CN108364740A - A kind of nanocrystalline mischmetal permanent magnet and its preparation method and application - Google Patents

A kind of nanocrystalline mischmetal permanent magnet and its preparation method and application Download PDF

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CN108364740A
CN108364740A CN201810314110.3A CN201810314110A CN108364740A CN 108364740 A CN108364740 A CN 108364740A CN 201810314110 A CN201810314110 A CN 201810314110A CN 108364740 A CN108364740 A CN 108364740A
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permanent magnet
nanocrystalline
magnet
mischmetal
rare earth
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熊杰夫
赵鑫
沈保根
赵同云
李锐
胡凤霞
孙继荣
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Institute of Physics of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/058—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IVa elements, e.g. Gd2Fe14C
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/06—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 in the form of particles, e.g. powder
    • H01F1/068—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 in the form of particles, e.g. powder having a L10 crystallographic structure, e.g. [Co,Fe][Pt,Pd] (nano)particles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H01F41/0266—Moulding; Pressing

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  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing Cores, Coils, And Magnets (AREA)
  • Powder Metallurgy (AREA)
  • Hard Magnetic Materials (AREA)

Abstract

A kind of nanocrystalline mischmetal permanent magnet of present invention offer and its preparation method and application, chemical formula is：MMCo5, wherein MM is the impure misch metal alloy with native element ratio extracted from the primary light rare earth mine of total association in rare earth purification process；The main phase of the permanent-magnet material has CaCu5The hexagonal structure of type；The intrinsic coercivity H of the permanent-magnet materialcj>=4kOe, remanent magnetism Br>=3kGs, maximum magnetic energy product (BH)max≥5MGOe.The present invention prepares cobalt-based permanent magnet using the primary norium raw material of total association without rare earth purification processes; application suitable for particular surroundings; therefore raw material process is simple, few to the energy and resource consumption, cheap, and is conducive to the balanced use of environmental protection and rare earth resources.The nanocrystalline M MCo of the present invention5Permanent magnet has good magnetic property, thermal stability, corrosion resistance and mechanical property.

Description

A kind of nanocrystalline mischmetal permanent magnet and its preparation method and application
Technical field
The present invention relates to a kind of nanocrystalline mischmetal permanent magnets and its preparation method and application, belong to rare earth permanent magnet technology Field.
Background technology
Rare earth permanent-magnetic material is that one kind is formed by intermetallic compound with thulium and transiting group metal elements It is a kind of highest permanent-magnet material of currently known comprehensive performance for the permanent-magnet material of matrix main phase.Wherein, rare earth cobalt-based permanent magnetism closes Gold utensil has good high-temperature magnetic energy, can meet the military service demand under specific condition, in the fields such as aerospace and military project national defence With great application prospect, have become the critical function material for promoting productivity dynamics and social progress.But with certainly The fast development of dynamicization, information and New Energy Industry, Global Rare-earth Permanent Magnet materials demand amount are continuously increased so that rare earth is golden The usage amount and price for belonging to neodymium (Nd), praseodymium (Pr) and samarium (Sm) greatly increase, and cause the cost of rare earth permanent-magnetic material continuous It is soaring, cause no small pressure to rare earth permanent-magnetic material manufacturer and consumer.
However in natural Rare Earth Mine, various rare earth elements are total associations.In the production process of rare earth metal, rare earth Element needs to first pass through pickling to be extracted from ore, is finally detached again.Before separation, rare earth metal is according to ore The natural percentage of each element exists with alloy form, referred to as norium, this is indicated using MM in chemical formula hereafter Kind metal.By taking the baiyuneboite of packet header as an example, the content of each rare earth element is in mischmetal：La=26~29wt%, Ce =49~53wt%, Pr=4~6wt%, Nd=15~17wt%.The wherein wilderness demand of the Partial Elements such as Pr, Nd so that rich It spends a large amount of of higher light rare earth La, Ce rare earth metal to overstock, causes the waste of rare earth resources.On the other hand, dilute from total association Specific high-purity rare earth metal is isolated in native mine to need to consume a large amount of energy and resource, further increases raw material Cost and carrying capacity of environment.Thus directly separated single Pr, Nd, Tb, Dy are substituted using the primary norium of association altogether Permanent magnet is prepared etc. type rare earth metal in short supply, complicated rare earth purification process can be not only reduced or remitted significantly, reduce the energy and resource Consumption, reduce cost, and the balanced use problem of China's rare earth resources can be substantially solved, mitigate carrying capacity of environment, have Very important application value and strategic importance.
