CN106601401A - Preparation method of high-abundance rare earth sintered neodymium-iron-boron magnet capable of regulating and controlling grain boundary multi-layer structure and product prepared by preparation method - Google Patents
Preparation method of high-abundance rare earth sintered neodymium-iron-boron magnet capable of regulating and controlling grain boundary multi-layer structure and product prepared by preparation method Download PDFInfo
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- CN106601401A CN106601401A CN201611150726.9A CN201611150726A CN106601401A CN 106601401 A CN106601401 A CN 106601401A CN 201611150726 A CN201611150726 A CN 201611150726A CN 106601401 A CN106601401 A CN 106601401A
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 205
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 194
- 229910001172 neodymium magnet Inorganic materials 0.000 title claims abstract description 109
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 230000001105 regulatory Effects 0.000 title abstract description 11
- 230000001276 controlling effect Effects 0.000 title abstract 3
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- 239000000956 alloy Substances 0.000 claims abstract description 77
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- 238000005245 sintering Methods 0.000 claims abstract description 12
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims description 117
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical class [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims description 72
- 238000002844 melting Methods 0.000 claims description 49
- -1 neodymium iron boron Chemical compound 0.000 claims description 46
- 239000000203 mixture Substances 0.000 claims description 44
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 22
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- 229910052751 metal Inorganic materials 0.000 claims description 14
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- 238000000465 moulding Methods 0.000 claims description 10
- 229910052803 cobalt Inorganic materials 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 6
- 230000014759 maintenance of location Effects 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 4
- 150000002602 lanthanoids Chemical class 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 125000004429 atoms Chemical group 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 23
- 238000000034 method Methods 0.000 abstract description 19
- 229910052779 Neodymium Inorganic materials 0.000 abstract description 7
- 239000002699 waste material Substances 0.000 abstract description 7
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- 238000005516 engineering process Methods 0.000 abstract description 3
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000001939 inductive effect Effects 0.000 description 2
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- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—BASIC 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—BASIC 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
Abstract
The invention discloses a preparation method of a high-abundance rare earth sintered neodymium-iron-boron magnet capable of regulating and controlling a grain boundary multi-layer structure and a product prepared by the preparation method, and aims at solving the problems that the grain boundary strengthening effect is single and waste of heavy rare earth resources is serious due to the fact that fine regulation and control on the grain crystal structure cannot be achieved by an existing method, and limited rare earth resources are greatly consumed along with a dramatic increase in the dosage of the magnet. According to the preparation method, preparation of the high-abundance rare earth sintered neodymium-iron-boron magnet capable of regulating and controlling the grain boundary multi-layer structure is achieved by adopting a double-alloy process and a second sintering technology. The prepared magnet has a double main phase structure and has an Nd2Fe14B main phase and an (La, Nd)2Fe14B/(Ce, Nd)2Fe14B main phase at the same time; and the grain boundary phase has a multi-layer grain boundary structure of a heavy rare earth thin shell layer/a high-potential grain boundary center layer containing high-abundance rare-earth/another heavy rare earth thin shell layer. According to the preparation method, overall improvement of the magnetic property and the corrosion resistance of the magnet is achieved through fine regulation and control on the grain crystal structure on the basis of achieving full utilization of the high-abundance rare earth; and the preparation method has relatively high application value and economic value.
Description
Technical field
The present invention relates to permanent magnet material field, the high abundance rare earth sintering neodymium ferrum of specially a kind of crystal boundary multiple structure regulation and control
Preparation method of boron magnet and products thereof, i.e., a kind of high abundance rare earth sintered NdFeB magnetic of achievable crystal boundary multiple structure regulation and control
Preparation method of body and products thereof.
Background technology
Nd-Fe-B permanent magnet material has excellent magnetic property, is to manufacture high-effect, small volume, lightweight magnetic function device
The ideal material of part, it has been widely used in electric bicycle, electric motor of automobile, computer hard disc, electronic toy, electric tool etc.
Product, and the field such as stereo set, communication product, consumer electronics, armarium, household appliances, magnetic plant, its product shelves
Secondary high, added value is high, operation strategies are wide.Especially in the voice coil motor of computer hard disc driver（VCM）And motor
（HDD）, New-type electric machine, NMR (Nuclear Magnetic Resonance)-imaging（MRL）In application Deng core component, Nd-Fe-B permanent magnet material has irreplaceable
Effect.
In recent years, the fast development of wind-power electricity generation and electric automobile, has magnetic based on Nd-Fe-B permanent magnet material itself
High, abundant raw material and lower-price characteristic, wind-power electricity generation and electric automobile field are in the demand of high-performance neodymium-iron-boron magnet
Explosive increase.Therefore, neodymium iron boron industry is also considered as the Chaoyang industry of 21 century.
The principal phase of neodymium iron boron magnetic body is Nd2Fe14B Hard Magnetic phases, Grain-Boundary Phase is rich-Nd phase.Wherein, the composition of Grain-Boundary Phase, structure
With distribution for magnet magnetic property, corrosion resistance and mechanical performance, having obviously affects.
At present, researcher is realized to Grain-Boundary Phase mainly by methods such as alloying addition, crystal boundary modified and grain boundary decisions
Reinforcing, so as to improve magnet performance.Existing method cannot realize the finely regulating to grain boundary structure, cause intercrystalline strengthening effect list
First, the problems such as heavy rare earth serious waste of resources.Additionally, with the sharp increase of magnet consumption, limited rare earth resources become restriction neodymium
The major issue of ferrum boron application.
For this purpose, in the urgent need to a kind of new method or material, to alleviate the problems referred to above.
