CN111554504A - Nano-scale textured rare earth permanent magnet material and preparation method thereof - Google Patents

Nano-scale textured rare earth permanent magnet material and preparation method thereof Download PDF

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CN111554504A
CN111554504A CN202010453527.5A CN202010453527A CN111554504A CN 111554504 A CN111554504 A CN 111554504A CN 202010453527 A CN202010453527 A CN 202010453527A CN 111554504 A CN111554504 A CN 111554504A
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CN111554504B (en
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杨金波
查亮
孔祥东
韩立
杨文云
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Peking University
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    • 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
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    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/06—Continuous casting of metals, i.e. casting in indefinite lengths into moulds with travelling walls, e.g. with rolls, plates, belts, caterpillars
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    • C21D1/26—Methods of annealing
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    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • C21D1/773—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material under reduced pressure or vacuum
    • C—CHEMISTRY; METALLURGY
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    • C22C33/04—Making ferrous alloys by melting
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    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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    • 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
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    • 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
    • H01F41/0273—Imparting anisotropy
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2201/00—Treatment for obtaining particular effects
    • C21D2201/05—Grain orientation

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Abstract

The invention discloses a nano-scale textured rare earth permanent magnet material and a preparation method thereof, relates to the field of nano-scale rare earth permanent magnet materials, and particularly relates to a method for preparing a nano-scale textured rare earth permanent magnet material by smelting and crushing a rare earth transition group intermetallic compound to prepare an amorphous ribbon and then rapidly annealing by adopting an electron beam. The invention provides a new application of an electron beam as a rapid heating method for controlling nano-particle crystallization, which is more efficient and environment-friendly due to the characteristic of rapid heat treatment. The electron beam rapid annealing can simultaneously and accurately control the size, the form and the orientation of hard magnetic phase grains, realize the anisotropy of the rare earth permanent magnetic material, obtain a texture nano structure and realize the coercive force of broken record, wherein the coercive force is 29.1kOe at the ambient temperature and 105.8kOe at 10K.

Description

Nano-scale textured rare earth permanent magnet material and preparation method thereof
Technical Field
The invention relates to the field of nano-scale rare earth permanent magnetic materials, in particular to a nano-scale textured rare earth permanent magnetic material and a preparation method thereof.
Background
Nanostructured permanent magnets have extremely high atom utilization efficiency and unique magnetic properties, and have attracted considerable attention in recent years in electronic systems, energy conversion and storage devices, and biotechnology. However, the nano-structured magnet can only be fully utilized by arranging the nano-scale grains of the hard magnetic phase into an anisotropic magnet, but the nano-materials prepared by the traditional methods (such as melt spinning and mechanical alloying) are always isotropic. Recent studies have attempted to exploit the properties of different crystallographic planes corresponding to different strain energies to promote the formation of anisotropy by introducing gradient fields, such as magnetic field assisted processes to enhance texture or large plastic deformations formed by hot-pressing thermal deformation. However, these methods inevitably introduce a lengthy heat treatment process, sometimes resulting in excessive growth of crystal grains and deterioration of magnetic properties.
The coercive force is a characteristic parameter index of the magnet material, and means that after saturation magnetization of the magnetic material, when an external magnetic field is returned to zero, the magnetic induction intensity B of the magnetic material is not returned to zero, and the magnetic induction intensity can be returned to zero only by adding a magnetic field with a certain magnitude in the direction opposite to the original magnetic field, so that the magnet material has high coercive force, and is a research hotspot and a general pursuit. Meanwhile, a permanent magnet with a texture on a nanoscale has better magnetic properties and thus has a wider application prospect, but the texture is usually difficult to form on the nanoscale because of the capability of accurately controlling the grain growth process. Over the past few decades, extensive research has been conducted to obtain high performance textured nanoscale magnets. However, to date, it remains a great challenge to produce structurally controlled nanostructured textured magnets while maintaining their high magnetic performance.