Currently, to reduce cost, the research without heavy rare earth or multi-purpose lanthanum ce metal has been obtained for considerable degree of attention. The characteristics of according to China's rare earth resources mine, is substituted single with the most abundant Ce and LaCe alloys of reserves or mischmetal (LaCePrNd) Rare earth metal becomes the hot spot studied at present.2014, Niu et al. system researches are direct to be taken completely using norium The anisotropic MM prepared for praseodymium neodymium alloy2F14Sintered magnet (J.Appl.Phys.115.113912) single-phase B, finds it Coercivity Hcj=0.457kOe, and maximum magnetic energy product (BH)max=2.397MGOe.This low synthesis permanent magnetism performance greatly limits The application range of the direct permanent-magnet material prepared using mischmetal is made.This is because La2Fe14B and Ce2Fe14B has remote low In Nd2Fe14The anisotropy field of B, and caused by being not easy into phase.Therefore, in actual production, Rare-Earth Ce or the replacement of La be all The decline of permanent magnet performance can be caused, especially when the content of La or Ce is more than 60%, magnet cost performance is extremely low, without practicality Value.Although the slightly higher permanent-magnet material of performance, this magnetism of material can be obtained using melt spinning technology (belt-rejecting technology) Can be still very low, and be isotropic thin slice, it is difficult to extensive use.
Rare-Earth Cobalt 1:5 phase permanent-magnet materials have high magnetic property and high Curie temperature, MMCo5The Curie temperature of magnet (about 460 DEG C) compare MM2F14B magnets (about 210 DEG C) are higher by very much, in 180~250 DEG C of operating temperature or more, still have height Magnetic energy product, coercivity and remanent magnetism, be therefore widely used in high-temperature field.SmCo5Magnet has been obtained for very extensive Using, and to MMCo5The research of magnet is considerably less.Although MMCo5Every permanent magnetism performance of magnet is compared to SmCo5Magnet wants low Some, but mischmetal resource ratio Sm is far richer, price is also cheap very much, MMCo5The development and utilization of magnet can be big The big cost for reducing rare earth permanent-magnetic material.Currently, about nanocrystalline anisotropic MMCo5The research of magnet is less.
Realize MMCo5The functionization of magnet, it is necessary to prepare block-like high-performance anisotropy magnet, and hot pressing thermal deformation Method can prepare anisotropic nanocrystalline magnet.MMCo5Magnet has CaCu5The hexagonal structure of type, only when particle size reaches When to nanoscale, thermal deformation field could be carried out higher than room temperature, the deflection of magnet can reach 90% or so, To obtain anisotropic nanocrystalline magnet.Size is distributed more uniform MMCo in order to obtain5Nano particle uses The multistep ball grinding method of addition surfactant auxiliary, can prepare more short grained material, in particular for complete crystalline substance The rare earth permanent-magnetic material of grain.The technology that hot pressing/heat distortion magnet is prepared using discharge plasma sintering (SPS) can be with hot pressed sintering Go out the magnet of nanocrystalline (20~50nm), magnet is then put into progress SPS thermal deformations in mold, obtains crystal grain c-axis direction (easily Magnetized axis) and pressure direction lath-shaped nanoscale arranged in parallel (about hundreds of nanometers) crystal grain, it is knitted to obtain ideal deformation Structure and high magnetic property.For MMCo5For magnet, only it can just be obtained along easy under larger deflection (75~90%) The high orientation arrangement of axis, to obtain good permanent magnetism performance.
