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CN119480412A - Preparation of a nanocomposite permanent magnetic material with high magnetic energy product and strong coercivity - Google Patents

Preparation of a nanocomposite permanent magnetic material with high magnetic energy product and strong coercivity Download PDF

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Publication number
CN119480412A
CN119480412A CN202411643680.9A CN202411643680A CN119480412A CN 119480412 A CN119480412 A CN 119480412A CN 202411643680 A CN202411643680 A CN 202411643680A CN 119480412 A CN119480412 A CN 119480412A
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powder
ball milling
preparation
epoxy resin
magnetic
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廖钟财
方彦雯
卫敏
冯健
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Heye Health Technology Co Ltd
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Heye Health Technology Co Ltd
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    • 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
    • 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
    • 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
    • H01F1/08—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 pressed, sintered, or bound together
    • H01F1/083—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 pressed, sintered, or bound together in a bonding agent
    • 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
    • H01F1/12—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 soft-magnetic materials
    • H01F1/14—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 soft-magnetic materials metals or alloys
    • H01F1/147—Alloys characterised by their composition
    • H01F1/14708—Fe-Ni based alloys
    • H01F1/14733—Fe-Ni based alloys in the form of particles
    • H01F1/14741—Fe-Ni based alloys in the form of particles pressed, sintered or bonded together
    • 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
    • H01F1/12—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 soft-magnetic materials
    • H01F1/14—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 soft-magnetic materials metals or alloys
    • H01F1/147—Alloys characterised by their composition
    • H01F1/153—Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15333—Amorphous metallic alloys, e.g. glassy metals containing nanocrystallites, e.g. obtained by annealing
    • 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
    • H01F1/12—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 soft-magnetic materials
    • H01F1/14—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 soft-magnetic materials metals or alloys
    • H01F1/147—Alloys characterised by their composition
    • H01F1/153—Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15341—Preparation processes therefor
    • 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
    • H01F1/12—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 soft-magnetic materials
    • H01F1/14—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 soft-magnetic materials metals or alloys
    • H01F1/147—Alloys characterised by their composition
    • H01F1/153—Amorphous metallic alloys, e.g. glassy metals
    • H01F1/15358—Making agglomerates therefrom, e.g. by pressing
    • H01F1/15366—Making agglomerates therefrom, e.g. by pressing using a binder
    • H01F1/15375—Making agglomerates therefrom, e.g. by pressing using a binder using polymers

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  • Crystallography & Structural Chemistry (AREA)
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Abstract

The invention relates to a preparation method of a nano composite permanent magnet material with high magnetic energy product and strong coercivity, which comprises the following steps: the preparation of solid epoxy resin, mnBi alloy cast ingot, mn 55Bi45 alloy hard magnetic phase bonded magnet, nanocrystalline Fe-Ni soft magnetic composite material and Mn 55Bi45/Fe-Ni nanocomposite permanent magnet material creatively combines the methods of arc melting method, mechanical alloying method, high-energy ball milling method, heat treatment process and the like, and the prepared nanocomposite permanent magnet material has the characteristics of higher magnetic energy product, excellent coercivity, high saturation magnetization, acid and alkali resistance, high performance, low cost and the like, so that the Mn 55Bi45/Fe-Ni nanocomposite permanent magnet material has remarkable advantages in medical equipment application occasions of large health industry.

Description

Preparation of nano composite permanent magnet material with high magnetic energy product and strong coercivity
Technical Field
The invention relates to a preparation method of a nano composite permanent magnet material with high magnetic energy product and strong coercivity, and belongs to the technical field of new materials.
Background
With the continuous development of human society, rare earth permanent magnet materials play an indispensable role in strategic emerging industries such as new energy automobiles, wind power generation, robots and the like. However, the excessive consumption of rare earth resources and the rapid increase of prices limit the application of rare earth permanent magnet materials, in order to cope with the limitation of rare earth permanent magnet materials, the invention adopts MnBi alloy as a raw material, and the MnBi alloy is a novel rare earth-free high-performance permanent magnet material, has the advantages of higher coercive force, moderate saturation magnetization, magnetic energy product and the like, mn 55Bi45 is used as a proportion of the MnBi alloy, has excellent magnetic performance, and Fe-Ni alloy is used as one of the raw materials, thus the rare earth permanent magnet material is a typical soft magnetic material, and has the characteristics of high saturation magnetization and low coercive force. And has positive coercive force temperature coefficient in a certain range, thus becoming a potential permanent magnetic material for medium and high temperature application.
In the field of nanocomposite permanent magnet materials, the high saturation magnetization of the soft magnetic phase can be combined with the high magnetocrystalline anisotropy of the hard magnetic phase to obtain excellent magnetic properties by ferromagnetic exchange coupling between two phase grains at the nanoscale.
Disclosure of Invention
Aiming at the problems, the invention provides a preparation method of a nano composite permanent magnet material with high magnetic energy product and strong coercivity.
The invention relates to a preparation method of a nano composite permanent magnet material with high magnetic energy product and strong coercivity, which comprises the following steps of preparing solid epoxy resin in step (1), preparing MnBi alloy cast ingots in step (2), preparing Mn 55Bi45 alloy hard magnetic phase bonded magnets in step (3), preparing nanocrystalline Fe-Ni soft magnetic composite materials in step (4), and preparing Mn 55Bi45/Fe-Ni nano composite permanent magnet materials in step (5);
wherein, the preparation of the nanocrystalline Fe-Ni soft magnetic composite material in the step (4) comprises the following steps:
Weighing Fe powder and Ni powder according to a certain metering ratio, performing high-energy ball milling, adding alcohol to prevent powder oxidation, wherein the ball milling atmosphere is argon, then weighing epoxy resin to dissolve in an acetone solution, mixing and stirring, adding the powder into the solution, uniformly mixing and stirring until complete evaporation, transferring into a mould, compacting and forming under a certain pressure, and finally annealing for a period of time at a high temperature to obtain the nanocrystalline Fe-Ni soft magnetic composite material;
the preparation of the Mn 55Bi45/Fe-Ni nanocomposite permanent magnet material in the step (5) comprises the following steps:
Uniformly mixing the Mn 55Bi45 alloy hard magnetic phase bonded magnet prepared in the step (3) with the nanocrystalline Fe-Ni soft magnetic composite material prepared in the step (4) in an inert gas glove box cavity with a certain oxygen content, performing ball milling to prepare powder, completing powder collection work after ball milling, placing a certain amount of ball-milled powder into a quartz glass tube after ball milling, mounting the quartz glass tube on a tube sealing machine for vacuumizing, completing tube sealing work when the vacuum degree is lower than a certain amount, and finally placing the vacuum-sealed quartz glass tube into a box-type resistance furnace to finally obtain the Mn 55Bi45/Fe-Ni nanocomposite permanent magnet material.
The Mn 55Bi45/Fe-Ni nanocomposite permanent magnet material prepared by the method has remarkable research value and application prospect in the current large environment, combines the advantages of high coercivity of Mn 55Bi45 and high saturation magnetization of Fe-Ni, has excellent magnetic performance, is beneficial to relieving the problem of excessive consumption of rare earth resources, and has wide application prospect.