Disclosure of Invention
The invention aims to provide a nano-textured rare earth permanent magnet material and a preparation method thereof, which are used for solving the problems in the prior art, realize the anisotropy of the rare earth permanent magnet material by accurately controlling the size, the form and the orientation of hard phase grains, and obtain a textured nano structure.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a preparation method of a nano-textured rare earth permanent magnet material, which comprises the following steps:
(1) smelting the rare earth transition group intermetallic compound under a protective atmosphere to ensure that the components are uniform;
(2) mechanically crushing the smelted rare earth transition group intermetallic compound to prepare an amorphous ribbon;
(3) and (4) annealing the amorphous thin strip by adopting an electron beam to prepare the nano-textured magnet.
Further, the smelting mode in the step (1) is arc smelting or induction smelting; the protective atmosphere is argon.
Further, the general formula of the rare earth transition group intermetallic compound in the step (1) is RExFeyB6.2X is more than or equal to 12 and less than or equal to 18, y is more than or equal to 76 and less than or equal to 82, and x + y is 93.8; wherein RE is any one or any combination of more of rare earth elements Y, Ce, Nd, Pr, Sm, Gd, Tb, Dy, Ho, Er, Tm and Lu.
Further, in the step (2), a vacuum strip throwing machine is adopted to prepare the amorphous thin strip, and the roller speed of the vacuum strip throwing machine is 30-60 m/s.
Further, in the step (2), the width of the thin strip is 5-10 mm, and the thickness of the thin strip is 15-30 microns.
Further, in the step (3), the process of electron beam annealing is as follows: placing the amorphous thin strip into a vacuum cavity of an electron beam welding machine, enabling the thin strip to be attached to a roller surface downwards, to be attached to a water cooling table tightly, enabling a free surface to be upward, and carrying out electron beam irradiation, vacuumizing and then annealing the thin strip by using an electron beam.
Further, in the step (3), when the electron beam welding machine is used for annealing, the vacuum cavity is vacuumized to 2 × 10-3The water cooling temperature below the thin strip is set to be 5-20 ℃, the accelerating voltage of electron beams is 10 kilovolts, the beam current is 0.3-1.6 milliamperes, and the continuous heating time is 1.2 seconds.
The invention also provides the nano-textured rare earth permanent magnet material prepared by the preparation method of the nano-textured rare earth permanent magnet material, wherein the length-width ratio of crystal grains of the nano-textured magnet is between 1.3 and 2.8, and the coercive force is 29.1 to 105.8kOe at 10 to 300K.
The invention discloses the following technical effects:
the invention utilizes the electron beam rapid annealing method to prepare the nano-textured magnet, rapidly heats and cools the amorphous thin strip, can heat the thin strip to the specified crystallization temperature within 0.1 second, and realizes atom transfer and rearrangement of the amorphous thin strip within the time range of about 1 second. The method can realize the heating of the amorphous material to the crystallization temperature or even higher temperature within 1.2 seconds, complete crystallization, then quickly cool, generate a great temperature gradient field on the thin strip heating surface and the water cooling surface through quick heating and cooling, and induce the orientation arrangement of the hard magnetic phase crystal grains. The invention has short annealing time, high temperature rising speed and high preparation efficiency. Compared with the traditional annealing method, the method provided by the invention overcomes the problems of excessive growth and coarsening of crystal grains caused by long preparation process time, and is more efficient and more environment-friendly.
The nanoscale textured magnet pasting roll surface prepared by the invention shows strong c-axis (006) preferred orientation, the grain size is kept between hundred nanometers, the nanoscale textured magnet pasting roll surface shows large plastic deformation, the length-width ratio of the nanoscale textured magnet pasting roll surface is 1.3-2.8, and the coercivity corresponding to 10-300K is 29.1-105.8kOe on a magnetic test.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 shows Pr prepared at 0.4 mA, 0.8 mA, and 1.2 mA beam currents in examples 1, 2, and 3, respectively17.2Fe76.6B6.2XRD patterns of the free surface and the surface of the roller of the thin strip.