Invention content
Therefore, the purpose of the present invention is to provide a kind of nano crystal permanent magnetic material of association primary norium base altogether, This permanent-magnet material is the permanent magnet for containing only the primary norium of total association, has price, environmental protection and rare earth money Various advantages such as source balanced use, and there is preferable squareness, higher coercivity and maximum magnetic energy product.
Unless otherwise stated, the term as used herein " mischmetal ", " norium ", " norium conjunction What gold " and " MM " all referred to extract from the primary mixed light rare earth mine of total association in rare earth purification process impure has naturally The misch metal alloy of element ratio.
The purpose of the present invention is achieved through the following technical solutions.
On the one hand, the present invention provides a kind of nanocrystalline mischmetal permanent magnet, chemical formula is：MMCo5, wherein MM is The impure mischmetal with native element ratio extracted from the primary light rare earth mine of total association in rare earth purification process Metal alloy；The main phase of the permanent-magnet material has CaCu5The hexagonal structure of type；The intrinsic coercivity H of the permanent-magnet materialcj≥ 4kOe, remanent magnetism Br>=3kGs, maximum magnetic energy product (BH)max≥5MGOe。
According to nanocrystalline mischmetal permanent magnet provided by the invention, wherein each dilute in the misch metal alloy The content of earth elements is：15~17wt% of La 26~29wt%, Ce 49~53wt%, Pr 4~6wt%, Nd.
According to nanocrystalline mischmetal permanent magnet provided by the invention, wherein the impurity include Sm, Fe, Si, Mg, Zn, W, one or more in Mo, Cu, Ti, Ca, Pb, Cr, Ni, Th, C, H and O.Therefore, can contain by institute in the permanent magnet State that misch metal alloy is introduced into Sm, Fe, Si, Mg, Zn, W, Mo, Cu, Ti, Ca, Pb, Cr, Ni, Th, C, H and O One or more impurity elements.
Preferably, total content of the impurity being introduced by the misch metal alloy in the permanent magnet is no more than 1.5wt%.
The permanent magnet is that impure have natural member with what is extracted from light rare earth mine in cobalt and rare earth purification process The misch metal alloy of plain ratio is raw material, coordinates SPS thermal deformation techniques using the multistep ball milling that surfactant assists It is prepared.
Preferably, the permanent magnet is the flaky crystalline grain that thickness is 50~200nm.Its high-coercive force is acted on by domain wall pinning Ensure, remanence ratio and squareness are optimized because of intergranular coupling.
Preferably, the intrinsic coercivity H of the permanent magnetcjFor 3~10kOe, more preferably 5~8kOe；Remanent magnetism BrFor 3~ 9kGs, more preferably 6~8kGs；Maximum magnetic energy product (BH)maxFor 5~11MGOe；More preferably 9~11MGOe.
On the other hand, nanocrystalline M MCo is prepared using SPS technology thermal deformation methods the present invention also provides a kind of5Rare-earth permanent magnet Method.Rare earth element in raw material impure has native element by what is extracted from light rare earth mine in rare earth purification process The misch metal alloy of ratio provides.The primary norium of total association for the present invention can be from white clouds Hubei Province The primary norium of total association of Bo Kuang.In order to realize that goal of the invention, the present invention provide the following technical solutions：
A kind of preparation method of nanocrystalline mischmetal permanent magnet, includes the following steps：
1) chemical formula MMCo is pressed5Preparation raw material, by the raw material of preparation under inert gas protection by electric arc melting at conjunction Ingot, melt back 3~5 times is to ensure the uniformity of alloy pig；
2) use the multistep ball-milling method that surfactant assists by MMCo5The nanometer powder of alloy pig ball milling slabbing；
3) air-dried ball-milled powder is packed under inert gas protection in sintered-carbide die, is put into hot isostatic press, Under the isostatic pressure of 50~400MPa, at a temperature of 400~1000 DEG C of isostatic pressed, suppress 0.01~4 hour, obtain it is each to The MMCo of the same sex5Nanocrystalline magnet；
4) magnet for obtaining step 3) is packed into graphite jig, using discharge plasma agglomerating plant, in vacuum, pressure 10~100MPa of power, 700~1000 DEG C of temperature, deflection are 50~90%；
5) magnet that step 4) obtains is put into tube furnace, 0.1~2 is kept the temperature under 600~650 DEG C of inert gas shieldings Hour.
