CN109545491B - Neodymium-iron-boron permanent magnet material and preparation method thereof - Google Patents
Neodymium-iron-boron permanent magnet material and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
- H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
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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
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Abstract
The inventionDiscloses a preparation method of a neodymium iron boron permanent magnet material, which comprises the following steps: providing main phase alloy magnetic powder and AlCoFeB alloy magnetic powder, wherein the main phase alloy magnetic powder comprises (Nd, Pr)xFe(100‑x‑y‑z)ByMzX is more than or equal to 29wt% and less than or equal to 33wt%, y is more than or equal to 0.85wt% and less than or equal to 0.98wt%, z is more than 0 and less than or equal to 4wt%, M comprises any one or combination of more than two of Co, Al, Cu, Zr and Ga, and AlCoFeB alloy magnetic powder consists of AlaCobFecB100‑a‑b‑cA is more than or equal to 30wt% and less than or equal to 40wt%, b is more than or equal to 42wt% and less than or equal to 50wt%, c is more than or equal to 15wt% and less than or equal to 20 wt%; the main phase alloy magnetic powder and the AlCoFeB alloy magnetic powder are uniformly mixed, and the AlCoFeB alloy magnetic powder accounts for more than or equal to 0.1wt% and less than or equal to 1.5 wt%; and then carrying out post-treatment to obtain the neodymium iron boron permanent magnet material. The invention can effectively improve the coercive force of the neodymium iron boron permanent magnetic material.
Description
Technical Field
The invention relates to the technical field of rare earth permanent magnets, in particular to a neodymium iron boron permanent magnet material with excellent magnetic property and a preparation method thereof.
Background
The rare earth permanent magnet is a permanent magnet material taking an intermetallic compound formed by rare earth metal elements and transition metals as a matrix, and a neodymium iron boron permanent magnet (also called as an NdFeB permanent magnet) is a permanent magnet material with the highest magnetic performance at present. Since the invention in 1983, the sintered NdFeB permanent magnetic material receives wide attention all over the world and is mainly applied to the high-tech fields of aerospace, computers, oil exploitation, traffic, machinery, new energy, communication, national defense and the like. However, the rare earth raw materials for producing the neodymium iron boron permanent magnet, especially the rare earth for improving the intrinsic coercivity index, are high in price and occupy a very large proportion in the production cost of the magnet. Therefore, the problem of how to improve the utilization rate of rare earth and improve the performance of the magnet is always the focus of attention of manufacturers of neodymium iron boron magnets.
Disclosure of Invention
The invention mainly aims to provide a neodymium iron boron permanent magnet material and a preparation method thereof, so as to overcome the defects in the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a neodymium iron boron permanent magnet material, which comprises the following steps:
(1) providing a main phase alloy magnetic powder and an AlCoFeB alloy magnetic powder respectively, wherein the main phase alloy magnetic powder consists of (Nd, Pr)xFe(100-x-y-z)ByMzWherein x is more than or equal to 29wt% and less than or equal to 33wt%, y is more than or equal to 0.85wt% and less than or equal to 0.98wt%, z is more than 0 and less than or equal to 4wt%, M comprises any one or combination of more than two of Co, Al, Cu, Zr and Ga, and the AlCoFeB alloy magnetic powder is composed of AlaCobFecB100-a-b-cWherein a is more than or equal to 30wt% and less than or equal to 40wt%, b is more than or equal to 42wt% and less than or equal to 50wt%, and c is more than or equal to 15wt% and less than or equal to 20 wt%;
(2) uniformly mixing the main-phase alloy magnetic powder and the AlCoFeB alloy magnetic powder to obtain mixed magnetic powder, wherein the AlCoFeB alloy magnetic powder in the mixed magnetic powder accounts for more than or equal to 0.1wt% and less than or equal to 1.5 wt%;
(3) and carrying out post-treatment on the mixed magnetic powder to obtain the neodymium iron boron permanent magnet material.
The embodiment of the invention also provides the neodymium iron boron permanent magnet material prepared by the preparation method.
Compared with the prior art, the invention has the advantages that:
1) according to the preparation method of the neodymium iron boron permanent magnet material, the coercive force of the neodymium iron boron permanent magnet material can be effectively improved under the condition that the remanence is hardly reduced, and the performance of the neodymium iron boron permanent magnet material is not influenced.
2) Through adding the hot pressing technology in the post-processing process, the magnetic property of the neodymium iron boron permanent magnet material is improved, the effective utilization rate of rare earth is improved, and the magnetic property of the neodymium iron boron permanent magnet material is excellent.
3) The preparation method of the neodymium iron boron permanent magnet material provided by the invention has the advantages of cleanness, no pollution, low production cost, simplicity, feasibility and the like, and is easy to operate and industrialize.