Preferably, the preparation of the solid epoxy resin of step (1)
Adding E51 resin and E20 resin into a four-neck flask, heating the temperature, regulating the stirring rate, dropwise adding polyaspartic acid ester resin serving as a chain extender under the condition, controlling the dropwise adding time, performing heat preservation reaction to obtain chain-extended epoxy resin, adding 1, 4-cyclohexanedimethanol diglycidyl ether, adding a mixed solvent (dimethylbenzene: n-butyl alcohol), and regulating the solid content to obtain solid epoxy resin;
step (2) preparation of MnBi alloy ingot
Grinding a high-purity manganese metal raw material and a bismuth metal raw material, crushing the raw materials to proper sizes, respectively weighing certain raw materials, putting the raw materials into a copper crucible of an arc melting furnace, vacuumizing the inside of the arc melting furnace chamber, then flushing argon gas, ensuring that the melting environment is in an anaerobic environment, and repeatedly melting to obtain a blocky cast ingot with uniform components;
preparation of Mn 55Bi45 alloy hard magnetic phase bonded magnet in step (3)
Putting the MnBi alloy cast ingot prepared in the step (2) into a tubular vacuum annealing furnace for annealing, setting a certain annealing temperature and time, cooling to room temperature after taking out, taking out the cast ingot for polishing oxide skin, crushing and grinding in a glove box to obtain coarse powder, sieving, putting the powder into a ball milling tank, setting a ball-to-material ratio, adding oleic acid as a surfactant and ethanol as a solvent, then putting into a ball mill for a certain ball milling time, washing slurry through absolute ethanol after ball milling, mixing paraffin to prepare anisotropic Mn 55Bi45 alloy magnetic powder, adding acetone into the epoxy resin prepared in the step (1), completely melting, adding the epoxy resin into the magnetic powder, stirring by a stirrer, gradually volatilizing the acetone along with stirring, uniformly mixing the epoxy resin and the magnetic powder together, performing compression molding on the magnetic powder mixed with the epoxy resin, and solidifying at a certain temperature to obtain the Mn 55Bi45 alloy hard magnetic phase bonded magnet;
preparation of nanocrystalline Fe-Ni soft magnetic composite material in step (4)
Weighing Fe powder and Ni powder according to a certain metering ratio, adding the Fe powder and the Ni powder into a stainless steel ball grinding tank, performing high-energy ball milling by using a planetary high-energy ball mill, adding alcohol to prevent powder oxidation during the high-energy ball milling, wherein the ball milling atmosphere is argon, fixing the ball milling rotating speed, setting the ball milling time, then weighing epoxy resin to dissolve in an acetone solution, mixing and stirring for a certain time, adding the powder into the solution, uniformly mixing and stirring until complete evaporation, transferring the powder into an annular mold, compacting and forming under a certain pressure, and finally annealing for a period of time at a high temperature to obtain the nanocrystalline Fe-Ni soft magnetic composite material;
Preparation of Mn 55Bi45/Fe-Ni nanocomposite permanent magnet material in step (5)
Uniformly mixing the Mn 55Bi45 alloy hard magnetic phase bonded magnet prepared in the step (3) with the nanocrystalline Fe-Ni soft magnetic composite material prepared in the step (4) in an inert gas glove box cavity with certain oxygen content, then placing the mixture in a high-energy ball milling tank with steel balls, screwing up a ball milling cover, taking out the mixture from the inert gas glove box, wherein the ball milling tank contains a certain amount of Ar gas which can play a role in protecting powder materials to alleviate oxidization in the subsequent grinding process, taking out the screwed ball milling tank from the inert gas glove box, installing and fixing the screwed ball milling tank in the high-energy ball mill, carrying out ball milling according to experimental set conditions, completing powder collection in the inert gas glove box after ball milling, placing a certain amount of ball milling powder in a quartz glass tube, installing the quartz glass tube on a tube sealing machine, vacuumizing the quartz glass tube after the vacuum degree is lower than a certain amount, and finally placing the vacuum-sealed quartz glass tube in a box type resistance furnace to complete the sealing operation, thereby finally obtaining the Mn 55Bi45/Fe-Ni nano composite permanent magnet material.
Preferably, the preparation of the solid epoxy resin of step (1)
Adding E51 resin and E20 resin into a four-neck flask, heating to 70-80 ℃, regulating the stirring rate to 300-400r/min, dropwise adding polyaspartic acid ester resin serving as a chain extender under the condition, controlling the dropwise adding time to be 2-3h, carrying out heat preservation reaction for 2-3h, thus obtaining the epoxy resin after chain extension, adding 1, 4-cyclohexanedimethanol diglycidyl ether, adding a mixed solvent (dimethylbenzene: n-butanol=3:1-5:2), and regulating the solid content to 85-90%, thus obtaining the solid epoxy resin.
The invention has the advantages that the solid epoxy resin prepared by the step combines two traditional resins and is modified by adding the chain extender, the defect of low molecular epoxy resin is overcome, and the addition of the 1, 4-cyclohexanedimethanol diglycidyl ether reduces the viscosity of the system, so that the obtained solid epoxy resin has the advantage of high toughness, provides excellent performance for the subsequent preparation steps of the composite magnetic material, and has very broad application prospect.
Preferably, the preparation of the MnBi alloy ingot of the step (2)
Grinding a high-purity manganese metal raw material and a bismuth metal raw material, crushing the raw materials to proper sizes, weighing the raw materials according to nominal components of Mn: bi=55:45-60:50, putting the raw materials into a copper crucible of an arc melting furnace, vacuumizing the inside of the arc melting furnace chamber, vacuumizing the vacuum degree to (3-3.5) multiplied by 10 -3 Pa, then charging argon to- (0.05-0.07) Pa, ensuring that the melting environment is in an anaerobic environment, and then repeatedly melting for 6-7 times to obtain a blocky ingot with uniform components;
The method has the advantages that the MnBi alloy is selected as a raw material, the MnBi alloy is a novel non-rare earth permanent magnet material with higher coercive force, and an arc melting method is used in the step, so that the melting speed of the method is relatively high, a large amount of metal materials can be melted in a shorter time, the efficiency of preparing MnBi alloy ingots is improved, the production cost is reduced, the production period is shortened, the production cost is reduced, the MnBi alloy with uniform components is simultaneously facilitated to be obtained, and the alloy with good component uniformity has better magnetic property and mechanical property, thereby improving the overall property of the MnBi alloy ingots and laying the ingots for the subsequent steps.
Preferably, the preparation of the Mn 55Bi45 alloy hard magnetic phase bonded magnet in the step (3)
Putting the MnBi alloy cast ingot prepared in the step (2) into a tubular vacuum annealing furnace for annealing at 563-570K for 24-26 hours, cooling to room temperature in a water way, taking out the cast ingot for polishing oxide skin, crushing and grinding to obtain coarse powder in a glove box, sieving with a 100-150 mesh sieve, putting 2-4g of powder into a ball milling tank, taking 2-25 g of powder with a ball material ratio of 12.5:1-25:2, adding oleic acid with 3-3.5% of the powder mass as a surfactant, taking 60-80mL of ethanol as a solvent, putting into a ball mill for ball milling for 0.5-6 hours, washing the slurry through absolute ethyl alcohol after ball milling, mixing paraffin to prepare anisotropic Mn 55Bi45 alloy magnetic powder, adding acetone into the epoxy resin prepared in the step (1), completely melting, adding into the magnetic powder, stirring with a stirrer, gradually volatilizing the acetone, uniformly mixing the epoxy resin and the magnetic powder together, performing compression molding on the mixed epoxy resin, and solidifying the magnetic powder at 120-140 ℃ for 393- 55Bi45 hours to obtain a hard phase magnet;
The invention has the advantages that the high-energy ball milling method and the annealing treatment are adopted in the step, the high-energy ball milling method can lead the Mn 55Bi45 alloy to reach the optimal magnetic property in the shortest time, so that the Mn 55Bi45 alloy has excellent coercivity, the efficiency is improved for the invention, the annealing treatment can effectively improve the saturated magnetization intensity of the Mn 55Bi45 alloy, so that the Mn 55Bi45 alloy has excellent magnetic property, and an excellent performance foundation is provided for the subsequent preparation of the composite permanent magnet material.
Preferably, the nano-crystalline Fe-Ni soft magnetic composite material in the step (4) is prepared
Weighing Fe powder and Ni powder according to a metering ratio of 100:5-200:10, adding the Fe powder and the Ni powder into a stainless steel ball grinding tank, performing high-energy ball grinding by using a planetary high-energy ball mill, adding 3-4% alcohol to prevent powder oxidation, fixing ball grinding speed to 300-350r/min by argon, ball grinding for 20-50h, then weighing epoxy resin with mass fraction of 2-3% to dissolve in acetone solution, mixing and stirring for 30-45min, adding the powder into the solution, uniformly mixing and stirring until complete evaporation, transferring the powder into an annular die, compacting and forming under pressure of 400-450MPa, and finally annealing for 3-4h at temperature of 550-700 ℃ to obtain the nanocrystalline Fe-Ni soft magnetic composite material;
The invention has the advantages that the planetary high-energy ball milling method is adopted in the step, the complex motion track greatly enhances the impact force and grinding effect of grinding medium on materials, so that raw materials can be efficiently thinned to the nanometer level, in addition, the high-strength mechanical acting force can ensure the full mixing of raw materials with different components, in the preparation of the Fe-Ni soft magnetic composite material, fe and Ni elements can be uniformly distributed on the nanometer scale by the efficient thinning and mixing, thereby optimizing the magnetic property of the material, and finally, the Fe-Ni soft magnetic composite material has the advantages of high magnetic energy product and good coercivity.
Preferably, the Mn 55Bi45/Fe-Ni nanocomposite permanent magnet material in the step (5) is prepared
Uniformly mixing the Mn 55Bi45 alloy hard magnetic phase bonding magnet prepared in the step (3) and the nanocrystalline Fe-Ni soft magnetic composite material prepared in the step (4) in an inert gas glove box cavity with the oxygen content controlled at 6-8ppm, then placing the mixture in a high-energy ball milling tank with steel balls, screwing up a ball milling cover, taking out the mixture from the inert gas glove box, wherein Ar gas is contained in the ball milling tank, protecting powder materials in the subsequent milling process to relieve oxidization, taking out the screwed ball milling tank from the inert gas glove box, installing the screwed ball milling tank in the high-energy ball milling machine, carrying out ball milling according to the experimentally set conditions, completing the work of collecting powder in the inert gas glove box after ball milling, placing the ball milled powder of about 0.4-0.5g into a quartz glass tube, carrying out vacuumizing on the quartz glass tube after ball milling powder is collected, and finally placing the vacuum sealed glass tube into a box type resistance furnace to complete the work of sealing the quartz tube when the vacuum degree is lower than (2-3) multiplied by 10 Pa -4 Pa, and finally obtaining the permanent magnet 55Bi45 Fe-Mn nano composite material.