According to preparation method provided by the invention, it is preferable that the additional scaling loss of MM additions 2~4% in the raw material of step 1) Than.
According to preparation method provided by the invention, it is preferable that the multistep ball of the surfactant auxiliary described in step 2) Mill method includes specifically following three phases：First stage use ethyl alcohol, acetone and normal heptane in it is a kind of be used as organic solvent, Ball milling speed is 1~150rpm, and the time is 1~20 hour；Surfactant (such as oleic acid, oleyl amine and three pungent is added in second stage One kind in amine, dosage MMCo55~20wt% of alloy pig), ball milling speed is 150~250rpm, and the time is 1~20 small When；Phase III ball milling speed is 250~400rpm, and the time is 0.1~3 hour.
According to preparation method provided by the invention, wherein the obtained powder average thickness of step 2) is 50~200nm.
According to preparation method provided by the invention, it is preferable that the hot isostatic pressing power in step 3) is 50~200MPa, heat etc. Static pressure temperature is 600~700 DEG C, and the hot isostatic pressing time is 0.5~2 hour.
According to preparation method provided by the invention, magnet densification process, therefore magnetic of the present invention are realized by hot isostatic pressing The promotion of body performance is mainly grown up realization by inhibition crystal grain.Wherein, step 3) obtains isotropism by hot isostatic pressing MMCo5Nanocrystalline magnet；Step 4) obtains anisotropic MMCo by plasma sintering5Nanocrystalline permanent magnet；Step 5) Intra-die stress and surface defect are eliminated by isothermal holding, the magnetic isolation between crystal grain is enhanced, to improve magnetic The coercivity of body.
The present invention also provides above-mentioned nanocrystalline mischmetal permanent magnet or according to nanocrystalline made from the method for the present invention Application of the mischmetal permanent magnet in magneto, wind-power electricity generation or communication equipment.
Compared with prior art, the invention has the advantages that：
1) compared to La, Ce or MM base rare earth permanent magnet material prepared at present, the present invention is used without rare earth purification processes The primary norium raw material of total association prepare cobalt-based permanent magnet, be suitable for the application of particular surroundings, therefore raw material process Simply, few to the energy and resource consumption, cheap, and be conducive to the balanced use of environmental protection and rare earth resources；
2) it uses the multistep ball-milling method of surfactant auxiliary that can prepare the nano particle that Size Distribution compares concentration, protects The uniformity and consistency for having demonstrate,proved magnet contribute to the comprehensive performance for promoting magnet；
3) hot-pressing thermal deformation method is used, not only simplifies preparation process, and effectively inhibit crystal grain and grow up, further Improve comprehensive permanent magnetism performance；
4) the nanocrystalline M MCo obtained5Permanent magnet has good magnetic property, thermal stability, corrosion resistance and mechanics Performance.
Specific implementation mode
The present invention is further described in detail With reference to embodiment, the embodiment provided is only for explaining The bright present invention, the range being not intended to be limiting of the invention.
It is commercialized misch metal alloy that mischmetal is used in following embodiment, and wherein norium closes Golden purity is：The weight percent of total rare earth (TRE)=99.70wt%, wherein La, Ce, Pr, Nd is respectively：28.38wt%, The content of 50.66wt%, 5.24wt% and 15.27wt%, major impurity is respectively：Sm≤0.05wt%, Mg=0.05wt%, Fe=0.04wt%, Cr≤0.03wt%, Si=0.02wt%, Zn, W, Mo, Cu, Ti, Ca, Pb, Ni, Th, C, H≤ 0.01wt%, O≤0.1wt%.