The content of the invention
The present invention goal of the invention be：The finely regulating to grain boundary structure cannot be realized for existing method, causes crystalline substance
Boundary's reinforcing single effect, heavy rare earth serious waste of resources, and with the sharp increase of magnet consumption, by causing, limited rare earth resources are big
The problem that amount is consumed, there is provided a kind of preparation method of the high abundance rare earth Sintered NdFeB magnet of crystal boundary multiple structure regulation and control and its
Product.In the present invention, using pairing gold process and double sintering technology, the high abundance rare earth of crystal boundary multiple structure regulation and control is realized
The preparation of Sintered NdFeB magnet.Magnet prepared by the present invention has double principal phase structures, i.e., have Nd simultaneously2Fe14B principal phases and
(La,Nd)2Fe14B/(Ce,Nd)2Fe14B principal phases；And Grain-Boundary Phase has heavy rare earth shell layer/high potential containing high abundance rare earth brilliant
Boundary's central core/heavy rare earth shell layer multi-layer grain boundary structure.The present invention is being realized on the basis of high abundance rare earth makes full use of, and is led to
The finely regulating to grain boundary structure is crossed, comprehensive raising of magnet magnetic property and corrosion resistance is realized.Wherein, double principal phase structures
The deterioration of principal phase magnetic property can be suppressed, the heavy rare earth shell layer for being distributed in main phase grain border has higher magnetocrystalline different
Property field, the magnetic domain therefore, it is possible to suppress the crystal boundary weakness zone in opposing magnetic field inverts, and then improves the coercivity and height of magnet
Temperature stability.Meanwhile, heavy rare earth shell layer is only distributed in main phase grain border, is seldom diffused into principal phase and crystal boundary central area,
Heavy rare earth consumption is greatly reduced, magnet generation cost is reduced.And contain the shape of the high potential crystal boundary central core of high abundance rare earth
Into the consumption of light rare earth then further being improved, while reducing Grain-Boundary Phase and Nd2Fe14The difference in Electrode Potential of B principal phases, reduces electricity
Chemical attack driving force, hence it is evident that improve the corrosion resistance of magnet.
To achieve these goals, the present invention is adopted the following technical scheme that：
The preparation method of the high abundance rare earth Sintered NdFeB magnet of crystal boundary multiple structure regulation and control, comprises the steps：
（1）Low rare-earth Nd-Fe-B main-phase alloy powder A1, neodymium iron boron main-phase alloy powder A2 of the MM of rare earth containing high abundance are taken respectively, will be low
Rare-earth Nd-Fe-B main-phase alloy powder A1, neodymium iron boron main-phase alloy powder A2 of the MM of rare earth containing high abundance and low melting point heavy rare earth crystal boundary weight
Structure alloyed powder R1xM1yMixing, obtains the first mixture, and the first mixture is heated to into low melting point heavy rare earth crystal boundary reconstruct alloyed powder
R1xM1yMore than fusing point, and heating-up temperature is less than 1100 DEG C, makes low rare-earth Nd-Fe-B main-phase alloy A1, main-phase alloy A2 crystal grain side
Edge forms the heavy rare earth shell layer of high magnetocrystalline anisotropy, obtains intermediate；
（2）By step（1）After the intermediate of preparation is broken, gained powder body and the low melting point high potential crystal boundary containing high abundance rare earth
Reconstruct alloy MMaM2bMixing, obtains the second mixture, and the second mixture is carried out after magnetic field orientating molding, be sintered successively,
Heat treatment, obtains final product product.
The MM is one or more in La, Ce.
The particle mean size of low rare-earth Nd-Fe-B main-phase alloy powder A1 is less than 5 μm, and rare earth element content is less than 29
Wt.%, Nd2Fe14B phases proportion is more than 95 %.
The particle mean size of neodymium iron boron main-phase alloy powder A2 of the MM of rare earth containing high abundance is less than 5 μm, high abundance therein
Rare earth MM accounts for 3 more than wt.% of main-phase alloy powder A2 gross mass.
High abundance rare earth MM accounts for 3 wt.% ~ 20 wt.% of main-phase alloy powder A2 gross mass.
The low melting point heavy rare earth crystal boundary reconstructs alloyed powder R1xM1yIn, R1 is the one kind in lanthanide series metal Gd, Tb, Dy, Ho
Or it is various, M1 is one or more in O, F, H, Cu, Ni, Fe, Co, Sn, Ti, Nb, Zr, and x, y are respectively the atom hundred of R1, M1
Fraction, the scope of x is 5 ~ 80, x with y's and for 100.
The low melting point heavy rare earth crystal boundary reconstructs alloyed powder R1xM1yFusing point be less than 900 DEG C.
The low melting point high potential crystal boundary reconstructs alloy MMaM2bIn, MM is one or two in lanthanide series metal La, Ce,
M2 is one or more in high standard noble potential metal Cu, Ni, Fe, Co, and a, b are respectively the atomic percentage of MM and M2, the model of a
Enclose is 5 ~ 80, a with b's and for 100.
The low melting point heavy rare earth crystal boundary reconstructs alloyed powder R1xM1y, low melting point high potential crystal boundary reconstruct alloyed powder MMaM2b
Granularity be 0.1-100 μm respectively.
The step（2）In, the second mixture is carried out after magnetic field orientating molding, to be sintered, sintering temperature is 950-
1100 DEG C, sintering time is 2-5h, then carries out two-stage heat treatment, and one-level heat treatment temperature is 850-950 DEG C, and temperature retention time is
1-5h, two grades of heat treatment temperatures are 300-600 DEG C, and temperature retention time is 1-5h, obtains final product product.
Using the product prepared by preceding method.