FIG. 2 is Pr prepared in example 117.2Fe76.6B6.2Atomic force microscope images (AFM) and magnetic force microscope images (MFM) of the free and nip roll surfaces of the thin strip.
FIG. 3 is Pr prepared in example 217.2Fe76.6B6.2Atomic force microscope images (AFM) and magnetic force microscope images (MFM) of the free and nip roll surfaces of the thin strip.
FIG. 4 is Pr prepared in example 317.2Fe76.6B6.2Atomic force microscope images (AFM) and magnetic force microscope images (MFM) of the free and nip roll surfaces of the thin strip.
FIG. 5 shows Pr prepared by irradiating the free surface and the roll surface with electron beams of 1.2 mA respectively in examples 1 and 417.2Fe76.6B6.2XRD patterns of a free surface and a roll attaching surface of the thin strip;
wherein (a) is Pr prepared by irradiating the electron beam to the roll surface in example 417.2Fe76.6B6.2XRD patterns of a free surface and a roll attaching surface of the thin strip; (b) pr prepared for the free surface irradiated with the Electron Beam of example 117.2Fe76.6B6.2XRD patterns of the free surface and the surface of the roller of the thin strip.
FIG. 6 shows Pr prepared at 0.4 mA, 0.8 mA, and 1.2 mA beam currents in examples 1, 2, and 3, respectively17.2Fe76.6B6.2And demagnetization curves (10K-300K) of the thin strip magnetic field at different temperatures along the direction parallel to the plane of the thin strip and the direction vertical to the plane of the thin strip.
Wherein(a) (b) (c) Pr prepared for 0.4 mA of example 117.2Fe76.6B6.2The thin-strip magnetic field is along the demagnetization curve (10K-300K) under different temperatures in the direction parallel to the plane of the thin strip and in the direction vertical to the plane of the thin strip; (d) (e) (f) Pr prepared for 0.8 mA of example 217.2Fe76.6B6.2The thin-strip magnetic field is along the demagnetization curve (10K-300K) under different temperatures in the direction parallel to the plane of the thin strip and in the direction vertical to the plane of the thin strip; (g) (h) (i) Pr prepared for 1.2 mA of example 317.2Fe76.6B6.2And demagnetization curves (10K-300K) of the thin strip magnetic field at different temperatures along the direction parallel to the plane of the thin strip and the direction vertical to the plane of the thin strip.
FIG. 7 shows Pr prepared at 0.4 mA, 0.8 mA, and 1.2 mA beam currents in examples 1, 2, and 3, respectively17.2Fe76.6B6.2And (4) carrying out statistics on the thin-strip Lorentz transmission electron microscope image and the grain size distribution.
Wherein (a) (d) is Pr prepared at 0.4 mA of example 117.2Fe76.6B6.2Counting the thin-strip Lorentz transmission electron microscope image and the grain size distribution; (b) (e) Pr prepared for 0.8 mA of example 217.2Fe76.6B6.2Counting the thin-strip Lorentz transmission electron microscope image and the grain size distribution; (c) (f) Pr prepared for 1.2 mA of example 317.2Fe76.6B6.2Thin-band lorentz transmission electron microscope images and grain size distribution statistics.
FIG. 8 is Ce prepared corresponding to 0.3 mA in example 512.2Fe81.6B6.2The result of the thin strip test, wherein (a) is the result of the magnetic property test and (b) is the microstructure.
FIG. 9 shows Nd prepared in example 6 at 1.2 mA12.2Fe81.6B6.2A thin band microstructure.
FIGS. 10 and 11 show experimental results for thin bands of Nd-Ce-Fe-B prepared in example 7 at 0.4, 0.8, 1.2, and 1.6 mA.