Embodiment 1
1) chemical formula MMCo is pressed5Preparation raw material, wherein the additional scaling loss ratio of MM additions 2%, by the raw material of preparation in argon By electric arc melting at alloy pig under gas shielded, melt back 3 times is to ensure the uniformity of alloy pig；
2) use the multistep ball-milling method that surfactant assists by MMCo5Alloy pig ball milling at nano-scale particle；The The organic solvent in one stage is ethyl alcohol, and ball milling speed 100rpm, the time is 5 hours, and second stage then needs that surface work is added Property agent oleic acid, dosage be magnetic material mass 5%, ball milling speed 200rpm, the time be 8 hours, the phase III ball milling speed Degree is 300rpm, and the time is 3 hours；
3) air-dried ball-milled powder is packed under inert gas protection in sintered-carbide die, is put into hot isostatic press, Under the isostatic pressure of 300MPa, at a temperature of 670 DEG C of isostatic pressed, suppresses 0.5 hour, obtain isotropic MMCo5It receives The brilliant magnet of rice；
4) magnet for obtaining step 3) is packed into graphite jig, using discharge plasma agglomerating plant, in vacuum, pressure Power 40MPa, 880 DEG C of temperature, deflection 90% obtain anisotropic MMCo5Nanocrystalline permanent magnet；
5) magnet that step 4) obtains is put into tube furnace, keeps the temperature 1 hour in the case where 600 DEG C of argon gas are protected to get to originally The nanocrystalline mischmetal permanent magnet of invention.
Comparative example 1
Anisotropic MMCo is prepared in the same manner as shown in Example 15Nanocrystalline permanent magnet, the difference is that, Without step 2) described in embodiment 1, and step 2) is changed to：It will using the multistep ball-milling method of surfactant auxiliary MMCo5Alloy pig ball milling is at the particle of nano-scale, and organic solvent is ethyl alcohol, and ball milling speed 100rpm, the time is 16 hours.
Embodiment 2
1) chemical formula MMCo is pressed5Preparation raw material, wherein the additional scaling loss ratio of MM additions 2%, by the raw material of preparation in argon By electric arc melting at alloy pig under gas shielded, melt back 3 times is to ensure the uniformity of alloy pig；
2) use the multistep ball-milling method that surfactant assists by MMCo5Alloy pig ball milling at nano-scale particle；The The organic solvent in one stage is ethyl alcohol, and ball milling speed 100rpm, the time is 5 hours, and second stage then needs that surface work is added Property agent oleic acid, dosage be magnetic material mass 5%, ball milling speed 200rpm, the time be 8 hours, the phase III ball milling speed Degree is 300rpm, and the time is 3 hours；
3) air-dried ball-milled powder is packed under inert gas protection in sintered-carbide die, is put into hot isostatic press, Under the isostatic pressure of 300MPa, at a temperature of 670 DEG C of isostatic pressed, suppresses 0.5 hour, obtain isotropic MMCo5It receives The brilliant magnet of rice；
4) magnet for obtaining step 3) is packed into graphite jig, using discharge plasma agglomerating plant, in vacuum, pressure Power 40MPa, 840 DEG C of temperature, deflection 80% obtain anisotropic MMCo5Nanocrystalline permanent magnet；
5) magnet that step 4) obtains is put into tube furnace, keeps the temperature 1 hour in the case where 600 DEG C of argon gas are protected to get to originally The nanocrystalline mischmetal permanent magnet of invention.
Comparative example 2
Anisotropic MMCo is prepared according to step same as Example 25Nanocrystalline permanent magnet, the difference is that, Without the step 2) described in embodiment 2, and step 2) is changed to：It will using the multistep ball-milling method of surfactant auxiliary MMCo5Alloy pig ball milling is at the particle of nano-scale, and organic solvent is ethyl alcohol, and ball milling speed 100rpm, the time is 16 hours.