In terms of intercrystalline strengthening mechanism, the coercivity of magnet is improved, need to form a floor height magnetocrystalline on main phase grain border
Anisotropic heavy rare earth shell layer；And improve magnet corrosion resistance, then need crystal boundary be centrally formed high potential stablize
Grain-Boundary Phase；The seriality of Grain-Boundary Phase is improved, needs to reduce Grain-Boundary Phase fusing point, and improve its wettability with principal phase.
At present, Grain-Boundary Phase often by as an entirety studying its fusing point, magnetocrystalline anisotropy field and the change of corrosion potential
Change, it is impossible to realize finely regulating to grain boundary structure, the problems such as cause intercrystalline strengthening single effect, heavy rare earth serious waste of resources
Occur.Additionally, with the sharp increase of magnet consumption, limited rare earth resources become the major issue for limiting neodymium iron boron magnetic body application.
And during rare earth mining, high abundance rare earth La, Ce of rich reserves etc. as rare earth Nd association product, because its 2:14:1
The theoretical magnetic property of phase is less than Nd2Fe14B does not obtain enough attention and utilization, causes the waste of high abundance rare earth resources.
To sum up, the current urgent problem of sintered neodymium iron boron material is concentrated mainly on following two aspects：1）Magnet
Coercivity is low, and corrosion resistance is poor；2）High abundance rare earth La, Ce etc. are poor because of intrinsic magnetic property, are not fully used.
For the problem that neodymium iron boron magnetic body coercivity is low, corrosion resistance is poor, researcher mainly by alloying addition and
Crystal boundary modified and reconstruct method realizes reinforcing to Grain-Boundary Phase, so as to improve the coercivity of Sintered NdFeB magnet and anticorrosive
Performance.
Many researchers have studied the oligo-element alloying such as Al, Co, Cu, Ga, P, Cr, Ti, Zr, Pb, to improve magnet
Decay resistance；These elements can be generated relatively stable with Nd, the Fe in Grain-Boundary Phase or B element generation chemical reaction
Grain-Boundary Phase, suppresses corrosion and dissolving of the Grain-Boundary Phase in corrosive environment, so as to prevent coming off and magnetic device for main phase grain
Failure.Although melting adds metal or alloy and can form relatively stable Grain-Boundary Phase in crystal boundary, to a certain degree improving magnetic
The corrosion resistance of body；But the element of melting addition typically has and is partially into Nd2Fe14B principal phases, part replace rare earth Nd or
Transition-metal Fe, causes the decline of the intrinsic performance of magnet.Meanwhile, some nonmagnetic elements can cause magnetic dilution to make into principal phase
With the remanent magnetism and maximum magnetic energy product of reduction magnet.
Crystal boundary modified and reconstruct refers to and prepare respectively Nd-Fe-B magnetic powders and crystal boundary addition powder, and by mechanical mixture by two
Plant powder mix homogeneously, the method that compacting sintering is carried out afterwards.Using crystal boundary adding method, the crystalline substance of design addition that can be artificial
Boundary's modified powder, and follow-up sintering process temperature is typically at 1050-1100 DEG C or so, well below smelting temperature.Therefore, phase
Than melting addition, its additive can concentrate on Grain-Boundary Phase, and can try one's best it is few be diffused in principal phase, so as to maximum limit
The additive that plays of degree improves the effect of Grain-Boundary Phase.It is different that addition heavy rare earth alloy can form high magnetocrystalline in magnet grain boundaries
The heavy rare earth shell of property, so as to improve the coercivity of magnet；And add high potential alloy, chemical property can be formed in grain boundaries
Stable Grain-Boundary Phase, reduces principal phase and Grain-Boundary Phase potential difference, so as to improve magnet corrosion resistance.
However, research before is all studying using Grain-Boundary Phase as an entirety, crystal boundary is strengthened by different methods,
The finely regulating to crystal boundary internal structure is not realized, so as to cause unnecessary waste.For example, it is brilliant in heavy rare earth alloy
Boundary is modified and reconstructs, and heavy rare earth shell that main phase grain border is formed can effectively improve magnet coercivity, and remaining big portion
Divide heavy rare earth element to concentrate on crystal boundary central area, cause unnecessary waste.Meanwhile, reconstruct magnetic in high potential alloy crystal boundary
In body, grain boundaries are defined and continuously stablize Grain-Boundary Phase, and the intrinsic corrosion resistance of magnet greatly improved, but in order to reduce into
This, in general high potential reconstruct alloy heavy rare earth element is not contained, so being lifted to coercivity little.At present, cannot also realize
It is substantially improved while neodymium iron boron magnetic body coercivity and corrosion resistance.
Think after inventor's analysis, the reason for cause the problems referred to above, be mainly, it is brilliant under current process conditions
Boundary's composition and structure cannot realize finely regulating, can't simultaneously control the magnetic reversal farmland forming core field of crystal boundary, grain boundary potentials and steady
It is qualitative, and the magnetic exchange coupling effect between main phase grain.
Meanwhile, in order to solve rare earth Nd shortage, high abundance rare earth La, the problem of the Ce wastings of resources, the main employing of the present invention
The mode such as double principal phase technologies and crystal boundary addition high abundance rare earth, to improve the utilization rate of La, Ce high abundance rare earth.Double principal phase structures
Refer in neodymium iron boron magnetic body, while having Nd2Fe14B principal phases and (La, Nd)2Fe14B/(Ce,Nd)2Fe14B principal phases, it is biphase
Between produce magnetic exchange coupling effect, magnetocrystalline anisotropy fieldH ARelatively low (La, Nd)2Fe14B/(Ce,Nd)2Fe14B principal phases are brilliant
Grain border is due to definingH AHigher Nd2Fe14B shells, improve the coercivity of magnet.Therefore, the double principal phases in the present invention
Structure compensate for the poor shortcoming of the intrinsic magnetic property of high abundance rare earth.