Detailed Description
In view of the defects of the prior art, the inventor of the present invention has made extensive research and practice to propose the technical solution of the present invention, and further explains the technical solution, the implementation process and the principle, etc. as follows. It is to be understood, however, that within the scope of the present invention, each of the above-described features of the present invention and each of the features described in detail below (examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
One aspect of the embodiments of the present invention provides a method for preparing a neodymium iron boron permanent magnet material, including:
(1) respectively providing main phase alloy magnetic powder and AlCoFeB alloy magnetic powder, wherein the main phase alloy magnetic powder is composed of (Nd, Pr))xFe(100-x-y-z)ByMzWherein x is more than or equal to 29wt% and less than or equal to 33wt%, y is more than or equal to 0.85wt% and less than or equal to 0.98wt%, z is more than 0 and less than or equal to 4wt%, M comprises any one or combination of more than two of Co, Al, Cu, Zr and Ga, and the AlCoFeB alloy magnetic powder is composed of AlaCobFecB100-a-b-cWherein a is more than or equal to 30wt% and less than or equal to 40wt%, b is more than or equal to 42wt% and less than or equal to 50wt%, and c is more than or equal to 15wt% and less than or equal to 20 wt%;
(2) uniformly mixing the main-phase alloy magnetic powder and the AlCoFeB alloy magnetic powder to obtain mixed magnetic powder, wherein the AlCoFeB alloy magnetic powder in the mixed magnetic powder accounts for more than or equal to 0.1wt% and less than or equal to 1.5 wt%;
(3) and carrying out post-treatment on the mixed magnetic powder to obtain the neodymium iron boron permanent magnet material.
In some embodiments, the post-treatment comprises subjecting the mixed magnetic powder to orientation press forming, pre-sintering, hot pressing and tempering sequentially.
In some embodiments, step (1) specifically comprises:
mixing the materials according to the proportion of each element in the main-phase alloy magnetic powder;
mixing the prepared raw materials and smelting in an inert atmosphere to obtain a master alloy;
rapidly solidifying the master alloy to prepare an alloy sheet; and
and crushing the alloy sheet by hydrogen crushing and jet milling to obtain the main-phase alloy magnetic powder.
In some embodiments, the main phase alloy magnetic powder has a particle size of 1.0 μm to 4.0 μm.
In some embodiments, 32% ≦ a ≦ 38%, 42.5% ≦ b ≦ 49%, and 16.5% ≦ c ≦ 18.5%.
In some embodiments, step (2) specifically comprises: and mixing the main-phase alloy magnetic powder and the AlCoFeB alloy magnetic powder in a mixer according to the mass ratio of 99.9: 0.1-98.5: 1.5 for 0.5-5 h to obtain mixed magnetic powder.
In some preferred embodiments, the orientation profiling specifically comprises: and pressing the mixed magnetic powder into a mold under a magnetic field of 1.5T-2.5T, and pressing under isostatic pressure of 100 MPa-300 MPa to obtain a blank magnet.
In some preferred embodiments, the pre-sintering specifically comprises: after the mixed magnetic powder is subjected to orientation compression, the mixed magnetic powder is placed in a vacuum environment and sintered for 0.5 to 6 hours at the temperature of 700 to 950 ℃ to obtain a pre-sintered magnet.
The pre-sintering specifically comprises the steps of carrying out orientation compression on the mixed magnetic powder to obtain a blank magnet, and sintering the blank magnet in a vacuum sintering furnace at 700-950 ℃ for 0.5-6 h to obtain the pre-sintered magnet.
In some preferred embodiments, the hot pressing specifically comprises: and (3) pre-sintering the mixed magnetic powder, and then preserving heat and pressurizing for 1-15 min to obtain a preform.
Further, the temperature of the heat preservation is 700-900 ℃, and the pressure of the pressurization is 1-5 Mpa.
Furthermore, the temperature of the heat preservation is 790-820 ℃, and the pressure of the pressurization is 2.5-3.5 MPa.
The hot pressing specifically comprises the steps of putting the pre-sintered magnet into a vacuum hot press for heat preservation and pressurization after the mixed magnetic powder is pre-sintered, wherein the heat preservation temperature is 790-820 ℃, and the pressurization pressure is 2.5-3.5 MPa.
In some more preferred embodiments, the tempering treatment comprises sequentially performing primary tempering and secondary tempering in a vacuum environment or a protective atmosphere, wherein the temperature of the primary tempering is 800-950 ℃, the time of the primary tempering is 0.5-6 h, the temperature of the secondary tempering is 450-650 ℃, and the time of the secondary tempering is 0.5-6 h.