Wherein FIG. 10(a) (B) (c) (d) corresponds to the hysteresis loops of the magnetic field of Nd-Ce-Fe-B thin strip prepared by 0.4, 0.8, 1.2 and 1.6 milliamperes respectively along the direction parallel to the plane of the thin strip and the direction perpendicular to the plane of the thin strip; FIG. 11(a), (B), (c), (d) shows the statistical distribution of the grain sizes of Nd-Ce-Fe-B prepared at 0.4, 0.8, 1.2, 1.6 mA respectively, and (e), (f), (g), (h) shows the statistical distribution of the grain sizes of Nd-Ce-Fe-B prepared at 0.4, 0.8, 1.2, 1.6 mA respectively.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Further, for numerical ranges in this disclosure, it is understood that each intervening value, between the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The specification and examples are exemplary only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The "parts" in the present invention are all parts by mass unless otherwise specified.
Example 1
(1) The nominal component is Pr17.2Fe76.6B6.2The master alloy is melted by an induction arc furnace under the protection of argon atmosphere, and the melting is repeated for four times to ensure the uniform components.
The nominal component is Pr17.2Fe76.6B6.2The mother alloy raw materials of the alloy are Pr elementary substance with the purity of more than 99 percent, Fe elementary substance and FeB alloy (B:18.6 percent), and the Pr elementary substance is added by 5 percent in consideration of the burning loss and volatilization of rare earth metal.
(2) Preparation of thin Pr-Fe-B strip
Polishing the smelted master alloy, removing surface oxides, mechanically crushing the master alloy until the longest edge is less than 2cm, and obtaining Pr by a high-speed strip-spinning (molybdenum wheel, 35 m/s) method under the protection of argon atmosphere17.2Fe76.6B6.2And (3) an amorphous thin strip, wherein the width of the thin strip is 10 millimeters, and the thickness of the thin strip is 15 micrometers.
(3) Electron beam annealing process
Placing the prepared amorphous thin strip into a vacuum cavity of an electron beam welding machine with the roller surface facing downwards, tightly adhering to a water cooling table with the free surface facing upwards, and receiving electron beam irradiation with the air pressure in a bin lower than 2 × 10-3And uniformly setting the water cooling temperature to be 5 ℃. The accelerating voltage is 10 kilovolts, the focusing current is 165 milliamperes, the irradiation time is 1.2 seconds (0.1 second is increased, 1 second is kept warm, 0.1 second is reduced in voltage), the beam current is 0.4 milliamperes, and the nano-textured magnet is prepared.
The XRD diffraction pattern of the prepared nano-scale textured magnet is shown in figure 1, the microstructure is shown in figures 2 and 7, and the magnetic property test result is shown in figure 6.
Example 2:
(1) the nominal component is Pr17.2Fe76.6B6.2Under the protection of argon atmosphere, the master alloy is electrified by inductionSmelting in an arc furnace, and repeatedly smelting for four times to ensure uniform components.
The nominal component is Pr17.2Fe76.6B6.2The mother alloy raw materials of the alloy are Pr elementary substance with the purity of more than 99 percent, Fe elementary substance and FeB alloy (B:18.6 percent), and the Pr elementary substance is added by 5 percent in consideration of the burning loss and volatilization of rare earth metal.
(2) Preparation of thin Pr-Fe-B strip
Polishing the smelted master alloy, removing surface oxides, mechanically crushing until the longest edge is less than 2cm, and obtaining Pr by a high-speed strip throwing (molybdenum wheel, 35 m/s) method under the protection of argon atmosphere17.2Fe76.6B6.2And (3) an amorphous thin strip, wherein the width of the thin strip is 8 millimeters, and the thickness of the thin strip is 20 micrometers.
(3) Electron beam annealing process
The prepared amorphous thin strip is attached with the roller surface facing downwards, tightly attached to a water cooling table and the free surface facing upwards, and is irradiated by electron beams, and the air pressure in a bin is lower than 2 × 10-3And uniformly setting the water cooling temperature to be 5 ℃. The accelerating voltage is 10 kilovolts, the focusing current is 165 milliamps, the irradiation time is 1.2 seconds (0.1 second rise pressure, 1 second heat preservation and 0.1 second drop pressure) in total, the beam current is 0.8 milliamps, and the nano-textured magnet is prepared.