The invention has the advantages that the uniform combination of Mn 55Bi45 and Fe-Ni on the nanometer scale can be realized by adopting a planetary high-energy ball milling method, mn 55Bi45 is used as a hard magnetic phase, fe-Ni is used as a soft magnetic phase, and the combination of Mn 55Bi45 and Fe-Ni on the nanometer scale can generate strong exchange coupling effect, and the exchange coupling effect is beneficial to improving the coercive force and magnetic energy product of the composite material, so that the permanent magnetic performance of the composite material is improved, the advantages of the Mn 55Bi45/Fe-Ni nanocomposite permanent magnetic material finally obtained are integrated, and the advantages of high magnetic energy product and strong coercive force are obtained, so that the composite material has wide application prospect and important research value in the field of permanent magnetic materials.
In summary, the invention has the following beneficial effects:
1. The invention has the advantages that the solid epoxy resin prepared by the step combines two traditional resins and is modified by adding the chain extender, the defect of low molecular epoxy resin is improved, and the addition of the 1, 4-cyclohexanedimethanol diglycidyl ether reduces the viscosity of the system, so that the obtained solid epoxy resin has the advantage of high toughness, provides excellent performance for the subsequent preparation steps of the composite magnetic material, and has very wide application prospect;
2. The method has the advantages that the MnBi alloy is selected as the raw material, and is a novel non-rare earth permanent magnetic material with higher coercive force, and an arc smelting method is used in the step, so that the smelting speed of the method is relatively high, a large amount of metal materials can be smelted in a shorter time, the efficiency of preparing MnBi alloy ingots is improved, the production cost is reduced, the production period is shortened, the MnBi alloy with uniform components is simultaneously facilitated to be obtained, and the alloy with good component uniformity has better magnetic property and mechanical property, thereby improving the overall property of the MnBi alloy ingots and laying the ingots for the subsequent steps;
3. The invention has the advantages that the high-energy ball milling method and the annealing treatment are adopted in the step, the high-energy ball milling method can lead the Mn 55Bi45 alloy to reach the optimal magnetic property in the shortest time, so that the Mn 55Bi45 alloy has excellent coercivity, the efficiency is improved for the invention, the annealing treatment can effectively improve the saturated magnetization intensity of the Mn 55Bi45 alloy, so that the Mn 55Bi45 alloy has excellent magnetic property, and an excellent performance foundation is provided for the subsequent preparation of the composite permanent magnet material;
4. The invention has the advantages that the planetary high-energy ball milling method is adopted in the step, the complex motion track greatly enhances the impact force and grinding effect of grinding medium on materials, so that raw materials can be efficiently thinned to the nanometer level, in addition, the high-strength mechanical acting force can ensure the full mixing of raw materials with different components, in the preparation of the Fe-Ni soft magnetic composite material, fe and Ni elements can be uniformly distributed on the nanometer scale by the efficient thinning and mixing, thereby optimizing the magnetic property of the material, and finally, the Fe-Ni soft magnetic composite material has the advantages of high magnetic energy product and good coercivity;
5. The invention has the advantages that the uniform combination of Mn 55Bi45 and Fe-Ni on the nanometer scale can be realized by adopting a planetary high-energy ball milling method, mn 55Bi45 is used as a hard magnetic phase, fe-Ni is used as a soft magnetic phase, and the combination of Mn 55Bi45 and Fe-Ni on the nanometer scale can generate strong exchange coupling effect, and the exchange coupling effect is beneficial to improving the coercive force and magnetic energy product of the composite material, so that the permanent magnetic performance of the composite material is improved, the advantages of the Mn 55Bi45/Fe-Ni nanocomposite permanent magnetic material finally obtained are integrated, and the advantages of high magnetic energy product and strong coercive force are obtained, so that the composite material has wide application prospect and important research value in the field of permanent magnetic materials.
Drawings
FIG. 1 is a flow chart of the preparation of a nanocomposite permanent magnet material with high magnetic energy product and strong coercivity.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention. Modifications and substitutions to methods, procedures, or conditions of the present invention without departing from the spirit and nature of the invention are intended to be within the scope of the present invention.
The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated. In addition, all the component materials used in the examples are known commercial products.
Example 1
Preparation of solid epoxy resin in step (1)
Adding E51 resin and E20 resin into a four-neck flask, heating to 70 ℃, then regulating the stirring speed to 300r/min, dropwise adding polyaspartic acid ester resin serving as a chain extender under the condition, controlling the dropwise adding time to be 2 hours, carrying out heat preservation reaction for 2 hours, thus obtaining the epoxy resin after chain extension, then adding 1, 4-cyclohexanedimethanol diglycidyl ether, adding a mixed solvent (dimethylbenzene: n-butanol=3:1), and regulating the solid content to 85%, thus obtaining the solid epoxy resin;
step (2) preparation of MnBi alloy ingot
Grinding a high-purity manganese metal raw material and a bismuth metal raw material, crushing the raw materials to a proper size, weighing the raw materials according to nominal components of Mn: bi=55:45, putting the raw materials into a copper crucible of an arc melting furnace, vacuumizing the inside of a furnace chamber of the arc melting furnace, vacuumizing the vacuum degree to 3×10 -3 Pa, then charging argon to-0.05 Pa, ensuring that the melting environment is in an anaerobic environment, and repeating the melting for 6 times to obtain a blocky ingot with uniform components;
preparation of Mn 55Bi45 alloy hard magnetic phase bonded magnet in step (3)
Putting the MnBi alloy cast ingot prepared in the step (2) into a tubular vacuum annealing furnace for annealing at 563K for 24 hours, cooling the cast ingot to room temperature after taking out, taking out the cast ingot for polishing oxide skin, crushing and grinding the cast ingot in a glove box to obtain coarse powder, sieving the coarse powder by using a 100-mesh sieve, putting 2 powder into a ball milling tank, setting the ball material ratio of 12.5:1, adding oleic acid with 3% of the powder mass as a surfactant, setting 60mL of ethanol as a solvent, putting the solvent into a ball mill, setting the ball milling time for 2 hours, washing the slurry through absolute ethanol after ball milling, mixing paraffin to prepare anisotropic Mn 55Bi45 alloy magnetic powder, adding acetone into the epoxy resin prepared in the step (1), adding the epoxy resin into the magnetic powder after complete melting, stirring the epoxy resin by a stirrer, gradually volatilizing the acetone along with the stirring, uniformly mixing the epoxy resin and the magnetic powder, molding the magnetic powder mixed with the epoxy resin, and curing the magnetic powder for 2 hours at 120 ℃ to obtain a Mn 55Bi45 alloy hard magnetic phase bonded magnet;
preparation of nanocrystalline Fe-Ni soft magnetic composite material in step (4)
Weighing Fe powder and Ni powder according to a metering ratio of 100:5, adding the Fe powder and the Ni powder into a stainless steel ball grinding tank, performing high-energy ball milling by using a planetary high-energy ball mill, adding 3% alcohol to prevent powder oxidation during the high-energy ball milling, wherein the ball milling atmosphere is argon, the fixed ball milling rotating speed is 300r/min, the ball milling time is 20h, then weighing epoxy resin with mass fraction of 2% to dissolve in acetone solution, mixing and stirring for 30min, adding the powder into the solution, uniformly mixing and stirring until complete evaporation, transferring the powder into an annular mold, compacting and molding under the pressure of 400MPa, and finally annealing for 3h at the temperature of 650 ℃ to obtain the nanocrystalline Fe-Ni soft magnetic composite material;
Preparation of Mn 55Bi45/Fe-Ni nanocomposite permanent magnet material in step (5)
Uniformly mixing the Mn 55Bi45 alloy hard magnetic phase bonding magnet prepared in the step (3) and the nanocrystalline Fe-Ni soft magnetic composite material prepared in the step (4) in an inert gas glove box cavity with the oxygen content controlled at 8ppm, then placing the mixture in a high-energy ball milling tank with steel balls, screwing up a ball milling cover, taking out the mixture from the inert gas glove box, wherein the ball milling tank contains a certain amount of Ar gas which can play a role in protecting powder materials from oxidization in the subsequent grinding process, taking out the screwed ball milling tank from the inert gas glove box and installing the screwed ball milling tank in the high-energy ball milling tank, carrying out ball milling according to the experimental set conditions, completing powder collection work in the inert gas glove box after ball milling, placing about 0.4g of ball milled powder in a quartz glass tube, carrying out vacuumizing on a tube sealing machine, completing tube sealing work when the vacuum degree is lower than 2X 10 -4 Pa, and finally placing the vacuum-sealed quartz glass tube in a box type resistance furnace to complete the sealing work, thus obtaining the Mn 55Bi45/Fe-Ni nano composite material.