In some specific embodiments, the preparation method of the neodymium iron boron permanent magnet material comprises the following steps
(1) Respectively providing main phase alloy magnetic powder and AlCoFeB alloy magnetic powder, wherein the main phase alloy magnetic powder has a chemical formula of (Nd, Pr) according to mass percentagexFe(100-x-y-z)ByMzWherein x is more than or equal to 29 percent and less than or equal to 33 percent, y is more than or equal to 0.85 percent and less than or equal to 0.95 percent, z is more than 0 and less than or equal to 4 percent, M comprises any one or the combination of more than two of Co, Al, Cu, Zr and Ga, and the chemical formula of the AlCoFeB alloy magnetic powder is Al according to the mass percentageaCobFecB100-a-b-c;
(2) Uniformly mixing the main-phase alloy magnetic powder and the AlCoFeB alloy magnetic powder to obtain mixed magnetic powder, wherein the mass ratio of the AlCoFeB alloy magnetic powder in the mixed magnetic powder is more than or equal to 0.1% and less than or equal to 1.5%;
(3) carrying out orientation compression molding and pre-sintering on the obtained mixed magnetic powder:
pressing and molding the mixed magnetic powder at 1.5T-2.5T, then carrying out static pressure at 100 MPa-300 MPa to obtain a blank magnet, and then putting the blank magnet into a vacuum sintering furnace to be sintered for 0.5 h-6 h at 700-950 ℃ to obtain a pre-sintered magnet;
(4) carrying out hot pressing treatment on the obtained pre-sintered magnet:
putting the pre-sintered magnet into a vacuum hot press, preserving heat and pressurizing for 1-15 min, wherein the heat preservation temperature is 700-900 ℃, and the added pressure is 1-5 Mpa, so as to obtain a prefabricated body;
(5) obtaining the neodymium iron boron permanent magnet material through tempering treatment:
and sequentially carrying out primary tempering and secondary tempering on the obtained prefabricated body in a vacuum environment or a protective atmosphere, wherein the temperature of the primary tempering is 800-950 ℃, the time of the primary tempering is 0.5-6 h, the temperature of the secondary tempering is 450-650 ℃, and the time of the secondary tempering is 0.5-6 h.
In another aspect of the embodiment of the invention, the neodymium iron boron permanent magnet material prepared by the preparation method is also provided.
In some embodiments, the composition of the ndfeb permanent magnet material includes a main phase alloy magnetic powder and an AlCoFeB alloy magnetic powder.
The technical solution of the present invention is further described in detail by the following examples. However, the examples are chosen only for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
Example 1
The chemical formula of the main phase alloy magnetic powder is (NdPr)29Cu0.15Al0.05Zr0.3Co0.5Febal.B0.98The chemical formula of AlCoFeB alloy magnetic powder is Al35Co46.3Fe17.72B0.98. The doping amount of the AlCoFeB alloy magnetic powder is 1 percent of that of the mixed magnetic powder.
Preparation: the raw material with the purity of more than 99 percent is (NdPr)29Cu0.15Al0.05Zr0.3Co0.5Febal .B0.98Proportioning, preparing alloy sheet with thickness of about 0.3 mm by rapid hardening industry, and preparing powder with average grain size of 1-4 μm by hydrogen crushing and airflow milling. The AlCoFeB alloy is smelted, broken by hydrogen and ball-milled to obtain powder with the average grain diameter of 1-15 mu m. Mixing AlCoFeB alloy powder and main phase alloy magnetic powder according to the weight ratio of 1: 99, mixing in a mixer for 0.5-5 hours. Pressing and molding the uniformly mixed powder in an orientation field of 1.5T-2.5T, and then carrying out cold isostatic pressing under the pressure of 100-300 MPa to obtain a blank magnet; putting the blank magnet into a vacuum sintering furnace to be sintered for 0.5 to 6 hours at 700 to 950 ℃, then preserving the heat for 1 to 15 minutes at the temperature of 700 to 900 ℃ and under the pressure of 1 to 5MPa in a vacuum hot press, then carrying out primary tempering for 0.5 to 6 hours at the temperature of 800 to 950 ℃, and carrying out primary tempering at 450 ℃ for 0.5 to 6 hoursTempering at 650 ℃ for 0.5-6 h, performing air quenching and air cooling, cooling to room temperature, and discharging to obtain the neodymium iron boron permanent magnet material.
The prepared neodymium iron boron permanent magnet material is tested, the coercive force H of the obtained neodymium iron boron permanent magnet material is higher than that of a permanent magnet material which is not doped with AlCoFeB alloy magnetic powder by nearly 1.5kOe, and the result is shown in Table 1.
Table 1.
