogenation at 560 DEG C, when namely completing Dehydroepiandrosterone derivative after the mixing slab hydrogen content≤250ppm carrying out Dehydroepiandrosterone derivative, inhale after hydrogen-Dehydroepiandrosterone derivative completes and obtain the hybrid alloys coarse crushing particle that particle diameter is 10 ~ 300 μm, gained hybrid alloys coarse crushing particle is carried out airflow milling fragmentation under nitrogen protection, obtain the hybrid alloys powder that average grain diameter is 4.0 μm,
(3) preparation of green compact
In step (2) gained hybrid alloys powder, add antioxidant and lubricant and mix formation blank, the quality sum of described antioxidant and lubricant is 0.25% of hybrid alloys powder quality, the mass ratio of antioxidant and lubricant is 1:1, antioxidant is the neodymium iron boron special antioxidant purchased from Beijing Jun Cefeng development in science and technology Co., Ltd, and lubricant is zinc stearate; Blank being loaded die cavity juxtaposition is in the magnetic field of 1.8T in magnetic field intensity, and in room temperature, 50MPa briquetting pressure, 12s of lower dwell time is compressing under nitrogen protection, obtains green compact;
(4) isostatic cool pressing of green compact
The green compact that step (3) obtains being placed in cold isostatic press at pressure is 200MPa pressurize compacting 200s, obtains isostatic cool pressing green compact after release;
(5) sinter
The isostatic cool pressing green compact that step (4) obtains are put into vacuum sintering furnace, 10 -3~ 10 -2in 1045 DEG C of heat preservation sintering 4h under Pa vacuum condition, pass into argon gas after terminating and be cooled to room temperature, obtain sintered magnet;
(6) heat treatment
Step (5) gained sintered magnet is incubated 1.5h at 910 DEG C, after insulation terminates, is cooled to less than 100 DEG C, then be heated to 520 DEG C of insulation 4h, pass into argon gas after insulation terminates and be cooled to room temperature, namely sintered cerium-rich rare earth permanent magnetic material.
Measure through AMT-4 characteristic of magnetization automatic measuring instrument, the magnetic property of gained sintering cerium-rich rare earth permanent magnetic material is: B r=1.273T, H cj=702.4kA/m, (BH) max=295.6kJ/m 3.
Embodiment 12
Described in the present embodiment, the preparation method of rare earth permanent-magnetic material is as follows:
(1) preparation of master alloying slab, the auxiliary alloy casting piece of intergranular
1. prepare burden
Raw material adopt the praseodymium content of technical pure purity is the praseodymium neodymium alloy of 20% quality, pure iron, fine aluminium, fine copper, Boron contents are 20% quality ferro-boron and composition to be the mishmetal MM of 53.93%Ce, 29.35%La, 12.01%Nd, 4.71%Pr quality.