In addition, thinking after inventor's research, the high potential alloy of crystal boundary addition high abundance rare earth can reduce principal phase and crystal boundary
The potential difference of phase, improves the corrosion resistance of magnet.Containing for low melting point is designed by alloy phase diagram and metal master electrode potential
The high potential alloy of high abundance rare earth, prepares neodymium iron boron magnetic body using pairing gold process afterwards, can realize high abundance rare earth collection
In grain boundary area purpose, improve corrosion resistance while, because high abundance rare earth is mainly distributed on grain boundaries, do not have
Principal phase is diffused in a large number such that it is able to keep the magnetic property that magnet is higher.
While in order to realize that high abundance rare earth makes full use of, keep even improving the magnetic property and corrosion resistance of magnet
Can, the present invention adopts following design principle：1）With double principal phase structures, by the interaction between principal phase, the magnetic of magnet is kept
Performance；2）Main phase grain border forms heavy rare earth shell layer, improves the coercivity and heat stability of magnet；3）Crystal boundary center be containing
High abundance rare earth high potential Grain-Boundary Phase, improves the corrosion resistance of magnet.
Based on this, the present invention provides a kind of preparation of the high abundance rare earth Sintered NdFeB magnet of crystal boundary multiple structure regulation and control
Method and products thereof, the method mainly comprises the steps.
In the present invention, first, the Nd-Fe-B principal phases powder of low content of rare earth and the neodymium iron boron master containing high abundance rare earth are prepared
Be harmonious bronze.Wherein, the method that the Nd-Fe-B principal phase powder A1 of low content of rare earth is quickly cooled down using melting and rejection tablet, is first obtained
Strip, subsequently by the way that hydrogen is quick-fried and air-flow grinding process, obtains principal phase powder of the average particle size particle size less than 5 μm.The MM of rare earth containing high abundance
Main-phase alloy powder adopt alloyage process, addition part high abundance rare earth replaces rare earth Nd, is formed and has (La, Nd)2Fe14B/
(Ce,Nd)2Fe14The alloy of B principal phases, and by the way that hydrogen is quick-fried and air-flow grinding process, obtain principal phase of the average particle size particle size less than 5 μm
Powder.Wherein, the particle mean size of low rare-earth Nd-Fe-B main-phase alloy powder A1 powder is less than 5 μm（Particle diameter may range from 0.01 ~ 5 μ
m）, rare earth element content is less than 29 wt.%, Nd2Fe14B phases proportion is more than 95 %.The MM of rare earth containing high abundance（MM=La、Ce
In one or two）Neodymium iron boron main-phase alloy powder A2 particle mean size be less than 5 μm（Particle diameter may range from 0.01 ~ 5 μ
m）, high abundance rare earth MM therein accounts for 3 more than wt.% of main-phase alloy powder A2 gross mass（Can be 3 ~ 20 wt.%）.The present invention
In, the high abundance rare earth of indication is primarily referred to as La, Ce, and both mixture.
Secondly, low melting point heavy rare earth crystal boundary reconstruct alloyed powder is prepared.According to enthalpy of mixing between alloy phase diagram, element, design low
The composition of fusing point heavy rare earth crystal boundary reconstruct alloy, generally eutectic composition, using vacuum arc melting or vacuum induction melting,
Alloy pig is prepared, followed by modes such as ball milling or airflow millings, by alloy breaks down into the powder that granularity is 0.1-100 μm,
Obtain final product low melting point heavy rare earth crystal boundary reconstruct alloyed powder R1xM1y.Low melting point heavy rare earth crystal boundary reconstructs alloyed powder R1xM1yIn, R1 is lanthanum
It is one or more in metal Gd, Tb, Dy, Ho, M1 is the one kind or many in O, F, H, Cu, Ni, Fe, Co, Sn, Ti, Nb, Zr
Kind, x, y are respectively the atomic percentage of R1, M1, wherein, 5≤x≤80,20≤y≤95.The fusing point of alloyed powder R1xM1y is less than
900℃。
Then, the reconstruct alloyed powder of the low melting point high potential crystal boundary containing high abundance rare earth is prepared.According between alloy phase diagram, element
Enthalpy of mixing and metal master electrode potential, design alloying component, using vacuum arc melting or vacuum induction melting, prepare
Alloy pig, followed by modes such as ball milling or airflow millings, by alloy breaks down into the powder that granularity is 0.1-100 μm, obtains final product eutectic
Point high potential crystal boundary reconstruct alloy MMaM2b.Wherein, a and b are respectively the atomic percentages of MM and M, wherein, 5≤a≤80,20≤
B≤95, alloyed powder MMaM2bFusing point be less than 900 DEG C, the granularity of powder is 0.1-100 μm.
Again by low rare-earth Nd-Fe-B main-phase alloy powder A1, neodymium iron boron main-phase alloy powder A2 of the MM of rare earth containing high abundance and eutectic
Point heavy rare earth crystal boundary reconstruct alloyed powder R1xM1yMixing, obtains the first mixture, and the first mixture is heated to into low melting point heavy rare earth
Crystal boundary reconstructs alloyed powder R1xM1yMore than fusing point, and heating-up temperature is less than 1100 DEG C so that crystal boundary reconstruct powder melts and is uniformly distributed
Around main phase grain, react with principal phase in heat treatment process, make low rare-earth Nd-Fe-B main-phase alloy A1, main-phase alloy
A2 crystal edges generate the higher heavy rare earth shell layer of magnetocrystalline anisotropy field, and then improve magnet coercivity, obtain intermediate.