Example 2
Preparation of solid epoxy resin in step (1)
Adding E51 resin and E20 resin into a four-neck flask, heating to 70 ℃, then regulating the stirring speed to 300r/min, dropwise adding polyaspartic acid ester resin serving as a chain extender under the condition, controlling the dropwise adding time to be 2 hours, carrying out heat preservation reaction for 2 hours, thus obtaining the epoxy resin after chain extension, then adding 1, 4-cyclohexanedimethanol diglycidyl ether, adding a mixed solvent (dimethylbenzene: n-butanol=3:1), and regulating the solid content to 85%, thus obtaining the solid epoxy resin;
step (2) preparation of MnBi alloy ingot
Grinding a high-purity manganese metal raw material and a bismuth metal raw material, crushing the raw materials to a proper size, weighing the raw materials according to nominal components of Mn: bi=55:45, putting the raw materials into a copper crucible of an arc melting furnace, vacuumizing the inside of a furnace chamber of the arc melting furnace, vacuumizing the vacuum degree to 3×10 -3 Pa, then charging argon to-0.05 Pa, ensuring that the melting environment is in an anaerobic environment, and repeating the melting for 6 times to obtain a blocky ingot with uniform components;
preparation of Mn 55Bi45 alloy hard magnetic phase bonded magnet in step (3)
Putting the MnBi alloy cast ingot prepared in the step (2) into a tubular vacuum annealing furnace for annealing at 563K for 24 hours, cooling the cast ingot to room temperature after taking out, taking out the cast ingot for polishing oxide skin, crushing and grinding in a glove box to obtain coarse powder, sieving the coarse powder by using a 100-mesh sieve, putting 2 powder into a ball milling tank, setting the ball material ratio of the ball milling tank to be 12.5:1, adding oleic acid with 3% of the powder mass as a surfactant, setting 60mL of ethanol as a solvent, putting the ball milling tank into a ball milling machine for 0.5 hour, cleaning the slurry through absolute ethanol after ball milling, mixing paraffin to prepare anisotropic Mn 55Bi45 alloy magnetic powder, adding acetone into the epoxy resin prepared in the step (1), completely melting the magnetic powder, adding the epoxy resin into the magnetic powder, stirring by a stirrer, gradually volatilizing the acetone along with the stirring, uniformly mixing the epoxy resin and the magnetic powder, performing compression molding on the magnetic powder mixed with the epoxy resin, and curing the magnetic powder for 2 hours at 120 ℃ to obtain a Mn 55Bi45 alloy hard magnetic phase bonded magnet;
preparation of nanocrystalline Fe-Ni soft magnetic composite material in step (4)
Weighing Fe powder and Ni powder according to a metering ratio of 100:5, adding the Fe powder and the Ni powder into a stainless steel ball grinding tank, performing high-energy ball milling by using a planetary high-energy ball mill, adding 3% alcohol to prevent powder oxidation during the high-energy ball milling, wherein the ball milling atmosphere is argon, the fixed ball milling rotating speed is 300r/min, the ball milling time is 20h, then weighing epoxy resin with mass fraction of 2% to dissolve in acetone solution, mixing and stirring for 30min, adding the powder into the solution, uniformly mixing and stirring until complete evaporation, transferring the powder into an annular mold, compacting and molding under the pressure of 400MPa, and finally annealing for 3h at the temperature of 600 ℃ to obtain the nanocrystalline Fe-Ni soft magnetic composite material;
Preparation of Mn 55Bi45/Fe-Ni nanocomposite permanent magnet material in step (5)
Uniformly mixing the Mn 55Bi45 alloy hard magnetic phase bonding magnet prepared in the step (3) and the nanocrystalline Fe-Ni soft magnetic composite material prepared in the step (4) in an inert gas glove box cavity with the oxygen content controlled at 8ppm, then placing the mixture in a high-energy ball milling tank with steel balls, screwing up a ball milling cover, taking out the mixture from the inert gas glove box, wherein the ball milling tank contains a certain amount of Ar gas which can play a role in protecting powder materials from oxidization in the subsequent grinding process, taking out the screwed ball milling tank from the inert gas glove box and installing the screwed ball milling tank in the high-energy ball milling tank, carrying out ball milling according to the experimental set conditions, completing powder collection work in the inert gas glove box after ball milling, placing about 0.4g of ball milled powder in a quartz glass tube, carrying out vacuumizing on a tube sealing machine, completing tube sealing work when the vacuum degree is lower than 2X 10 -4 Pa, and finally placing the vacuum-sealed quartz glass tube in a box type resistance furnace to complete the sealing work, thus obtaining the Mn 55Bi45/Fe-Ni nano composite material.
Example 3
Preparation of solid epoxy resin in step (1)
Adding E51 resin and E20 resin into a four-neck flask, heating to 70 ℃, then regulating the stirring speed to 300r/min, dropwise adding polyaspartic acid ester resin serving as a chain extender under the condition, controlling the dropwise adding time to be 2 hours, carrying out heat preservation reaction for 2 hours, thus obtaining the epoxy resin after chain extension, then adding 1, 4-cyclohexanedimethanol diglycidyl ether, adding a mixed solvent (dimethylbenzene: n-butanol=3:1), and regulating the solid content to be 85%, thus obtaining the solid epoxy resin;
step (2) preparation of MnBi alloy ingot
Grinding a high-purity manganese metal raw material and a bismuth metal raw material, crushing the raw materials to a proper size, weighing the raw materials according to nominal components of Mn: bi=55:45, putting the raw materials into a copper crucible of an arc melting furnace, vacuumizing the inside of a furnace chamber of the arc melting furnace, vacuumizing the vacuum degree to 3×10 -3 Pa, then charging argon to-0.05 Pa, ensuring that the melting environment is in an anaerobic environment, and repeating the melting for 6 times to obtain a blocky ingot with uniform components;
preparation of Mn 55Bi45 alloy hard magnetic phase bonded magnet in step (3)
Putting the MnBi alloy cast ingot prepared in the step (2) into a tubular vacuum annealing furnace for annealing at 563K for 24 hours, cooling the cast ingot to room temperature after taking out, taking out the cast ingot for polishing oxide skin, crushing and grinding the cast ingot in a glove box to obtain coarse powder, sieving the coarse powder by using a 100-mesh sieve, putting 2 powder into a ball milling tank, setting the ball material ratio of 12.5:1, adding oleic acid with 3% of the powder mass as a surfactant, setting 60mL of ethanol as a solvent, putting into a ball mill for ball milling for 1 hour, cleaning the slurry through absolute ethanol after ball milling, mixing paraffin to prepare anisotropic Mn 55Bi45 alloy magnetic powder, adding acetone into the epoxy resin prepared in the step (1), adding the epoxy resin into the magnetic powder after complete melting, stirring the epoxy resin by a stirrer, gradually volatilizing the acetone along with the stirring, uniformly mixing the epoxy resin and the magnetic powder, molding the magnetic powder mixed with the epoxy resin, and curing the magnetic powder for 2 hours at 120 ℃ to obtain a Mn 55Bi45 alloy hard magnetic phase bonded magnet;
preparation of nanocrystalline Fe-Ni soft magnetic composite material in step (4)
Weighing Fe powder and Ni powder according to a metering ratio of 100:5, adding the Fe powder and the Ni powder into a stainless steel ball grinding tank, performing high-energy ball milling by using a planetary high-energy ball mill, adding 3% alcohol to prevent powder oxidation during the high-energy ball milling, wherein the ball milling atmosphere is argon, the fixed ball milling rotating speed is 300r/min, the ball milling time is 20h, then weighing epoxy resin with mass fraction of 2% to dissolve in acetone solution, mixing and stirring for 30min, adding the powder into the solution, uniformly mixing and stirring until complete evaporation, transferring the powder into an annular mold, compacting and molding under pressure of 400MPa, and finally annealing for 3h at a temperature of 625 ℃ to obtain the nanocrystalline Fe-Ni soft magnetic composite material;
Preparation of Mn 55Bi45/Fe-Ni nanocomposite permanent magnet material in step (5)
Uniformly mixing the Mn 55Bi45 alloy hard magnetic phase bonding magnet prepared in the step (3) and the nanocrystalline Fe-Ni soft magnetic composite material prepared in the step (4) in an inert gas glove box cavity with the oxygen content controlled at 8ppm, then placing the mixture in a high-energy ball milling tank with steel balls, screwing up a ball milling cover, taking out the mixture from the inert gas glove box, wherein the ball milling tank contains a certain amount of Ar gas which can play a role in protecting powder materials from oxidization in the subsequent grinding process, taking out the screwed ball milling tank from the inert gas glove box and installing the screwed ball milling tank in the high-energy ball milling tank, carrying out ball milling according to the experimental set conditions, completing powder collection work in the inert gas glove box after ball milling, placing about 0.4g of ball milled powder in a quartz glass tube, carrying out vacuumizing on a tube sealing machine, completing tube sealing work when the vacuum degree is lower than 2X 10 -4 Pa, and finally placing the vacuum-sealed quartz glass tube in a box type resistance furnace to complete the sealing work, thus obtaining the Mn 55Bi45/Fe-Ni nano composite material.