Embodiment 3
1) chemical formula MMCo is pressed5Preparation raw material, wherein the additional scaling loss ratio of MM additions 2%, by the raw material of preparation in argon By electric arc melting at alloy pig under gas shielded, melt back 3 times is to ensure the uniformity of alloy pig；
2) use the multistep ball-milling method that surfactant assists by MMCo5Alloy pig ball milling at nano-scale particle；The The organic solvent in one stage is ethyl alcohol, and ball milling speed 100rpm, the time is 5 hours, and second stage then needs that surface work is added Property agent oleic acid, dosage be magnetic material mass 5%, ball milling speed 200rpm, the time be 8 hours, the phase III ball milling speed Degree is 300rpm, and the time is 3 hours；
3) air-dried ball-milled powder is packed under inert gas protection in sintered-carbide die, is put into hot isostatic press, Under the isostatic pressure of 300MPa, at a temperature of 670 DEG C of isostatic pressed, suppresses 0.5 hour, obtain isotropic MMCo5It receives The brilliant magnet of rice；
4) magnet for obtaining step 3) is packed into graphite jig, using discharge plasma agglomerating plant, in vacuum, pressure Power 40MPa, 800 DEG C of temperature, deflection 70% obtain anisotropic MMCo5Nanocrystalline permanent magnet；
5) magnet that step 4) obtains is put into tube furnace, keeps the temperature 1 hour in the case where 600 DEG C of argon gas are protected to get to originally The nanocrystalline mischmetal permanent magnet of invention.
Comparative example 3
Anisotropic MMCo is prepared according to step same as Example 35Nanocrystalline permanent magnet, the difference is that, Without step 2) described in embodiment 3, and step 2) is changed to：It will using the multistep ball-milling method of surfactant auxiliary MMCo5Alloy pig ball milling is at the particle of nano-scale, and organic solvent is ethyl alcohol, and ball milling speed 100rpm, the time is 16 hours.
Comparative example 4
Anisotropic MMCo is prepared according to step same as Example 35Nanocrystalline permanent magnet, the difference is that, Without step 2) described in embodiment 3, and step 2) is changed to：It will using the multistep ball-milling method of surfactant auxiliary MMCo5Alloy pig ball milling is at the particle of nano-scale, and organic solvent is ethyl alcohol, and ball milling speed 100rpm, the time is 5 hours, Surfactant oleic acid is added in second stage, and dosage is the 5% of magnetic material mass, and ball milling speed 200rpm, the time is 8 small When, phase III ball milling speed is 300rpm, and the time is 8 hours.
Embodiment 4
1) chemical formula MMCo is pressed5Preparation raw material, wherein the additional scaling loss ratio of MM additions 2%, by the raw material of preparation in argon By electric arc melting at alloy pig under gas shielded, melt back 3 times is to ensure the uniformity of alloy pig；
2) use the multistep ball-milling method that surfactant assists by MMCo5Alloy pig ball milling at nano-scale particle；The The organic solvent in one stage is ethyl alcohol, and ball milling speed 100rpm, the time is 5 hours, and second stage then needs that surface work is added Property agent oleic acid, dosage be magnetic material mass 5%, ball milling speed 200rpm, the time be 8 hours, the phase III ball milling speed Degree is 300rpm, and the time is 3 hours；
3) air-dried ball-milled powder is packed under inert gas protection in sintered-carbide die, is put into hot isostatic press, Under the isostatic pressure of 300MPa, at a temperature of 670 DEG C of isostatic pressed, suppresses 0.5 hour, obtain isotropic MMCo5It receives The brilliant magnet of rice；
4) magnet for obtaining step 3) is packed into graphite jig, using discharge plasma agglomerating plant, in vacuum, pressure Power 40MPa, 760 DEG C of temperature, deflection 60% obtain anisotropic MMCo5Nanocrystalline permanent magnet；
5) magnet that step 4) obtains is put into tube furnace, keeps the temperature 1 hour in the case where 600 DEG C of argon gas are protected to get to originally The nanocrystalline mischmetal permanent magnet of invention.