The XRD diffraction pattern of the prepared nano-scale textured magnet is shown in figure 1, the microstructure is shown in figures 3 and 7, and the magnetic property test result is shown in figure 6.
Example 3:
(1) the nominal component is Pr17.2Fe76.6B6.2The master alloy is melted by an induction arc furnace under the protection of argon atmosphere, and the melting is repeated for four times to ensure the uniform components.
The nominal component is Pr17.2Fe76.6B6.2The mother alloy raw materials of the alloy are Pr elementary substance with the purity of more than 99 percent, Fe elementary substance and FeB alloy (B:18.6 percent), and the Pr elementary substance is added by 5 percent in consideration of the burning loss and volatilization of rare earth metal.
(2) Preparation of thin Pr-Fe-B strip
Polishing the smelted master alloy, removing surface oxides, then mechanically crushing the master alloy in argon gasObtaining Pr by a high-speed melt spinning (molybdenum wheel, 30 m/s) method under the protection of atmosphere17.2Fe76.6B6.2And the width of the amorphous thin strip is 10 millimeters, and the thickness of the amorphous thin strip is 30 micrometers.
(3) Electron beam annealing process
The prepared amorphous thin strip is attached with the roller surface facing downwards, tightly attached to a water cooling table and the free surface facing upwards, and is irradiated by electron beams, and the air pressure in a bin is lower than 2 × 10-3And uniformly setting the water cooling temperature to be 5 ℃. The accelerating voltage is 10 kilovolts, the focusing current is 165 milliamps, the irradiation time is 1.2 seconds (0.1 second is increased, 1 second is kept warm, 0.1 second is reduced), the beam current is 1.2 milliamps, and the nano-textured magnet is prepared.
The XRD diffraction pattern of the prepared nano-scale textured magnet is shown in figure 1, the microstructure is shown in figures 4 and 7, and the magnetic property test result is shown in figure 6.
Example 4
(1) The nominal component is Pr17.2Fe76.6B6.2The master alloy is melted by an induction arc furnace under the protection of argon atmosphere, and the melting is repeated for four times to ensure the uniform components.
The nominal component is Pr17.2Fe76.6B6.2The mother alloy raw materials of the alloy are Pr elementary substance with the purity of more than 99 percent, Fe elementary substance and FeB alloy (B:18.6 percent), and the Pr elementary substance is added by 5 percent in consideration of the burning loss and volatilization of rare earth metal.
(2) Preparation of thin Pr-Fe-B strip
Polishing the smelted master alloy, removing surface oxides, then mechanically crushing, and obtaining Pr by a high-speed strip throwing (molybdenum wheel, 35 m/s) method under the protection of argon atmosphere17.2Fe76.6B6.2And (3) an amorphous thin strip, wherein the width of the thin strip is 5 mm, and the thickness of the thin strip is 25 microns.
(3) Electron beam annealing process
The prepared amorphous thin strip is tightly attached to a water cooling table with the free surface facing downwards and the roller facing upwards and is irradiated by electron beams, and the air pressure in a bin is lower than 2 × 10-3And uniformly setting the water cooling temperature to be 5 ℃. The accelerating voltage is 10 kV, the focusing current is 165 mA, and the irradiation time is longAnd (4) the total time is 1.2 seconds (0.1 second for increasing the pressure, 1 second for preserving the heat and 0.1 second for reducing the pressure), and the beam current is 1.2 milliamperes, so that the nano-textured magnet is prepared.
The XRD contrast diffractogram of the prepared nano-scale textured magnet is shown in figure 5.
Example 5
(1) Nominal component is Ce12.2Fe81.6B6.2The mother alloy is smelted by an electric arc smelting furnace under the protection of argon atmosphere, and the smelting is repeated for four times to ensure the uniformity of components.