Example 4
Preparation of solid epoxy resin in step (1)
Adding E51 resin and E20 resin into a four-neck flask, heating to 70 ℃, then regulating the stirring speed to 300r/min, dropwise adding polyaspartic acid ester resin serving as a chain extender under the condition, controlling the dropwise adding time to be 2 hours, carrying out heat preservation reaction for 2 hours, thus obtaining the epoxy resin after chain extension, then adding 1, 4-cyclohexanedimethanol diglycidyl ether, adding a mixed solvent (dimethylbenzene: n-butanol=3:1), and regulating the solid content to be 85%, thus obtaining the solid epoxy resin;
step (2) preparation of MnBi alloy ingot
Grinding a high-purity manganese metal raw material and a bismuth metal raw material, crushing the raw materials to a proper size, weighing the raw materials according to nominal components of Mn: bi=55:45, putting the raw materials into a copper crucible of an arc melting furnace, vacuumizing the inside of a furnace chamber of the arc melting furnace, vacuumizing the vacuum degree to 3×10 -3 Pa, then charging argon to-0.05 Pa, ensuring that the melting environment is in an anaerobic environment, and repeating the melting for 6 times to obtain a blocky ingot with uniform components;
preparation of Mn 55Bi45 alloy hard magnetic phase bonded magnet in step (3)
Putting the MnBi alloy cast ingot prepared in the step (2) into a tubular vacuum annealing furnace for annealing at 563K for 24 hours, cooling the cast ingot to room temperature after taking out, taking out the cast ingot for polishing oxide skin, crushing and grinding the cast ingot in a glove box to obtain coarse powder, sieving the coarse powder by using a 100-mesh sieve, putting 2 powder into a ball milling tank, setting the ball material ratio of 12.5:1, adding oleic acid with 3% of the powder mass as a surfactant, setting 60mL of ethanol as a solvent, putting the solvent into a ball mill, setting the ball milling time for 3 hours, washing the slurry through absolute ethanol after ball milling, mixing paraffin to prepare anisotropic Mn 55Bi45 alloy magnetic powder, adding acetone into the epoxy resin prepared in the step (1), adding the epoxy resin into the magnetic powder after complete melting, stirring the epoxy resin by a stirrer, gradually volatilizing the acetone along with the stirring, uniformly mixing the epoxy resin and the magnetic powder, molding the magnetic powder mixed with the epoxy resin, and curing the magnetic powder for 2 hours at 120 ℃ to obtain a Mn 55Bi45 alloy hard magnetic phase bonded magnet;
preparation of nanocrystalline Fe-Ni soft magnetic composite material in step (4)
Weighing Fe powder and Ni powder according to a metering ratio of 100:5, adding the Fe powder and the Ni powder into a stainless steel ball grinding tank, performing high-energy ball milling by using a planetary high-energy ball mill, adding 3% alcohol to prevent powder oxidation during the high-energy ball milling, wherein the ball milling atmosphere is argon, the fixed ball milling rotating speed is 300r/min, the ball milling time is 20h, then weighing epoxy resin with mass fraction of 2% to dissolve in acetone solution, mixing and stirring for 30min, adding the powder into the solution, uniformly mixing and stirring until complete evaporation, transferring the powder into an annular mold, compacting and molding under the pressure of 400MPa, and finally annealing for 3h at the temperature of 700 ℃ to obtain the nanocrystalline Fe-Ni soft magnetic composite material;
Preparation of Mn 55Bi45/Fe-Ni nanocomposite permanent magnet material in step (5)
Uniformly mixing the Mn 55Bi45 alloy hard magnetic phase bonding magnet prepared in the step (3) and the nanocrystalline Fe-Ni soft magnetic composite material prepared in the step (4) in an inert gas glove box cavity with the oxygen content controlled at 8ppm, then placing the mixture in a high-energy ball milling tank with steel balls, screwing up a ball milling cover, taking out the mixture from the inert gas glove box, wherein the ball milling tank contains a certain amount of Ar gas which can play a role in protecting powder materials from oxidization in the subsequent grinding process, taking out the screwed ball milling tank from the inert gas glove box and installing the screwed ball milling tank in the high-energy ball milling tank, carrying out ball milling according to the experimental set conditions, completing powder collection work in the inert gas glove box after ball milling, placing about 0.4g of ball milled powder in a quartz glass tube, carrying out vacuumizing on a tube sealing machine, completing tube sealing work when the vacuum degree is lower than 2X 10 -4 Pa, and finally placing the vacuum-sealed quartz glass tube in a box type resistance furnace to complete the sealing work, thus obtaining the Mn 55Bi45/Fe-Ni nano composite material.
Comparative example 1
Preparation of solid epoxy resin in step (1)
Adding E51 resin and E20 resin into a four-neck flask, heating to 70 ℃, then regulating the stirring speed to 300r/min, dropwise adding polyaspartic acid ester resin serving as a chain extender under the condition, controlling the dropwise adding time to be 2 hours, carrying out heat preservation reaction for 2 hours, thus obtaining the epoxy resin after chain extension, then adding 1, 4-cyclohexanedimethanol diglycidyl ether, adding a mixed solvent (dimethylbenzene: n-butanol=3:1), and regulating the solid content to 85%, thus obtaining the solid epoxy resin;
Preparation of Mn 55Bi45 alloy hard magnetic phase bonded magnet in step (2)
Putting a MnBi alloy cast ingot into a tubular vacuum annealing furnace for annealing at 563K for 24 hours, cooling the cast ingot to room temperature by water when taking out, taking out the cast ingot for polishing oxide skin, crushing and grinding in a glove box to obtain coarse powder, sieving with a 100-mesh sieve, putting 2 powder into a ball milling tank, putting the ball material ratio of 12.5:1, adding oleic acid with 3% of the powder mass as a surfactant, 60mL of ethanol as a solvent, putting into the ball milling tank for ball milling for 4 hours, washing the slurry through absolute ethanol after ball milling, mixing paraffin to prepare anisotropic Mn 55Bi45 alloy magnetic powder, adding acetone into the epoxy resin prepared in the step (1), adding into the magnetic powder after complete melting, stirring with a stirrer, gradually volatilizing the acetone, uniformly mixing the epoxy resin and the magnetic powder together, molding the magnetic powder mixed with the epoxy resin, and curing at 120 ℃ for 2 hours to obtain a Mn 55Bi45 alloy hard magnetic phase bonded magnet;
Preparation of nanocrystalline Fe-Ni soft magnetic composite material in step (3)
Weighing Fe powder and Ni powder according to a metering ratio of 100:5, adding the Fe powder and the Ni powder into a stainless steel ball grinding tank, performing high-energy ball milling by using a planetary high-energy ball mill, adding 3% alcohol to prevent powder oxidation during the high-energy ball milling, wherein the ball milling atmosphere is argon, the fixed ball milling rotating speed is 300r/min, the ball milling time is 20h, then weighing epoxy resin with mass fraction of 2% to dissolve in acetone solution, mixing and stirring for 30min, adding the powder into the solution, uniformly mixing and stirring until complete evaporation, transferring the powder into an annular mold, compacting and molding under the pressure of 400MPa, and finally annealing for 3h at the temperature of 575 ℃ to obtain the nanocrystalline Fe-Ni soft magnetic composite material;
Preparation of Mn 55Bi45/Fe-Ni nanocomposite permanent magnet material in step (4)
Uniformly mixing the Mn 55Bi45 alloy hard magnetic phase bonding magnet prepared in the step (2) and the nanocrystalline Fe-Ni soft magnetic composite material prepared in the step (3) in an inert gas glove box cavity with the oxygen content controlled at 8ppm, then placing the mixture in a high-energy ball milling tank with steel balls, screwing up a ball milling cover, taking out the mixture from the inert gas glove box, wherein the ball milling tank contains a certain amount of Ar gas which can play a role in protecting powder materials from oxidization in the subsequent grinding process, taking out the screwed ball milling tank from the inert gas glove box and installing the screwed ball milling tank in the high-energy ball milling tank, carrying out ball milling according to the experimental set conditions, completing powder collection work in the inert gas glove box after ball milling, placing about 0.4g of ball milled powder in a quartz glass tube, carrying out vacuumizing on a tube sealing machine, completing tube sealing work when the vacuum degree is lower than 2X 10 -4 Pa, and finally placing the vacuum-sealed quartz glass tube in a box type resistance furnace to complete the sealing work, thus obtaining the Mn 55Bi45/Fe-Ni nano composite material.