Finally, by the intermediate for preparing it is broken after, gained powder body and the low melting point high potential crystal boundary containing high abundance rare earth
Reconstruct alloy MMaM2bUniform mixing, obtains the second mixture, and the second mixture is carried out after magnetic field orientating molding, to carry out successively
Sintering, heat treatment, prepare the high abundance rare earth Sintered NdFeB magnet with multilamellar grain boundary structure.
Wherein, the intermediate powder for processing and the reconstruct alloyed powder magnetic of the low melting point high potential crystal boundary containing high abundance rare earth
After the oriented moulding of field, sinter at 950-1100 DEG C, be incubated 2-5 hours, then carry out heat treatment, one-level heat treatment temperature is
850-950 DEG C, temperature retention time is 1-5 hours, and two grades of heat treatment temperatures are 300-600 DEG C, and temperature retention time is 1-5 hours.
To sum up, the invention provides a kind of high abundance rare earth Sintered NdFeB magnet of achievable crystal boundary multiple structure regulation and control
Preparation method, the present invention prepared and meets desired multilamellar grain boundary structure by the finely regulating to grain boundary structure, be conducive to
Magnet prepare and use during, maintain the stability of the multiple structure, and study the multiple structure to magnet magnetic property, anti-
The influencing mechanism of corrosive nature, and at present the research of this respect is rarely reported.
As shown in Fig. 2 giving have in the present invention heavy rare earth shell layer/high potential crystal boundary center containing high abundance rare earth
The Sintered NdFeB magnet structural representation of layer/heavy rare earth shell layer multi-layer grain boundary structure.The magnet has double principal phase structures, together
When there is the heavy rare earth shell layer of high magnetocrystalline anisotropy on main phase grain border, be containing high abundance rare earth in crystal boundary center
High potential crystal boundary central core., using high abundance rare earth and a small amount of heavy rare earth, preparing grain boundary structure can finely regulating for the present invention
High-performance neodymium-iron-boron magnet, with higher using value.
Magnet prepared by the present invention is measured, measurement result shows, sintering of the present invention with crystal boundary multiple structure
Coercivity can reach 16 more than kOe under neodymium iron boron magnetic body room temperature, and heavy rare earth addition is less than 1 wt.%；In 3.5 wt.% chlorinations
Corrosion potential in sodium water solution is higher than -0.80V, at 120 DEG C, in the environment of 2 atmospheric pressure and 100% relative humidity 96 is corroded
The weight loss of hour is less than 0.78mg/cm2.In the present invention, the formation of heavy rare earth shell layer substantially increases the magnetocrystalline of Grain-Boundary Phase
Anisotropy fieldH A, and then improve the coercivity of magnetH cj, the formation of high potential crystal boundary central core substantially reduces Grain-Boundary Phase
And Nd2Fe14The potential difference of B principal phases, i.e. electrochemical corrosion driving force, and then improve the corrosion resistance of magnet；Meanwhile, Gao Feng
The a large amount of use of degree rare earth greatly reduces production cost, and the magnetic property of magnet does not occur corruptions.
Description of the drawings
Examples of the present invention will be described by way of reference to the accompanying drawings, wherein：
Fig. 1 is traditional sintered NdFeB structural representation.
Fig. 2 is the structural representation that the present invention prepares magnet.
Specific embodiment
All features disclosed in this specification, or disclosed all methods or during the step of, except mutually exclusive
Feature and/or step beyond, can combine by any way.
Any feature disclosed in this specification, unless specifically stated otherwise, can be equivalent or with similar purpose by other
Alternative features are replaced.I.e., unless specifically stated otherwise, each feature is an example in a series of equivalent or similar characteristics
.
Embodiment 1
The present embodiment comprises the steps.
（1）Prepare the Nd-Fe-B principal phases powder and the neodymium iron boron principal phase powder containing high abundance rare earth of low content of rare earth
When preparing the Nd-Fe-B principal phase powder of low content of rare earth, the method quickly cooled down using melting and rejection tablet is obtained neodymium iron boron speed
Solidifying thin slice.Subsequently, by the way that hydrogen is quick-fried and air-flow grinding process, the Nd- that average particle size particle size is about 3.8 μm of low content of rare earth is obtained
Fe-B principal phase powder.
The neodymium iron boron principal phase powder containing high abundance rare earth is prepared, composition is Nd12.3FebalB6.1(Nd10.3La2.0)
FebalB3.1.The method quickly cooled down using melting and rejection tablet, is obtained neodymium iron boron rapid hardening thin slice.Subsequently, by the way that hydrogen is quick-fried and airflow milling
Technique, obtains the neodymium iron boron principal phase powder containing high abundance rare earth that average particle size particle size is about 3.8 μm.
（2）Prepare low melting point heavy rare earth crystal boundary reconstruct alloy
According to enthalpy of mixing between alloy phase diagram, element, design low melting point heavy rare earth crystal boundary reconstruct alloying component, it is desirable to contain in alloy
More heavy rare earth element, while fusing point is relatively low, can melt and be evenly distributed on around main phase grain in heat treatment process.
Inventor have selected Dy-Ni binary eutectics point components D y69Ni31（Atomic percent）As the reconstruct of heavy rare earth crystal boundary
Alloy, its fusing point is 693 DEG C.Afterwards, the La-Co binary containing high abundance rare earth is have selected according to the standard electrode potential of metal
Eutectic composition La69Co31（Atomic percent）Alloy is reconstructed as high potential crystal boundary, its fusing point is 500 DEG C.Subsequently, by electricity
Arc melting is prepared for two kinds of crystal boundary reconstruct alloy pigs, and is prepared for the alloy powder that granularity is about 1.7 μm by ball milling.