The nominal component is Ce12.2Fe81.6B6.2The raw materials of the master alloy are a Ce simple substance with the purity of more than 99 percent, a Fe simple substance and a FeB alloy (B:18.6 percent), and the Ce simple substance is added by 5 percent in consideration of the burning loss and volatilization of rare earth metal.
(2) Preparation of thin Ce-Fe-B band
Polishing the smelted master alloy, removing surface oxides, then mechanically crushing, and obtaining Ce by a high-speed strip-spinning (copper wheel, 60 m/s) method under the protection of argon atmosphere12.2Fe81.6B6.2And (3) an amorphous thin strip, wherein the width of the thin strip is 7 millimeters, and the thickness of the thin strip is 18 micrometers.
(3) Electron beam annealing process
The prepared amorphous thin strip is attached with the roller surface facing downwards, tightly attached to a water cooling table and the free surface facing upwards, and is irradiated by electron beams, and the air pressure in a bin is lower than 2 × 10-3The water cooling temperature was set uniformly at 10 ℃. The accelerating voltage is 10 kilovolts, the focusing current is 165 milliamps, the irradiation time is 1.2 seconds (0.1 second rise pressure, 1 second heat preservation and 0.1 second drop pressure) in total, the beam current is 0.3 milliamps, and the nano-textured magnet is prepared.
The prepared nano-scale textured magnet has magnetic performance test as shown in fig. 8(a), and the microstructure as shown in fig. 8 (b).
Example 6
(1) The nominal component is Nd12.2Fe81.6B6.2The mother alloy is smelted by an electric arc smelting furnace under the protection of argon atmosphere, and the smelting is repeated for four times to ensure the uniformity of components.
The nominal component is Nd12.2Fe81.6B6.2The raw materials of the master alloy are Nd simple substance with the purity of more than 99 percent, Fe simple substance and FeB alloy (B:18.6 percent), and the Nd simple substance is added by 5 percent in consideration of the burning loss and volatilization of rare earth metal.
(2) Preparation of Nd-Fe-B thin strip
Polishing the smelted master alloy, removing surface oxides, then mechanically crushing, and obtaining Nd by a high-speed strip-spinning (copper wheel, 60 m/s) method under the protection of argon atmosphere12.2Fe81.6B6.2And (3) an amorphous thin strip, wherein the width of the thin strip is 10 millimeters, and the thickness of the thin strip is 23 micrometers.
(3) Electron beam annealing process
The prepared amorphous thin strip is attached with the roller surface facing downwards, tightly attached to a water cooling table and the free surface facing upwards, and is irradiated by electron beams, and the air pressure in a bin is lower than 2 × 10-3And uniformly setting the water cooling temperature to be 15 ℃. The accelerating voltage is 10 kilovolts, the focusing current is 165 milliamps, the irradiation time is 1.2 seconds (0.1 second rise pressure, 1 second heat preservation and 0.1 second drop pressure) in total, the beam current is 1.2 milliamps, and the nano-textured magnet is prepared.
The microstructure of the prepared nano-textured magnet is shown in figure 9.
Example 7
(1) Nominal composition is (Nd)0.8Ce0.2)12.2Fe81.6B6.2The mother alloy is melted by an electric arc melting furnace under the protection of argon atmosphere, and the melting is repeated for four times to ensure the uniformity of the components.
The nominal component is (Nd)0.8Ce0.2)12.2Fe81.6B6.2The raw materials of the master alloy are Nd and Ce simple substances with the purity of more than 99 percent, Fe simple substances and FeB alloy (B:18.6 percent), and the Nd and Ce simple substances are added by 5 percent in more consideration of the burning loss and volatilization of rare earth metal.
(2) Preparation of Nd-Ce-Fe-B thin strip
Polishing the smelted master alloy, removing surface oxides, then mechanically crushing, and obtaining (Nd) by a high-speed strip-spinning (copper wheel, 60 m/s) method under the protection of argon atmosphere0.8Ce0.2)12.2Fe81.6B6.2And (3) an amorphous thin strip, wherein the width of the thin strip is 10 millimeters, and the thickness of the thin strip is 15 micrometers.
