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 PDF

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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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rare earth
crystal boundary
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powder
high abundance
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CN106601401B (en
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张培
胡梅娟
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Institute of Materials of CAEP
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032Magnets 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
    • H01F1/04Magnets 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
    • H01F1/047Alloys characterised by their composition
    • H01F1/053Alloys characterised by their composition containing rare earth metals
    • H01F1/055Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H01F1/0571Alloys 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
    • H01F1/0575Alloys 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
    • H01F1/0577Alloys 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
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01FMAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00Apparatus 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
    • H01F41/02Apparatus 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
    • H01F41/0253Apparatus 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

The preparation method of the high abundance rare earth Sintered NdFeB magnet of crystal boundary multiple structure regulation and control And products thereof
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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