According to master alloying 27.57 (Nd 0.8pr 0.2) the mass percentage batching of each component and each component in-70.69Fe-1.02B-0.72Al, and the oxide on each feed metal surface and being mingled with is removed clean;
Prepare burden according to the mass percentage of each component and each component in auxiliary alloy 61.6MM-33.7Fe-4.1Cu-0.6B, and the oxide on each feed metal surface and being mingled with is removed clean;
2. founding
Master alloying raw material step 1. prepared and the auxiliary alloy raw material of intergranular put into vacuum induction melting furnace respectively, after melting, aluminium alloy is cast in respectively under argon shield on the water-cooled copper running roller that linear velocity is 3m/s and cools fast, obtain rapid hardening master alloying slab that average thickness is 0.25mm and the auxiliary alloy casting piece of intergranular;
(2) preparation of master alloying and the auxiliary mixed powder for alloy of intergranular
The component proportion of the rare earth permanent-magnetic material of required preparation is 24.96 (Nd, Pr)-7.71 (La, Ce)-65.14Fe-0.96B-1.23T m, root is the master alloying slab and the auxiliary alloy casting piece of intergranular that 85:15 weighs that step (1) obtains according to said ratio according to the mass ratio of master alloying slab and the auxiliary alloy casting piece of intergranular, suction hydrogen-Dehydroepiandrosterone derivative is carried out by putting into rotation hydrogen crushing furnace after two kinds of alloy casting piece mixing, the Hydrogen Vapor Pressure inhaling hydrogen process is 0.18MPa, adopt the hydrogen dynamically mended in hydrogen method supplementary furnace, namely complete after suction hydrogen reaches capacity and inhale hydrogen process (when in stove in 10min, hydrogen pressure drop is less than or equal to 0.02MPa, be suction hydrogen to reach capacity), Dehydroepiandrosterone derivative vacuumizes dehydrogenation at 560 DEG C, when namely completing Dehydroepiandrosterone derivative after the mixing slab hydrogen content≤250ppm carrying out Dehydroepiandrosterone derivative, inhale after hydrogen-Dehydroepiandrosterone derivative completes and obtain the hybrid alloys coarse crushing particle that particle diameter is 10 ~ 300 μm, gained hybrid alloys coarse crushing particle is carried out airflow milling fragmentation under nitrogen protection, obtain the hybrid alloys powder that average grain diameter is 4.5 μm,
(3) preparation of green compact
In step (2) gained hybrid alloys powder, add antioxidant and lubricant and mix formation blank, the quality sum of described antioxidant and lubricant is 0.5% of hybrid alloys powder quality, the mass ratio of antioxidant and lubricant is 1:1, antioxidant is the neodymium iron boron special antioxidant purchased from Beijing Jun Cefeng development in science and technology Co., Ltd, and lubricant is zinc stearate; Blank being loaded die cavity juxtaposition is in the magnetic field of 1.8T in magnetic field intensity, and in room temperature, 50MPa briquetting pressure, 12s of lower dwell time is compressing under nitrogen protection, obtains green compact;
(4) isostatic cool pressing of green compact
The green compact that step (3) obtains being placed in cold isostatic press at pressure is 200MPa pressurize compacting 200s, obtains isostatic cool pressing green compact after release;
(5) sinter
The isostatic cool pressing green compact that step (4) obtains are put into vacuum sintering furnace, 10 -3~ 10 -2in 1050 DEG C of heat preservation sintering 4h under Pa vacuum condition, pass into argon gas after terminating and be cooled to room temperature, obtain sintered magnet;
(6) heat treatment
Step (5) gained sintered magnet is incubated 1.5h at 910 DEG C, after insulation terminates, is cooled to less than 100 DEG C, then be heated to 520 DEG C of insulation 4h, pass into argon gas after insulation terminates and be cooled to room temperature, namely sintered cerium-rich rare earth permanent magnetic material.
Measure through AMT-4 characteristic of magnetization automatic measuring instrument, the magnetic property of gained sintering cerium-rich rare earth permanent magnetic material is: B r=1.267T, H cj=693.2kA/m, (BH) max=286.2kJ/m 3.

Claims (9)

1. sinter cerium-rich rare earth permanent magnetic material, it is characterized in that the mass percent of the component that this sintering cerium-rich rare earth permanent magnetic material comprises and each component is as follows: RE1 is 20% ~ 28%, RE2 be 4% ~ 15%, Fe is 60.5% ~ 70.5%, B is 0.8% ~ 1.2%, Tm is 0.1% ~ 5%; The principal phase of this sintering cerium-rich rare earth permanent magnetic material is Nd 2fe 14b or (Nd, Pr) 2fe 14b, is distributed with Ce around main phase grain, or Ce and La;
Described RE1 is Nd, Nd and Pr, rare earth element based on Nd or based on the rare earth element of Nd and Pr, described RE2 is Ce, or Ce and La, described T mfor at least one in Co, Cu, Al, Ga, Nb, Zr, Mo, Mn, Cr.