(3) Electron beam annealing process
The prepared amorphous thin strip is attached with the roller surface facing downwards, tightly attached to a water cooling table and the free surface facing upwards, and is irradiated by electron beams, and the air pressure in a bin is lower than 2 × 10-3The water cooling temperature was set uniformly at 20 ℃. The accelerating voltage is 10 kilovolts, the focusing current is 165 milliamps, the irradiation time is 1.2 seconds (0.1 second pressure rise, 1 second heat preservation and 0.1 second pressure drop), the beam current is 0.4, 0.8, 1.2 and 1.6 milliamps, and the nano-textured magnet is prepared.
The magnetic performance of the prepared nano-scale textured magnet is shown in figure 10, and the microstructure is shown in figure 11.
As can be seen from FIG. 1, XRD diffraction results show that when the current exceeds 0.4 mAmp, the material is mainly composed of 2:14:1 phase, and most grains on the roller surface are arranged along the (00l) easy magnetization axis direction and are parallel to the temperature gradient field direction; the easy magnetization axis direction of most crystal grains of the free surface forms a certain included angle with the temperature gradient field direction. The conclusion comes from the roll facing Pr2Fe14The (006) and (008) diffraction peaks of B and the (221) diffraction peak of the free surface were significantly increased.
As can be seen from fig. 2-4, as the beam current increases, the magnetic moment in the face of the roller increases in the direction perpendicular to the in-plane arrangement, and reaches a maximum at 1.2 ma; as the beam current increases, the difference between the free and clubbed surfaces begins to decrease. When a small beam current texture structure just begins to form, the difference of the upper and lower magnetic domain structures begins to appear; when the beam current is 1.2 milliampere, the magnetic domain of the surface of the pasting roller is clearer and more distinguishable than the magnetic domain of the free surface, and is finer and denser.
When the beam current is too large to exceed 1.2 milliampere, the magnetic domains on the upper surface and the lower surface are almost completely consistent.
As can be seen from fig. 7, in the lorentz picture, as the beam current increases, the crystal grains grow gradually; meanwhile, the crystal grains are greatly deformed, flaky crystal grains begin to appear, and the length-width ratio is increased from 1.25 of 0.4 milliampere to 2.75 of 1.2 milliampere, which is the same as the shape of the texture magnet crystal grains generated by hot-pressing thermal deformation induction.
The appearance of the flaky crystal grains shows that after the induction of the temperature gradient field is carried out twice, a texture structure is formed, and the coercive force is greatly improved. The tendency of coercivity to vary with electron beam current is determined by the relationship between coercivity and grain size. These results again demonstrate that by controlling the beam current magnitude, i.e., the magnitude of the second temperature gradient, the grain shape, grain size, texture structure, and coercivity can be simultaneously controlled.
The method for preparing the nano-textured rare earth permanent magnet material by electron beam annealing can provide a basis for inducing textures of other nano systems, including magnetic recording, magnetic refrigeration materials and the like.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements made to the technical solution of the present invention by those skilled in the art without departing from the spirit of the present invention are intended to fall within the scope of the present invention defined by the claims.

Claims (8)

1. A preparation method of a nano-textured rare earth permanent magnet material is characterized by comprising the following steps:
(1) smelting the rare earth transition group intermetallic compound under a protective atmosphere to ensure that the components are uniform;
(2) mechanically crushing the smelted rare earth transition group intermetallic compound to prepare an amorphous ribbon;
(3) and (4) annealing the amorphous thin strip by adopting an electron beam to prepare the nano-textured magnet.
2. The method for preparing the nano-textured rare earth permanent magnet material according to claim 1, wherein the smelting mode in the step (1) is arc smelting or induction smelting; the protective atmosphere is argon.