（3）Prepare product
In mass ratio it is 1 by low rare-earth Nd-Fe-B main-phase alloy powder and neodymium iron boron principal phase powder containing high abundance rare earth:1 ratio
Uniform mixing, subsequently reconstructs alloyed powder Dy by mixed powder and heavy rare earth crystal boundary69Ni31Uniform mixing, obtains the first mixture, will
First mixture vacuum heat 2 hours at 800 DEG C, obtain intermediate.The intermediate powder for obtaining is crushed, is disperseed, and
With high potential alloyed powder La69Co31Uniform mixing, obtains the second mixture.Wherein, low rare earth principal phase powder（I.e. low rare-earth Nd-Fe-B
The mixture of main-phase alloy powder and the neodymium iron boron principal phase powder containing high abundance rare earth）：Heavy rare earth crystal boundary reconstructs alloyed powder
Dy69Ni31：High potential alloyed powder La69Co31Mass ratio be 97:1:2.By the second mixture under 1.6 T, 200 MPa, carry out
Magnetic field orientating molding, sinters 4 hours afterwards, then heat treatment 2 hours at 890 DEG C at 1070 DEG C, then at heat at 400 DEG C
Reason 2 hours, is obtained and has double principal phase structures, while with heavy rare earth shell layer/high potential crystal boundary center containing high abundance rare earth
The neodymium iron boron magnetic body of layer/heavy rare earth shell layer multi-layer grain boundary structure.
Jing is determined, the obtained neodymium iron boron magnetic body with double principal phases and multilamellar grain boundary structure of the present embodiment, and its coercivity is
16.78 kOe, corrosion potential of the magnet in 25 DEG C, 3.5 wt.% sodium chloride solutions is -0.771 V；Magnet is at 120 DEG C, 2
In the environment of atmospheric pressure and 100% relative humidity, the weight loss for corroding 96 hours is 0.65 mg/cm2。
Embodiment 2
The present embodiment comprises the steps.
（1）Prepare the Nd-Fe-B principal phases powder and the neodymium iron boron principal phase powder containing high abundance rare earth of low content of rare earth
The Nd-Fe-B principal phase powder of low content of rare earth, and the neodymium iron boron principal phase powder containing high abundance rare earth are prepared first（Composition is
Nd12.3FebalB6.1(Nd10.3Ce2.0)FebalB3.1）.The method quickly cooled down using melting and rejection tablet, is obtained neodymium iron boron rapid hardening
Thin slice.Subsequently, by the way that hydrogen is quick-fried and air-flow grinding process, two kinds of principal phase powder that average particle size particle size is about 3.8 μm are obtained.
（2）Prepare low melting point heavy rare earth crystal boundary reconstruct alloy
According to enthalpy of mixing between alloy phase diagram, element, design low melting point heavy rare earth crystal boundary reconstruct alloying component, it is desirable to contain in alloy
More heavy rare earth element, while fusing point is relatively low, can melt in heat treatment process, and be evenly distributed on around main phase grain.
The present embodiment have selected y-Ni binary eutectics point components D y71.5Fe28.5（Atomic percent）As heavy rare earth crystal boundary weight
Structure alloy, its fusing point is 890 DEG C.Afterwards, the La-Co binary containing high abundance rare earth is selected according to the standard electrode potential of metal
Eutectic composition La69Co31（Atomic percent）Alloy is reconstructed as high potential crystal boundary, its fusing point is 500 DEG C.Subsequently, by electricity
Arc melting is prepared for two kinds of crystal boundary reconstruct alloy pigs, and is prepared for the alloy powder that granularity is about 1.7 μm by ball milling.
（3）Prepare product
In mass ratio it is 1 by the Nd-Fe-B principal phases powder of low content of rare earth and neodymium iron boron principal phase powder containing high abundance rare earth:1
Ratio uniform mixes, and subsequently mixed powder and heavy rare earth crystal boundary is reconstructed into alloyed powder Dy71.5Fe28.5Uniform mixing, obtains the first mixing
Thing, by the first mixture at 800 DEG C vacuum heat 2 hours, obtain intermediate.The intermediate powder for obtaining is crushed, is divided
Dissipate, and with high potential alloyed powder La69Co31Uniform mixing, obtains the second mixture.Wherein, low rare earth principal phase powder：Heavy rare earth is brilliant
Boundary reconstructs alloyed powder Dy69Ni31：High potential crystal boundary reconstructs alloy La69Co31Mass ratio be 96:2:2.Second mixture is existed
1.6 T, under 200 MPa, carry out magnetic field orientating molding, afterwards sintering 4 hours at 1070 DEG C, then the heat treatment 2 at 890 DEG C
Hour, then heat treatment 2 hours is obtained and has double principal phase structures at 400 DEG C, while having heavy rare earth shell layer/dilute containing high abundance
The neodymium iron boron magnetic body of the high potential crystal boundary central core/heavy rare earth shell layer multi-layer grain boundary structure of soil.
Jing is determined, the obtained neodymium iron boron magnetic body with double principal phases and multilamellar grain boundary structure of the present embodiment, and its coercivity is
18.46 kOe, corrosion potential of the magnet in 25 DEG C, 3.5 wt.% sodium chloride solutions is -0.777 V；Magnet is at 120 DEG C, 2
The weight loss for corroding in the environment of atmospheric pressure and 100% relative humidity 96 hours is 0.68 mg/cm2。
Embodiment 3
The present embodiment comprises the steps.
（1）Prepare the Nd-Fe-B principal phases powder and the neodymium iron boron principal phase powder containing high abundance rare earth of low content of rare earth
The Nd-Fe-B principal phase powder of low content of rare earth, and the neodymium iron boron principal phase powder containing high abundance rare earth are prepared first（Composition is
Nd12.3FebalB6.1(Nd9.3La3.0)FebalB3.1）.The method quickly cooled down using melting and rejection tablet, is obtained neodymium iron boron rapid hardening
Thin slice.Subsequently, two kinds of principal phase powder that average particle size particle size is about 3.8 μm are obtained with air-flow grinding process by the way that hydrogen is quick-fried.