2. sinter cerium-rich rare earth permanent magnetic material according to claim 1, it is characterized in that described RE1 is that rare earth element based on Nd refers to that the quality of Nd is more than or equal to 95% of RE1 quality, based on the rare earth element of Nd and Pr, described RE1 refers to that the quality of Nd and Pr is more than or equal to 95% of RE1 quality, when RE1 be the rare earth element based on Nd or the rare earth element based on Nd and Pr time, also comprise at least one rare earth element in Dy, Tb, Gd, Ho in RE1.
3. sinter a preparation method for cerium-rich rare earth permanent magnetic material, it is characterized in that processing step is as follows:
(1) preparation of master alloying slab, the auxiliary alloy casting piece of intergranular or block
1. prepare burden
Master alloying RE3-Fe-B-M athe mass percent of the component comprised and each component: RE3 is 27% ~ 30%, Fe is 65% ~ 72%, B is 0.9% ~ 1.1%, M abe 0.1% ~ 4%, described RE3 be Nd, Nd and Pr, rare earth element based on Nd or based on the rare earth element of Nd and Pr, described M afor at least one in Co, Cu, Al, Ga, Nb, Zr, Mo, Mn, Cr;
The auxiliary alloy RE4-Fe-B-M of intergranular bthe mass percent of the component comprised and each component: RE4 is 38% ~ 85%, Fe is 6% ~ 60%, B is 0.1% ~ 1.2%, M bbe 0.1% ~ 20%; Described RE4 is Ce, or based on the rare earth element of Ce and La, described M bfor at least one in Co, Cu, Al, Ga, Nb, Zr, Mo, Mn, Cr;
According to master alloying RE3-Fe-B-M a, the auxiliary alloy RE4-Fe-B-M of intergranular bsaid components and each component mass percent batching;
2. founding or founding and fragmentation
Master alloying raw material step 1. prepared, the auxiliary alloy raw material of intergranular carry out founding respectively and obtain master alloying slab and the auxiliary alloy casting piece of intergranular;
Or master alloying raw material step 1. to be prepared is prepared into slab by founding, pour into the auxiliary alloy cast ingot of intergranular after the melting of intergranular step 1. prepared auxiliary alloy raw material, after auxiliary for intergranular alloy cast ingot is carried out homogenizing annealing, be broken into the auxiliary alloy block of the intergranular being of a size of 10 ~ 30mm again;
(2) preparation of master alloying powder, the auxiliary alloy powder of intergranular or master alloying and the auxiliary mixed powder for alloy of intergranular
Master alloying slab step (1) obtained, the auxiliary alloy block of intergranular carry out suction hydrogen-Dehydroepiandrosterone derivative respectively, obtain the master alloying coarse crushing particle of particle diameter 10 ~ 300 μm and the intergranular auxiliary alloy coarse crushing particle of particle diameter 0.1 ~ 3mm, described master alloying coarse crushing particle is broken by airflow milling under nitrogen or inert gas shielding, obtain the master alloying powder of particle diameter 1 ~ 5 μm, auxiliary for described intergranular alloy coarse crushing particle is carried out ball milling, obtains the auxiliary alloy powder of intergranular of particle diameter 0.5 ~ 3 μm;
Or weigh according to the mass percent of the component of prepared rare earth permanent-magnetic material and each component the master alloying slab and the auxiliary alloy casting piece of intergranular that step (2) obtains, suction hydrogen-Dehydroepiandrosterone derivative is carried out after they being mixed, obtain the hybrid alloys coarse crushing particle that particle diameter is 10 ~ 300 μm, gained hybrid alloys coarse crushing particle is carried out airflow milling fragmentation under nitrogen or inert gas shielding, obtains the hybrid alloys powder that particle diameter is 1 ~ 5 μm;
(3) preparation of green compact
In step (2) gained hybrid alloys powder, add antioxidant and lubricant and mix formation blank, then blank being loaded die cavity juxtaposition in magnetic field, obtain green compact in room temperature is compressing under nitrogen protection;
Or weigh step (2) gained master alloying powder, the auxiliary alloy powder of intergranular they mixed and form hybrid alloys powder according to the mass percent of the component of prepared rare earth permanent-magnetic material and each component, formation blank is mixed after adding antioxidant and lubricant again, then blank is loaded die cavity juxtaposition in magnetic field, compressingly under nitrogen protection obtain green compact;
(4) isostatic cool pressing of green compact
The green compact that step (3) obtains are carried out the isostatic cool pressing green compact that isostatic cool pressing obtains;
(5) sinter
The isostatic cool pressing green compact that step (4) obtains are put into vacuum sintering furnace, under vacuum in 990 ~ 1070 DEG C of sintering 1 ~ 6h, passes into inert gas after terminating or nitrogen is cooled to room temperature, obtain sintered magnet;
(6) heat treatment
Step (5) gained sintered magnet is heated to 800 ~ 950 DEG C of insulation 0.5 ~ 4h, 100 ~ 40 DEG C are cooled to after insulation terminates, be heated to 460 ~ 600 DEG C of insulation 1 ~ 6h again, after insulation terminates, pass into inert gas or nitrogen is cooled to room temperature, namely obtain sintering cerium-rich rare earth permanent magnetic material.