3. The method for preparing nano-textured rare earth permanent magnet material according to claim 1Characterized in that the general formula of the rare earth transition group intermetallic compound in the step (1) is RExFeyB6.2X is more than or equal to 12 and less than or equal to 18, y is more than or equal to 76 and less than or equal to 82, and x + y is 93.8; wherein RE is any one or any combination of more of rare earth elements Y, Ce, Nd, Pr, Sm, Gd, Tb, Dy, Ho, Er, Tm and Lu.
4. The method for preparing a nano-textured rare earth permanent magnet material according to claim 1, wherein in the step (2), an amorphous thin belt is prepared by a vacuum belt throwing machine, and the roller speed of the vacuum belt throwing machine is 30-60 m/s.
5. The method for preparing nano-textured rare earth permanent magnet material according to claim 1, wherein in the step (2), the width of the thin strip is 5-10 mm, and the thickness of the thin strip is 15-30 μm.
6. The method for preparing the nano-textured rare earth permanent magnet material according to claim 1, wherein in the step (3), the electron beam annealing process comprises: placing the amorphous thin strip into a vacuum cavity of an electron beam welding machine, enabling the thin strip to be attached to a roller surface downwards, be attached to a water cooling table tightly, enabling a free surface to be upwards, receiving electron beam irradiation, and annealing the thin strip by applying the electron beam after vacuumizing.
7. The method for preparing nano-textured rare earth permanent magnet material according to claim 6, wherein in the step (3), when the annealing is carried out by using an electron beam welding machine, the vacuum cavity is vacuumized to 2 × 10-3The water cooling temperature below the thin strip is set to be 5-20 ℃, the accelerating voltage of electron beams is 10 kilovolts, the beam current is 0.3-1.6 milliamperes, and the continuous heating time is 1.2 seconds.
8. The nano-scale textured rare earth permanent magnet material prepared by the preparation method of the nano-scale textured rare earth permanent magnet material according to any one of claims 1 to 7, wherein the aspect ratio of the crystal grains of the nano-scale textured magnet is between 1.3 and 2.8, and the coercive force is between 29.1 and 105.8kOe at 10 to 300K.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06251920A (en) * 1993-02-26 1994-09-09 Hitachi Metals Ltd Rare earth element permanent magnet
CN101724800A (en) * 2009-12-11 2010-06-09 河北师范大学 Method for crystallizing nanometer composite permanent magnetic material
CN105321646A (en) * 2015-11-25 2016-02-10 中国科学院宁波材料技术与工程研究所 Nanocrystalline thermal deformation rare-earth permanent magnet with high coercivity and preparation method of nanocrystalline thermal deformation rare-earth permanent magnet
CN106205919A (en) * 2016-09-05 2016-12-07 北京大学 Use the method that nanometer two-phase composite permanent-magnetic material is quickly prepared in electron beam heating
CN108346508A (en) * 2017-01-23 2018-07-31 中国科学院宁波材料技术与工程研究所 A kind of preparation method of nanocrystalline complex phase Nd-Fe-B permanent magnet texturing enhancing

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH06251920A (en) * 1993-02-26 1994-09-09 Hitachi Metals Ltd Rare earth element permanent magnet
CN101724800A (en) * 2009-12-11 2010-06-09 河北师范大学 Method for crystallizing nanometer composite permanent magnetic material
CN105321646A (en) * 2015-11-25 2016-02-10 中国科学院宁波材料技术与工程研究所 Nanocrystalline thermal deformation rare-earth permanent magnet with high coercivity and preparation method of nanocrystalline thermal deformation rare-earth permanent magnet
CN106205919A (en) * 2016-09-05 2016-12-07 北京大学 Use the method that nanometer two-phase composite permanent-magnetic material is quickly prepared in electron beam heating
CN108346508A (en) * 2017-01-23 2018-07-31 中国科学院宁波材料技术与工程研究所 A kind of preparation method of nanocrystalline complex phase Nd-Fe-B permanent magnet texturing enhancing

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