Comparative example 2
Preparation of solid epoxy resin in step (1)
Adding E51 resin and E20 resin into a four-neck flask, heating to 70 ℃, then regulating the stirring speed to 300r/min, dropwise adding polyaspartic acid ester resin serving as a chain extender under the condition, controlling the dropwise adding time to be 2 hours, carrying out heat preservation reaction for 2 hours, thus obtaining the epoxy resin after chain extension, then adding 1, 4-cyclohexanedimethanol diglycidyl ether, adding a mixed solvent (dimethylbenzene: n-butanol=3:1), and regulating the solid content to 85%, thus obtaining the solid epoxy resin;
Preparation of Mn 55Bi45 alloy hard magnetic phase bonded magnet in step (2)
Putting a MnBi alloy cast ingot into a tubular vacuum annealing furnace for annealing at 563K for 24 hours, cooling the cast ingot to room temperature by water when taking out, taking out the cast ingot for polishing oxide skin, crushing and grinding in a glove box to obtain coarse powder, sieving with a 100-mesh sieve, putting 2 powder into a ball milling tank, putting the ball material ratio of 12.5:1, adding oleic acid with 3% of the powder mass as a surfactant, 60mL of ethanol as a solvent, putting into the ball milling tank for 5 hours, washing the slurry through absolute ethanol after ball milling, mixing paraffin to prepare anisotropic Mn 55Bi45 alloy magnetic powder, adding acetone into the epoxy resin prepared in the step (1), adding the epoxy resin into the magnetic powder after complete melting, stirring by a stirrer, gradually volatilizing the acetone along with the stirring, uniformly mixing the epoxy resin and the magnetic powder, molding the magnetic powder mixed with the epoxy resin, and curing for 2 hours at 120 ℃ to obtain a Mn 55Bi45 alloy hard magnetic phase bonded magnet;
Preparation of nanocrystalline Fe-Ni soft magnetic composite material in step (3)
Weighing Fe powder and Ni powder according to a metering ratio of 100:5, adding the Fe powder and the Ni powder into a stainless steel ball grinding tank, performing high-energy ball milling by using a planetary high-energy ball mill, adding 3% alcohol to prevent powder oxidation during the high-energy ball milling, wherein the ball milling atmosphere is argon, the fixed ball milling rotating speed is 300r/min, the ball milling time is 20h, then weighing epoxy resin with mass fraction of 2% to dissolve in acetone solution, mixing and stirring for 30min, adding the powder into the solution, uniformly mixing and stirring until complete evaporation, transferring the powder into an annular mold, compacting and molding under the pressure of 400MPa, and finally annealing for 3h at the temperature of 550 ℃ to obtain the nanocrystalline Fe-Ni soft magnetic composite material;
Preparation of Mn 55Bi45/Fe-Ni nanocomposite permanent magnet material in step (4)
Uniformly mixing the Mn 55Bi45 alloy hard magnetic phase bonding magnet prepared in the step (2) and the nanocrystalline Fe-Ni soft magnetic composite material prepared in the step (3) in an inert gas glove box cavity with the oxygen content controlled at 7ppm, then placing the mixture in a high-energy ball milling tank with steel balls, screwing up a ball milling cover, taking out the mixture from the inert gas glove box, wherein the ball milling tank contains a certain amount of Ar gas which can play a role in protecting powder materials from oxidization in the subsequent grinding process, taking out the screwed ball milling tank from the inert gas glove box and installing the screwed ball milling tank in the high-energy ball milling tank, carrying out ball milling according to the experimental set conditions, completing powder collection work in the inert gas glove box after ball milling, placing about 0.4g of ball milled powder in a quartz glass tube, carrying out vacuumizing on a tube sealing machine, completing tube sealing work when the vacuum degree is lower than 2X 10 -4 Pa, and finally placing the vacuum-sealed quartz glass tube in a box type resistance furnace to complete the sealing work, thus obtaining the Mn 55Bi45/Fe-Ni nano composite material.
Comparison of detection experiments:
the nanocomposite permanent magnet materials obtained in examples 1 to 4 and comparative example products 1 and 2 were tested as follows:
Viscosity detection
Detecting the viscosity of the epoxy resin system by using a digital display viscometer, detecting the viscosity of different epoxy resins, selecting a rotor with the temperature set at 25 ℃, selecting a measuring range, adjusting the retention level of the digital display viscometer, setting each item of data, carrying out the viscosity test for 3 times for each sample of the epoxy resin, and taking the average value of 3 times.
Magnetic property analysis
The annealed Mn 55Bi45 alloy cast ingot is crushed, ground and sieved, and then subjected to high-energy ball milling for 0.5 hour, 1 hour, 2 hours, 4 hours, 5 hours and 6 hours respectively to prepare Mn 55Bi45 alloy.
TABLE 1 viscosity detection
As can be seen from Table 1, the viscosity performance of example 1 was optimal and comparative example 2 was poor. In example 1, the viscosity of the epoxy resin reached 42000mpa·s, and in comparative example 2 only 24000mpa·s, it can be seen that the viscosity of the epoxy resin decreases with increasing mass of the raw material E51 resin, the more mass of the raw material E51 resin is, the lower the viscosity of the epoxy resin is, the higher the viscosity is, which indicates that the toughness of the epoxy resin is more excellent, and the improvement of toughness plays an important role in the subsequent compounding of magnetic materials, providing excellent performance basis for the subsequent.
TABLE 2 coercivity detection
As can be seen from table 2, example 1 has the most excellent performance. The intrinsic coercivity reaches 13.4Oe, which is the highest, the comparative example 2 is worse, and the intrinsic coercivity is 5.1, which shows that the intrinsic coercivity increases with the extension of the ball milling time, but when the ball milling time is 2 hours, the intrinsic coercivity reaches the peak, and then decreases with the extension of the ball milling time, so that the ball milling time is 2 hours, and the intrinsic coercivity of the Mn 55Bi45 alloy hard-phase bonded magnet is the best.
TABLE 3 magnetic property detection
As can be seen from Table 3, example 1 has the most excellent performance and comparative example 2 has a poor performance. The saturated magnetization of example 1 was as high as 33.1Am 2/kg, and that of comparative example 2 was 20.1Am 2/kg, and it was found that the saturated magnetization increased with increasing annealing temperature, and the saturated magnetization reached the peak when the annealing temperature reached 650 ℃, and then decreased with increasing annealing temperature, and that the nanocrystalline fe—ni soft magnetic composite material was the best saturated magnetization and the most excellent magnetic property when the annealing temperature was 650 ℃.
The present embodiment is merely illustrative of the present invention and is not intended to limit the present invention to modifications which would be obvious to those skilled in the art to which the present invention pertains without inventive contribution from the skilled artisan upon reading the specification, but which are intended to be protected by the patent law within the scope of the present claims.

Claims (7)