（2）Prepare low melting point heavy rare earth crystal boundary reconstruct alloy
According to enthalpy of mixing between alloy phase diagram, element, design low melting point heavy rare earth crystal boundary reconstruct alloying component, it is desirable to contain in alloy
More heavy rare earth element, while fusing point is relatively low, can melt and be evenly distributed on around main phase grain in heat treatment process.
The present embodiment selects Dy-Ni binary eutectic point components Ds y69Ni31（Atomic percent）As the reconstruct of heavy rare earth crystal boundary
Alloy, its fusing point is 693 DEG C.Afterwards, the La-Co binary containing high abundance rare earth is selected to be total to according to the standard electrode potential of metal
Fisheye composition La69Co31（Atomic percent）Alloy is reconstructed as high potential crystal boundary, its fusing point is 500 DEG C.Subsequently, by electric arc
Melting is prepared for two kinds of crystal boundary reconstruct alloy pigs, and is prepared for the alloy powder that granularity is about 1.7 μm by ball milling.
（3）Prepare product
In mass ratio it is 1 by the Nd-Fe-B principal phases powder of low content of rare earth and neodymium iron boron principal phase powder containing high abundance rare earth:1
Ratio uniform mixes, and subsequently mixed powder and heavy rare earth crystal boundary is reconstructed into alloyed powder Dy69Ni31Uniform mixing, obtains the first mixing
Thing, by the first mixture at 800 DEG C vacuum heat 2 hours, obtain intermediate.The intermediate powder for obtaining is crushed, is divided
Dissipate, and with high potential alloyed powder La69Co31Uniform mixing, obtains the second mixture.Wherein, low rare earth principal phase powder：Heavy rare earth is brilliant
Boundary's alloyed powder：The mass ratio of high potential grain boundary alloys powder is 96:2:2.By the second mixture under 1.6 T, 200 MPa, carry out
Magnetic field orientating molding, sinters 4 hours afterwards, then heat treatment 2 hours at 890 DEG C at 1070 DEG C, then at heat at 400 DEG C
Reason is obtained for 2 hours has double principal phase structures, while with heavy rare earth shell layer/high potential crystal boundary center containing high abundance rare earth
The neodymium iron boron magnetic body of layer/heavy rare earth shell layer multi-layer grain boundary structure.
Jing is determined, the obtained neodymium iron boron magnetic body with double principal phases and multilamellar grain boundary structure of the present embodiment, and its coercivity is
18.12 kOe, corrosion potential of the magnet in 25 DEG C, 3.5 wt.% sodium chloride solutions is -0.784 V；Magnet is at 120 DEG C, 2
The weight loss for corroding in the environment of atmospheric pressure and 100% relative humidity 96 hours is 0.69 mg/cm2。
Embodiment 4
The present embodiment comprises the steps.
（1）Prepare the Nd-Fe-B principal phases powder and the neodymium iron boron principal phase powder containing high abundance rare earth of low content of rare earth
The Nd-Fe-B principal phase powder of low content of rare earth, and the neodymium iron boron principal phase powder containing high abundance rare earth are prepared first（Composition is
Nd12.3FebalB6.1(Nd9.3La2.0Ce1.0)FebalB3.1）.The method quickly cooled down using melting and rejection tablet, is obtained neodymium iron boron
Rapid hardening thin slice.Subsequently, two kinds of principal phase powder that average particle size particle size is about 3.8 μm are obtained with air-flow grinding process by the way that hydrogen is quick-fried.
（2）Prepare low melting point heavy rare earth crystal boundary reconstruct alloy
According to enthalpy of mixing between alloy phase diagram, element, design low melting point heavy rare earth crystal boundary reconstruct alloying component, it is desirable to contain in alloy
More heavy rare earth element, while fusing point is relatively low, can melt and be evenly distributed on around main phase grain in heat treatment process.
Inventor selects Dy-Ni binary eutectic point components Ds y71.5Fe28.5（Atomic percent）As the reconstruct of heavy rare earth crystal boundary
Alloy, its fusing point is 890 DEG C.Afterwards, the La-Co binary containing high abundance rare earth is selected to be total to according to the standard electrode potential of metal
Fisheye composition La69Co31（Atomic percent）Alloy is reconstructed as high potential crystal boundary, its fusing point is 500 DEG C.Subsequently, by electric arc
Melting is prepared for two kinds of crystal boundary reconstruct alloy pigs, and is prepared for the alloy powder that granularity is about 1.7 μm by ball milling.
（3）Prepare product
In mass ratio it is 4 by the Nd-Fe-B principal phases powder of low content of rare earth and neodymium iron boron principal phase powder containing high abundance rare earth:6
Ratio uniform mixes, and subsequently mixed powder and heavy rare earth crystal boundary is reconstructed into alloyed powder Dy71.5Fe28.5Uniform mixing, obtains the first mixing
Thing, by the first mixture at 800 DEG C vacuum heat 2 hours, obtain intermediate.The intermediate powder for obtaining is crushed, is divided
Dissipate, and with high potential alloyed powder La69Co31Uniform mixing, obtains the second mixture.Wherein, low rare earth principal phase powder：Heavy rare earth is brilliant
Boundary's alloyed powder：The mass ratio of high potential grain boundary alloys powder is 96:2:2.Second mixture is mixed after powder in 1.6 T, 200 MPa
Under, magnetic field orientating molding is carried out, afterwards sintering 4 hours at 1070 DEG C, then heat treatment 2 hours at 890 DEG C, then 400
Heat treatment 2 hours at DEG C, are obtained and have double principal phase structures, while with heavy rare earth shell layer/high potential containing high abundance rare earth
The neodymium iron boron magnetic body of crystal boundary central core/heavy rare earth shell layer multi-layer grain boundary structure.