Comparative example 5
Anisotropic MMCo is prepared according to step same as Example 45Nanocrystalline permanent magnet, the difference is that, Without the step 2) described in embodiment 4, and step 2) is changed to：It will using the multistep ball-milling method of surfactant auxiliary MMCo5Alloy pig ball milling is at the particle of nano-scale, and organic solvent is ethyl alcohol, and ball milling speed 100rpm, the time is 16 hours.
Table 1 gives magnetic property and the density comparison for the permanent magnet that under room temperature (20 DEG C) prepared by embodiment and comparative example.
Table 1
Performance Coercivity (kOe) Remanent magnetism (kGs) Density (g/cm3)
Embodiment 1 4.28 6.11 8.31
Comparative example 1 3.37 6.02 8.26
Embodiment 2 8.15 5.98 8.27
Comparative example 2 6.72 5.76 8.22
Embodiment 3 8.32 5.78 8.24
Comparative example 3 6.95 5.34 8.18
Comparative example 4 7.34 5.48 8.23
Embodiment 4 7.98 5.21 8.19
Comparative example 5 7.23 5.02 8.11
It can be seen that magnetic of the powder feature to final magnet of ball milling in permanent magnetism production procedure by the data in table 1 Performance influences clearly.Surfactant assists particle size distribution that multistep ball milling obtains than traditional single step ball milling more It concentrates, the defect of grain surface is less, to more be beneficial to obtain higher coercivity by thermal deformation process.But it is long The ball milling of time is also unfavorable for magnet and obtains preferable magnetic property (such as comparison of comparative example 4 and embodiment 3).Meanwhile deflection Increase the degree of orientation higher so that magnet, but excessively high deflection is then unfavorable for the coercitive promotion of magnet.By rationally controlling Control surface activating agent assists each step of multistep ball milling and the process of thermal deformation, can obtain anisotropic nanocrystalline MMCo5Permanent magnet has good magnetic property, thermal stability, corrosion resistance and mechanical property.
Technical scheme of the present invention is described in detail in embodiment described above, it should be understood that specific reality of the invention Example is applied, is not intended to restrict the invention, every technical solution of the present invention for meeting condition of the present invention can realize this hair It is bright, embodiment numerous to list herein；All any modifications made in spirit of the present invention, supplement or similar replacement, It should be included within protection scope of the present invention.

Claims (10)

1. a kind of nanocrystalline mischmetal permanent magnet, chemical formula are：MMCo5, wherein MM is in rare earth purification process from total association The impure misch metal alloy with native element ratio extracted in primary light rare earth mine；The permanent-magnet material Main phase has CaCu5The hexagonal structure of type；The intrinsic coercivity H of the permanent-magnet materialcj>=4kOe, remanent magnetism Br>=3kGs, it is maximum Magnetic energy product (BH)max≥5MGOe。
2. nanocrystalline mischmetal permanent magnet according to claim 1, wherein each dilute in the misch metal alloy The content of earth elements is：15~17wt% of La 26~29wt%, Ce 49~53wt%, Pr 4~6wt%, Nd.
3. nanocrystalline mischmetal permanent magnet according to claim 1 or 2, wherein containing by described in the permanent magnet Misch metal alloy be introduced into Sm, Fe, Si, Mg, Zn, W, Mo, Cu, Ti, Ca, Pb, Cr, Ni, Th, C, H and O One or more impurity elements.
4. nanocrystalline mischmetal permanent magnet according to any one of claim 1 to 3, wherein by the mischmetal Total content of the impurity that metal alloy is introduced into the permanent magnet is no more than 1.5wt%.
5. nanocrystalline mischmetal permanent magnet according to any one of claim 1 to 4, wherein the permanent magnet is thick Degree is the flaky crystalline grain of 50~200nm.