4. sinter the preparation method of cerium-rich rare earth permanent magnetic material according to claim 3; it is characterized in that in step (1); the homogenizing annealing of the auxiliary alloy cast ingot of intergranular is incubated 1 ~ 20h in 600 ~ 1000 DEG C under inert gas shielding, then cools to room temperature with the furnace.
5. according to claim 3 or 4, sinter the preparation method of cerium-rich rare earth permanent magnetic material, it is characterized in that in step (2), the auxiliary alloy block of master alloying slab, intergranular carries out suction hydrogen-Dehydroepiandrosterone derivative respectively, or when carrying out suction hydrogen-Dehydroepiandrosterone derivative after master alloying slab and the mixing of intergranular auxiliary alloy casting piece, the Hydrogen Vapor Pressure inhaling hydrogen process is 0.1 ~ 0.3MPa, namely complete after suction hydrogen reaches capacity and inhale hydrogen process, Dehydroepiandrosterone derivative vacuumizes dehydrogenation at 500 ~ 600 DEG C, when namely completing Dehydroepiandrosterone derivative after the slab of carrying out Dehydroepiandrosterone derivative or block hydrogen content≤250ppm.
6. according to claim 3 or 4, sinter the preparation method of cerium-rich rare earth permanent magnetic material, it is characterized in that in step (3), the magnetic field intensity preparing green compact is 1.5 ~ 3T, and briquetting pressure is 40 ~ 100MPa, and the dwell time is 1 ~ 15s.
7. according to claim 3 or 4, sinter the preparation method of cerium-rich rare earth permanent magnetic material, it is characterized in that in step (4), the pressure of green compact isostatic cool pressing is 120 ~ 320MPa, and the dwell time is 10 ~ 300s.
8. according to claim 3 or 4, sinter the preparation method of cerium-rich rare earth permanent magnetic material, it is characterized in that in step (3), the quality sum of antioxidant and lubricant is 0.05% ~ 0.5% of hybrid alloys powder quality, and the mass ratio of antioxidant and lubricant is 1:1.
9. according to claim 3 or 4, sinter the preparation method of cerium-rich rare earth permanent magnetic material, it is characterized in that in step (1), described RE3 is that the rare earth element based on Nd refers to that the quality of Nd is more than or equal to 95% of RE3 quality, based on the rare earth element of Nd and Pr, described RE3 refers to that the quality of Nd and Pr is more than or equal to 95% of RE3 quality, when RE3 be the rare earth element based on Nd or the rare earth element based on Nd and Pr time, also comprise at least one rare earth element in Ce, La, Dy, Tb, Gd, Ho in RE3; Based on the rare earth element of Ce and La, described RE4 refers to that the quality of Ce and La is more than or equal to 75% of RE4 quality, when RE4 is the rare earth element based on Ce and La, also comprise at least one rare earth element in Nd, Pr, Dy, Tb, Gd, Ho in RE4.
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