Jing is determined, the obtained neodymium iron boron magnetic body with double principal phases and multilamellar grain boundary structure of the present embodiment, and its coercivity is
17.88 kOe, corrosion potential of the magnet in 25 DEG C, 3.5 wt.% sodium chloride solutions is -0.790 V.Magnet is at 120 DEG C, 2
The weight loss for corroding in the environment of atmospheric pressure and 100% relative humidity 96 hours is 0.75 mg/cm2。
The invention is not limited in aforesaid specific embodiment.The present invention is expanded to and any in this manual disclosed
New feature or any new combination, and the arbitrary new method that discloses or the step of process or any new combination.
Claims (10)
1. crystal boundary multiple structure regulation and control high abundance rare earth Sintered NdFeB magnet preparation method, it is characterised in that include as
Lower step：
（1）Low rare-earth Nd-Fe-B main-phase alloy powder A1, neodymium iron boron main-phase alloy powder A2 of the MM of rare earth containing high abundance are taken respectively, will be low
Rare-earth Nd-Fe-B main-phase alloy powder A1, neodymium iron boron main-phase alloy powder A2 of the MM of rare earth containing high abundance and low melting point heavy rare earth crystal boundary weight
Structure alloyed powder R1xM1yMixing, obtains the first mixture, and the first mixture is heated to into low melting point heavy rare earth crystal boundary reconstruct alloyed powder
R1xM1yMore than fusing point, and heating-up temperature is less than 1100 DEG C, makes low rare-earth Nd-Fe-B main-phase alloy A1, main-phase alloy A2 crystal grain side
Edge forms the heavy rare earth shell layer of high magnetocrystalline anisotropy, obtains intermediate；
（2）By step（1）After the intermediate of preparation is broken, gained powder body and the low melting point high potential crystal boundary containing high abundance rare earth
Reconstruct alloy MMaM2bMixing, obtains the second mixture, and the second mixture is carried out after magnetic field orientating molding, be sintered successively,
Heat treatment, obtains final product product.
2. according to claim 1 crystal boundary multiple structure regulation and control high abundance rare earth Sintered NdFeB magnet preparation method,
Characterized in that, the MM is one or more in La, Ce.
3. according to claim 1 crystal boundary multiple structure regulation and control high abundance rare earth Sintered NdFeB magnet preparation method,
Characterized in that, the particle mean size of low rare-earth Nd-Fe-B main-phase alloy powder A1 is less than 5 μm, rare earth element content is less than 29
Wt.%, Nd2Fe14B phases proportion is more than 95 %.
4. according to claim 1 crystal boundary multiple structure regulation and control high abundance rare earth Sintered NdFeB magnet preparation method,
Characterized in that, the particle mean size of neodymium iron boron main-phase alloy powder A2 of the MM of rare earth containing high abundance is less than 5 μm, Gao Feng therein
Degree rare earth MM accounts for 3 more than wt.% of main-phase alloy powder A2 gross mass.
5. according to any one of claim 1-4 crystal boundary multiple structure regulation and control high abundance rare earth Sintered NdFeB magnet system
Preparation Method, it is characterised in that the low melting point heavy rare earth crystal boundary reconstructs alloyed powder R1xM1yIn, R1 be lanthanide series metal Gd, Tb, Dy,
One or more in Ho, M1 be O, F, H, Cu, Ni, Fe, Co, Sn, Ti, Nb, Zr in one or more, x, y be respectively R1,
The atomic percentage of M1, the scope of x is 5 ~ 80, x with y's and for 100.
6. according to claim 5 crystal boundary multiple structure regulation and control high abundance rare earth Sintered NdFeB magnet preparation method,
Characterized in that, the low melting point heavy rare earth crystal boundary reconstructs alloyed powder R1xM1yFusing point be less than 900 DEG C.
7. according to any one of claim 1-6 crystal boundary multiple structure regulation and control high abundance rare earth Sintered NdFeB magnet system
Preparation Method, it is characterised in that the low melting point high potential crystal boundary reconstructs alloy MMaM2bIn, MM is in lanthanide series metal La, Ce
Plant or two kinds, M2 is one or more in high standard noble potential metal Cu, Ni, Fe, Co, and a, b are respectively the atom hundred of MM and M2
Fraction, the scope of a is 5 ~ 80, a with b's and for 100.
8. according to claim 1 crystal boundary multiple structure regulation and control high abundance rare earth Sintered NdFeB magnet preparation method,
Characterized in that, the low melting point heavy rare earth crystal boundary reconstructs alloyed powder R1xM1y, low melting point high potential crystal boundary reconstruct alloyed powder
MMaM2bGranularity be 0.1-100 μm respectively.
9. according to any one of claim 1-8 crystal boundary multiple structure regulation and control high abundance rare earth Sintered NdFeB magnet system
Preparation Method, it is characterised in that the step（2）In, the second mixture is carried out after magnetic field orientating molding, to be sintered, sinter
Temperature is 950-1100 DEG C, and sintering time is 2-5h, then carries out two-stage heat treatment, and one-level heat treatment temperature is 850-950 DEG C,
Temperature retention time is 1-5h, and two grades of heat treatment temperatures are 300-600 DEG C, and temperature retention time is 1-5h, obtains final product product.
10. the product for being prepared using aforementioned any one of claim 1-9 methods described.
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