6. nanocrystalline mischmetal permanent magnet according to any one of claim 1 to 5, wherein the permanent-magnet material Intrinsic coercivity HcjFor 3~10kOe, more preferably 5~8kOe；Remanent magnetism BrFor 3~9kGs, more preferably 6~8kGs；Maximum magnetic flux Energy product (BH)maxFor 5~11MGOe；More preferably 9~11MGOe.
7. a kind of preparation method of nanocrystalline mischmetal permanent magnet, includes the following steps：
1) chemical formula MMCo is pressed5Preparation raw material, by the raw material of preparation under inert gas protection by electric arc melting at alloy pig, Melt back 3~5 times is to ensure the uniformity of alloy pig；
2) use the multistep ball-milling method that surfactant assists by MMCo5The nanometer powder of alloy pig ball milling slabbing；
3) air-dried ball-milled powder is packed under inert gas protection in sintered-carbide die, hot isostatic press is put into, 50 Under the isostatic pressure of~400MPa, at a temperature of 400~1000 DEG C of isostatic pressed, suppress 0.01~4 hour；
4) magnet for obtaining step 3) is packed into graphite jig, using discharge plasma agglomerating plant, in vacuum, pressure 10 ~100MPa, 700~1000 DEG C of temperature, deflection are 50~90%；
5) magnet that step 4) obtains is put into tube furnace, it is small that 0.1~2 is kept the temperature under 600~650 DEG C of inert gas shieldings When.
8. preparation method according to claim 7, wherein the multistep ball milling of the surfactant auxiliary described in step 2) Method includes following three phases：First stage uses a kind of as organic solvent, ball milling speed in ethyl alcohol, acetone and normal heptane For 1~150rpm, the time is 1~20 hour；Surfactant (one in such as oleic acid, oleyl amine and trioctylamine is added in second stage Kind, dosage MMCo55~20wt% of alloy pig), ball milling speed is 150~250rpm, and the time is 1~20 hour；Third rank Section ball milling speed is 250~400rpm, and the time is 0.1~3 hour.
9. according to the preparation method in claim 7 described in 8, wherein the hot isostatic pressing power in step 3) is 50~200MPa, heat Isostatic pressed temperature is 600~700 DEG C, and the hot isostatic pressing time is 0.5~2 hour.
10. nanocrystalline mischmetal permanent magnet according to any one of claims 1 to 6 is appointed according in claim 7 to 9 Application of the nanocrystalline mischmetal permanent magnet in magneto, wind-power electricity generation or communication equipment made from one the method.
CN201810314110.3A 2018-04-10 2018-04-10 A kind of nanocrystalline mischmetal permanent magnet and its preparation method and application Pending CN108364740A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113658791A (en) * 2021-07-23 2021-11-16 北京工业大学 Method for preparing nanocrystalline Co-based rare earth permanent magnet with high coercive force and high magnetic anisotropy

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EP1227165A1 (en) * 2000-06-09 2002-07-31 Mitsui Mining & Smelting Co., Ltd. Hydrogen-occluding alloy and process for producing the same
CN101476055A (en) * 2009-01-16 2009-07-08 北京工业大学 Preparation of fully dense massive anisotropic nanocrystalline SmCo5 magnet
CN102703764A (en) * 2012-05-31 2012-10-03 厦门钨业股份有限公司 Cu-contained rare earth system AB5-type hydrogen storage alloy and preparation method thereof

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Publication number Priority date Publication date Assignee Title
EP1227165A1 (en) * 2000-06-09 2002-07-31 Mitsui Mining & Smelting Co., Ltd. Hydrogen-occluding alloy and process for producing the same
CN101476055A (en) * 2009-01-16 2009-07-08 北京工业大学 Preparation of fully dense massive anisotropic nanocrystalline SmCo5 magnet
CN102703764A (en) * 2012-05-31 2012-10-03 厦门钨业股份有限公司 Cu-contained rare earth system AB5-type hydrogen storage alloy and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113658791A (en) * 2021-07-23 2021-11-16 北京工业大学 Method for preparing nanocrystalline Co-based rare earth permanent magnet with high coercive force and high magnetic anisotropy

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