1.一种具有高磁能积强矫顽力纳米复合永磁材料的制备，其特征在于，包括：步骤（1）固体环氧树脂的制备、步骤（2）MnBi合金铸锭的制备、步骤（3）Mn55Bi45合金硬磁相粘结磁体的制备、步骤（4）纳米晶Fe-Ni软磁复合材料的制备、步骤（5）Mn55Bi45/Fe-Ni纳米复合永磁材料的制备；1. A method for preparing a nanocomposite permanent magnetic material with high magnetic energy product and strong coercive force, characterized in that it comprises: step (1) preparing a solid epoxy resin, step (2) preparing a MnBi alloy ingot, step (3) preparing a Mn 55 Bi 45 alloy hard magnetic phase bonded magnet, step (4) preparing a nanocrystalline Fe-Ni soft magnetic composite material, and step (5) preparing a Mn 55 Bi 45 /Fe-Ni nanocomposite permanent magnetic material; 其中，步骤（4）纳米晶Fe-Ni软磁复合材料的制备包括：Wherein, the preparation of the nanocrystalline Fe-Ni soft magnetic composite material in step (4) comprises: 按照一定的计量比称取Fe粉和Ni粉，进行高能球磨，期间加入酒精防止粉末氧化，球磨气氛为氩气，随后，称取环氧树脂溶解在丙酮溶液中，混合搅拌，将上述粉末加入到溶液中，均匀混合搅拌直至彻底蒸发；然后在一定压力下压实成型；最后，在高温下退火一段时间，即得纳米晶Fe-Ni软磁复合材料；Fe powder and Ni powder are weighed according to a certain stoichiometric ratio, and high-energy ball milling is performed, during which alcohol is added to prevent oxidation of the powders, and the ball milling atmosphere is argon. Subsequently, epoxy resin is weighed and dissolved in an acetone solution, mixed and stirred, and the above powders are added to the solution, mixed and stirred evenly until completely evaporated; then compacted and formed under a certain pressure; finally, annealed at a high temperature for a period of time to obtain a nanocrystalline Fe-Ni soft magnetic composite material; 步骤（5）Mn55Bi45/Fe-Ni纳米复合永磁材料的制备包括：Step (5) Preparation of Mn 55 Bi 45 /Fe-Ni nanocomposite permanent magnetic material comprises: 将步骤（3）制得的Mn55Bi45合金硬磁相粘结磁体与步骤（4）制得的纳米晶Fe-Ni软磁复合材料均匀混合，然后进行球磨制粉，球磨结束后完成粉体的收取工作；收取球磨粉料后，将一定量球磨后粉末置于石英玻璃管中，安装到封管机上进行抽真空，待真空度低于一定量时，完成封管工作；最后将真空密封的石英玻璃管放在箱式电阻炉中完成，最终得到Mn55Bi45/Fe-Ni纳米复合永磁材料。The Mn55Bi45 alloy hard magnetic phase bonded magnet obtained in step ( 3 ) and the nanocrystalline Fe-Ni soft magnetic composite material obtained in step (4) are uniformly mixed, and then ball-milled to produce powder. After the ball milling is completed, the powder is collected. After the ball-milled powder is collected, a certain amount of the ball-milled powder is placed in a quartz glass tube, which is installed on a tube sealing machine for vacuuming. When the vacuum degree is lower than a certain amount, the tube is sealed. Finally, the vacuum-sealed quartz glass tube is placed in a box-type resistance furnace to obtain a Mn55Bi45 /Fe-Ni nano-composite permanent magnet material. 2.根据权利要求1所述的具有高磁能积强矫顽力纳米复合永磁材料的制备，其特征在于：2. The preparation of nanocomposite permanent magnetic material with high magnetic energy product and strong coercivity according to claim 1, characterized in that: 步骤（1）固体环氧树脂的制备Step (1) Preparation of solid epoxy resin 将E51树脂、E20树脂加入到四口烧瓶当中，再将温度升温，之后调节搅拌速率，并在此条件下滴加扩链剂聚天门冬氨酸酯树脂，控制滴加时间，再进行保温反应，从而得到扩链后的环氧树脂，之后加入1,4-环己烷二甲醇二缩水甘油醚，再加入混合溶剂（二甲苯:正丁醇），调整固含量，即得到固体环氧树脂；Add E51 resin and E20 resin into a four-necked flask, then raise the temperature, adjust the stirring rate, and under this condition, dropwise add the chain extender polyaspartic acid ester resin, control the dropping time, and then carry out heat preservation reaction to obtain the chain-extended epoxy resin, then add 1,4-cyclohexanedimethanol diglycidyl ether, and then add a mixed solvent (xylene: n-butanol), adjust the solid content, and obtain a solid epoxy resin; 步骤（2）MnBi合金铸锭的制备Step (2) Preparation of MnBi alloy ingot 将高纯度锰金属原料和铋金属原料经过打磨之后再破碎至合适尺寸，分别称取一定原料，将原料放入电弧熔炼炉铜坩埚中，再将电弧熔炼炉腔体内抽真空后，再充入氩气，确保熔炼环境处于无氧环境，然后进行反复的熔炼，从而获得成分均匀的块状铸锭；The high-purity manganese metal raw material and bismuth metal raw material are ground and then crushed to a suitable size, and a certain amount of raw materials are weighed respectively, and the raw materials are placed in a copper crucible of an arc melting furnace, and then the cavity of the arc melting furnace is evacuated and filled with argon gas to ensure that the melting environment is in an oxygen-free environment, and then the melting is repeated to obtain a block ingot with uniform composition; 步骤（3）Mn55Bi45合金硬磁相粘结磁体的制备Step (3) Preparation of Mn 55 Bi 45 alloy hard magnetic phase bonded magnet 将上述步骤（2）制得的MnBi合金铸锭放入管式真空退火炉中进行退火，设置一定退火温度与时间，取出时水冷至室温，取出铸锭进行氧化皮打磨，在手套箱中进行破碎研磨得到粗粉，进行过筛，取粉末置球磨罐中，设置球料比，并加入油酸做表面活性剂，乙醇作溶剂，然后放入球磨机中设置一定球磨时间，球磨完成后将浆料通过无水乙醇进行清洗，再混合石蜡制备各向异性Mn55Bi45合金磁粉，将丙酮加入到步骤（1）制得的环氧树脂中，完全融化后再加入到磁粉中，并用搅拌器加以搅拌，随着搅拌的进行，丙酮逐渐挥发，环氧树脂和磁粉均匀地混合在一起，将混有环氧树脂的磁粉模压成型，再于一定温度下固化，得到Mn55Bi45合金硬磁相粘结磁体；The MnBi alloy ingot obtained in the above step (2) is placed in a tubular vacuum annealing furnace for annealing, and a certain annealing temperature and time are set. When taking it out, it is water-cooled to room temperature, and the ingot is taken out for oxide scale grinding, and crushed and ground in a glove box to obtain coarse powder, which is sieved, and the powder is placed in a ball mill, and the ball-to-material ratio is set, and oleic acid is added as a surfactant and ethanol is used as a solvent, and then placed in a ball mill for a certain ball milling time. After the ball milling is completed, the slurry is washed with anhydrous ethanol, and then mixed with paraffin to prepare anisotropic Mn55Bi45 alloy magnetic powder, and acetone is added to the epoxy resin obtained in step (1), and after it is completely melted, it is added to the magnetic powder and stirred with a stirrer. As the stirring proceeds, the acetone gradually evaporates, and the epoxy resin and the magnetic powder are uniformly mixed together. The magnetic powder mixed with the epoxy resin is molded, and then cured at a certain temperature to obtain a Mn55Bi45 alloy hard magnetic phase bonded magnet; 步骤（4）纳米晶Fe-Ni软磁复合材料的制备Step (4) Preparation of nanocrystalline Fe-Ni soft magnetic composite material 按照一定的计量比称取Fe粉和Ni粉，加入到不锈钢球磨罐中，使用行星式高能球磨机进行高能球磨，期间加入酒精防止粉末氧化，球磨气氛为氩气，固定球磨转速，设置球磨时间，随后，称取环氧树脂溶解在丙酮溶液中，混合搅拌一定时间，将上述粉末加入到溶液中，均匀混合搅拌直至彻底蒸发；然后转移至环形模具中，在一定压力下压实成型；最后，在高温下退火一段时间，即得纳米晶Fe-Ni软磁复合材料；Fe powder and Ni powder are weighed according to a certain metering ratio, added into a stainless steel ball mill, and high-energy ball milling is performed using a planetary high-energy ball mill. During the process, alcohol is added to prevent oxidation of the powder. The ball milling atmosphere is argon gas. The ball milling speed is fixed and the ball milling time is set. Subsequently, epoxy resin is weighed and dissolved in an acetone solution, mixed and stirred for a certain period of time, and the above powders are added into the solution, mixed and stirred evenly until completely evaporated; then the powders are transferred into a ring mold and compacted under a certain pressure; finally, the nanocrystalline Fe-Ni soft magnetic composite material is obtained by annealing at high temperature for a period of time. 步骤（5）Mn55Bi45/Fe-Ni纳米复合永磁材料的制备Step (5) Preparation of Mn 55 Bi 45 /Fe-Ni nanocomposite permanent magnet material 在一定氧含量的惰性气体手套箱腔体中将步骤（3）制得的Mn55Bi45合金硬磁相粘结磁体与步骤（4）制得的纳米晶Fe-Ni软磁复合材料均匀混合，然后置于已配好钢球的高能球磨罐中，之后拧紧球磨盖，从惰性气体手套箱中拿出，此时球磨罐中已含有一定量的Ar气，可以在后续研磨过程中起到保护粉体材料减轻氧化的作用；从惰性气体手套箱中取出拧紧的球磨罐并安装固定在高能球磨机中，按照实验设定的条件进行球磨制粉，球磨结束后在惰性气体手套箱中完成粉体的收取工作；收取球磨粉料后，将一定量球磨后粉末置于石英玻璃管中，安装到封管机上进行抽真空，待真空度低于一定量时，完成封管工作；最后将真空密封的石英玻璃管放在箱式电阻炉中完成，最终得到Mn55Bi45/Fe-Ni纳米复合永磁材料。In an inert gas glove box chamber with a certain oxygen content, the Mn55Bi45 alloy hard magnetic phase bonded magnet obtained in step ( 3 ) and the nanocrystalline Fe-Ni soft magnetic composite material obtained in step (4) are uniformly mixed, and then placed in a high-energy ball mill equipped with steel balls. The ball mill cover is then tightened and taken out from the inert gas glove box. At this time, the ball mill contains a certain amount of Ar gas, which can protect the powder material from oxidation during the subsequent grinding process. The tightened ball mill is taken out from the inert gas glove box and fixed in a high-energy ball mill. Ball milling is performed according to the experimental conditions. After the ball milling is completed, the powder is collected in the inert gas glove box. After the ball milling is completed, a certain amount of the ball milled powder is placed in a quartz glass tube, which is installed on a tube sealing machine for vacuuming. When the vacuum degree is lower than a certain amount, the tube sealing is completed. Finally, the vacuum-sealed quartz glass tube is placed in a box-type resistance furnace to obtain a Mn55Bi45 /Fe-Ni nano-composite permanent magnet material. 3.根据权利要求2所述的具有高磁能积强矫顽力纳米复合永磁材料的制备，其特征在于：3. The preparation of nanocomposite permanent magnetic material with high magnetic energy product and strong coercivity according to claim 2, characterized in that: 步骤（1）固体环氧树脂的制备Step (1) Preparation of solid epoxy resin 将E51树脂、E20树脂加入到四口烧瓶当中，再将温度升温至70-80℃，之后调节搅拌速率在300-400r/min，并在此条件下滴加扩链剂聚天门冬氨酸酯树脂，滴加比例为4:1-12:3，滴加时间控制在2-3h之间，再保温反应2-3h，从而得到扩链后的环氧树脂，之后加入1,4-环己烷二甲醇二缩水甘油醚，再加入混合溶剂（二甲苯:正丁醇=3:1-5:2），调整固含量为85-90%，即得到固体环氧树脂。Add E51 resin and E20 resin into a four-necked flask, then raise the temperature to 70-80°C, then adjust the stirring rate to 300-400r/min, and under this condition, add the chain extender polyaspartic acid ester resin dropwise, the addition ratio is 4:1-12:3, the addition time is controlled between 2-3h, and then keep the temperature for 2-3h to obtain the chain-extended epoxy resin, then add 1,4-cyclohexanedimethanol diglycidyl ether, and then add a mixed solvent (xylene: n-butanol = 3:1-5:2), adjust the solid content to 85-90%, and obtain a solid epoxy resin. 4.根据权利要求3所述的具有高磁能积强矫顽力纳米复合永磁材料的制备，其特征在于：4. The preparation of nanocomposite permanent magnetic material with high magnetic energy product and strong coercivity according to claim 3, characterized in that: 步骤（2）MnBi合金铸锭的制备Step (2) Preparation of MnBi alloy ingot 将高纯度锰金属原料和铋金属原料经过打磨之后再破碎至合适尺寸，按照 Mn:Bi=55:45-60:50的名义成分称取原料，将原料放入电弧熔炼炉铜坩埚中，再将电弧熔炼炉腔体内抽真空，将真空度抽至（3-3.5）×10-3Pa后再冲入氩气至-（0.05-0.07）Pa，确保熔炼环境处于无氧环境，然后进行反复6-7次的熔炼，从而获得成分均匀的块状铸锭。The high-purity manganese metal raw material and bismuth metal raw material are ground and then crushed to a suitable size, and the raw materials are weighed according to the nominal composition of Mn:Bi=55:45-60:50, and the raw materials are placed in a copper crucible of an arc melting furnace. The arc melting furnace cavity is then evacuated to a vacuum degree of (3-3.5)× 10-3 Pa, and then argon gas is injected to -(0.05-0.07) Pa to ensure that the melting environment is in an oxygen-free environment. The melting is then repeated 6-7 times to obtain a block ingot with uniform composition. 5.根据权利要求4所述的具有高磁能积强矫顽力纳米复合永磁材料的制备，其特征在于：5. The preparation of nanocomposite permanent magnetic material with high magnetic energy product and strong coercivity according to claim 4, characterized in that: 步骤（3）Mn55Bi45合金硬磁相粘结磁体的制备Step (3) Preparation of Mn 55 Bi 45 alloy hard magnetic phase bonded magnet 将上述步骤（2）制得的MnBi合金铸锭放入管式真空退火炉中进行退火，退火温度为563-570K，退火时间为24-26小时，取出时水冷至室温，取出铸锭进行氧化皮打磨，在手套箱中进行破碎研磨得到粗粉，并用100-150目过筛，取2-4g粉末置球磨罐中，球料比为12.5:1-25:2，并加入粉末质量3-3.5%的油酸做表面活性剂，60-80mL乙醇作溶剂，然后放入球磨机中设置球磨时间0.5-6小时，球磨完成后将浆料通过无水乙醇进行清洗，再混合石蜡制备各向异性Mn55Bi45合金磁粉，将丙酮加入到步骤（1）制得的环氧树脂中，完全融化后再加入到磁粉中，并用搅拌器加以搅拌，随着搅拌的进行，丙酮逐渐挥发，环氧树脂和磁粉均匀地混合在一起，将混有环氧树脂的磁粉模压成型，再于120-140℃固化2-3h，得到Mn55Bi45合金硬磁相粘结磁体。The MnBi alloy ingot obtained in the above step (2) is placed in a tubular vacuum annealing furnace for annealing at an annealing temperature of 563-570K for an annealing time of 24-26 hours. When taken out, the ingot is cooled to room temperature with water. The ingot is taken out for oxide scale polishing, crushed and ground in a glove box to obtain a coarse powder, and sieved with 100-150 mesh. 2-4g of the powder is placed in a ball mill with a ball-to-material ratio of 12.5:1-25:2, and 3-3.5% of oleic acid by weight of the powder is added as a surfactant, 60-80mL of ethanol is used as a solvent, and then the ingot is placed in a ball mill for a ball milling time of 0.5-6 hours. After the ball milling is completed, the slurry is washed with anhydrous ethanol and then mixed with paraffin to prepare anisotropic Mn 55 Bi Acetone is added to the epoxy resin obtained in step (1) and added to the magnetic powder after it is completely melted. The mixture is stirred with a stirrer. As the stirring proceeds, the acetone gradually evaporates, and the epoxy resin and the magnetic powder are uniformly mixed together. The magnetic powder mixed with the epoxy resin is molded and then cured at 120-140°C for 2-3h to obtain a Mn 55 Bi 45 alloy hard magnetic phase bonded magnet. 6.根据权利要求5所述的具有高磁能积强矫顽力纳米复合永磁材料的制备，其特征在于：6. The preparation of nanocomposite permanent magnetic material with high magnetic energy product and strong coercivity according to claim 5, characterized in that: 步骤（4）纳米晶Fe-Ni软磁复合材料的制备Step (4) Preparation of nanocrystalline Fe-Ni soft magnetic composite material 按照100:5-200:10的计量比称取Fe粉和Ni粉，加入到不锈钢球磨罐中，使用行星式高能球磨机进行高能球磨，期间加入3-4％的酒精防止粉末氧化，球磨气氛为氩气，固定球磨转速为300-350r／min，球磨时间为20-50h，随后，称取质量分数为2-3％的环氧树脂溶解在丙酮溶液中，混合搅拌30-45min，将上述粉末加入到溶液中，均匀混合搅拌直至彻底蒸发；然后转移至环形模具中，在压力400-450MPa下压实成型；最后，在温度为550-700℃下退火3-4h，即得纳米晶Fe-Ni软磁复合材料。Fe powder and Ni powder are weighed according to a metering ratio of 100:5-200:10, added into a stainless steel ball mill, and high-energy ball milling is performed using a planetary high-energy ball mill. During the process, 3-4% alcohol is added to prevent powder oxidation. The ball milling atmosphere is argon, the fixed ball milling speed is 300-350r/min, and the ball milling time is 20-50h. Subsequently, 2-3% of epoxy resin with a mass fraction is weighed and dissolved in an acetone solution, mixed and stirred for 30-45min, and the above powders are added into the solution, mixed and stirred evenly until completely evaporated; then transferred to a ring mold, compacted and molded at a pressure of 400-450MPa; finally, annealed at a temperature of 550-700℃ for 3-4h to obtain a nanocrystalline Fe-Ni soft magnetic composite material. 7.根据权利要求6所述的具有高磁能积强矫顽力纳米复合永磁材料的制备，其特征在于：7. The preparation of nanocomposite permanent magnetic material with high magnetic energy product and strong coercivity according to claim 6, characterized in that: 步骤（5）Mn55Bi45/Fe-Ni纳米复合永磁材料的制备Step (5) Preparation of Mn 55 Bi 45 /Fe-Ni nanocomposite permanent magnet material 在氧含量控制在6-8ppm的惰性气体手套箱腔体中将步骤（3）制得的Mn55Bi45 In an inert gas glove box chamber with an oxygen content controlled at 6-8 ppm, the Mn 55 Bi 45 合金硬磁相粘结磁体与步骤（4）制得的纳米晶Fe-Ni软磁复合材料均匀混合，然后置于已配好钢球的高能球磨罐中，之后拧紧球磨盖，从惰性气体手套箱中拿出，此时球磨罐中已含有Ar气，可以在后续研磨过程中起到保护粉体材料减轻氧化的作用；从惰性气体手套箱中取出拧紧的球磨罐并安装固定在高能球磨机中，按条件进行球磨制粉，球磨结束后在惰性气体手套箱中完成粉体的收取工作；收取球磨粉料后，将大约0.4-0.5g的球磨后粉末置于石英玻璃管中，安装到封管机上进行抽真空，待真空度低于（2-3）×10-4Pa时，完成封管工作；最后将真空密封的石英玻璃管放在箱式电阻炉中完成，最终得到Mn55Bi45/Fe-Ni纳米复合永磁材料。The alloy hard magnetic phase bonded magnet is uniformly mixed with the nanocrystalline Fe-Ni soft magnetic composite material obtained in step (4), and then placed in a high-energy ball mill equipped with steel balls, and then the ball mill cover is tightened and taken out from the inert gas glove box. At this time, the ball mill contains Ar gas, which can protect the powder material from oxidation during the subsequent grinding process; the tightened ball mill is taken out from the inert gas glove box and fixed in a high-energy ball mill, and ball milling is performed according to conditions. After the ball milling is completed, the powder is collected in the inert gas glove box; after collecting the ball milled powder, about 0.4-0.5g of the ball milled powder is placed in a quartz glass tube, which is installed on a tube sealing machine for vacuuming, and the tube sealing is completed when the vacuum degree is lower than ( 2-3 )× 10-4 Pa; finally, the vacuum-sealed quartz glass tube is placed in a box-type resistance furnace to obtain a Mn55Bi45 /Fe-Ni nano-composite permanent magnet material.
CN202411643680.9A 2024-11-18 2024-11-18 Preparation of a nanocomposite permanent magnetic material with high magnetic energy product and strong coercivity Pending CN119480412A (en)

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