Br(kGs) | H(kOe) | (BH)m(MGOe) | |
Is not doped | 14.39 | 15.01 | 50.59 |
Doping is 1% | 14.15 | 16.48 | 51.41 |
Example 2
The manufacturing method is substantially the same as that of example 1 except that the chemical formula of the main phase alloy magnetic powder is (NdPr)29Cu0.15Al0.05Zr0.3Co0.5Febal.B0.94。
The prepared neodymium iron boron permanent magnet material is tested, and the coercive force H of the obtained neodymium iron boron permanent magnet material is 1.2kOe higher than that of the permanent magnet material which is not doped with AlCoFeB alloy magnetic powder, and the result is shown in Table 2.
Table 2.
Br(kGs) | H(kOe) | (BH)m(MGOe) | |
Is not doped | 14.34 | 14.98 | 50.42 |
Doping is 1% | 14.11 | 16.19 | 51.13 |
Example 3
The preparation method is basically the same as that of the embodiment 1, except that the doping amount of the AlCoFeB alloy magnetic powder is 0.5 percent of that of the mixed magnetic powder.
The prepared neodymium iron boron permanent magnet material is tested, and the coercive force H of the obtained neodymium iron boron permanent magnet material is higher than that of the permanent magnet material which is not doped with AlCoFeB alloy magnetic powder by 0.6kOe, and the result is shown in Table 3.
Table 3.
Br(kGs) | H(kOe) | (BH)m(MGOe) | |
Is not doped | 14.39 | 15.01 | 50.59 |
Doping 0.5% | 14.23 | 15.62 | 50.73 |
Example 4
The preparation method is basically the same as that of the embodiment 1, except that the doping amount of the AlCoFeB alloy magnetic powder is 1.5% of the mixed magnetic powder.
The prepared neodymium iron boron permanent magnet material is tested, the coercive force H of the obtained neodymium iron boron permanent magnet material is higher than that of the permanent magnet material which is not doped with AlCoFeB alloy magnetic powder by nearly 1.6kOe, and the result is shown in Table 4.
Table 4.
Br(kGs) | H(kOe) | (BH)m(MGOe) | |
Is not doped | 14.39 | 15.01 | 50.59 |
Doping is 1.5% | 14.12 | 16.59 | 51.33 |
Example 5
The preparation method is basically the same as that of the embodiment 1, except that the doping amount of the AlCoFeB alloy magnetic powder is 0.1% of the mixed magnetic powder.
The prepared neodymium iron boron permanent magnet material is tested, and the coercive force H of the obtained neodymium iron boron permanent magnet material is higher than that of the permanent magnet material which is not doped with AlCoFeB alloy magnetic powder by 0.1kOe, and the result is shown in Table 5.
Table 5.
Br(kGs) | H(kOe) | (BH)m(MGOe) | |
Is not doped | 14.39 | 15.01 | 50.59 |
Doping 0.1% | 14.37 | 15.12 | 50.62 |
Example 6
The preparation method is basically the same as that of example 1, except that the chemical formula of the AlCoFeB alloy magnetic powder is Al34Co47.5Fe17.56B0.94。
The prepared neodymium iron boron permanent magnet material is tested, and the coercive force H of the obtained neodymium iron boron permanent magnet material is 1.1kOe higher than that of the permanent magnet material which is not doped with AlCoFeB alloy magnetic powder, and the result is shown in Table 6.
Table 6.
Br(kGs) | H(kOe) | (BH)m(MGOe) | |
Is not doped | 14.39 | 15.01 | 50.59 |
Doping is 1% | 14.04 | 16.13 | 50.96 |
In addition, the inventor also carries out corresponding experiments by using other raw materials and other process conditions listed above to replace various raw materials and corresponding process conditions in the embodiments 1 to 6, and the contents to be verified are similar to the products in the embodiments 1 to 6. Therefore, the contents of the verification of the respective examples are not described herein, and the excellent points of the present invention will be described only by examples 1 to 6 as representative examples.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, and are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (7)
1. A preparation method of a neodymium iron boron permanent magnet material is characterized by comprising the following steps:
(1) providing a main phase alloy magnetic powder and an AlCoFeB alloy magnetic powder respectively, wherein the main phase alloy magnetic powder consists of (Nd, Pr)xFe(100-x-y-z)ByMzWherein x is more than or equal to 29wt% and less than or equal to 33wt%, y is more than or equal to 0.85wt% and less than or equal to 0.98wt%, z is more than 0 and less than or equal to 4wt%, M comprises any one or combination of more than two of Co, Al, Cu, Zr and Ga, and the AlCoFeB alloy magnetic powder is composed of AlaCobFecB100-a-b-cWherein a is more than or equal to 30wt% and less than or equal to 40wt%, b is more than or equal to 42wt% and less than or equal to 50wt%, and c is more than or equal to 15wt% and less than or equal to 20 wt%;
(2) uniformly mixing the main-phase alloy magnetic powder and the AlCoFeB alloy magnetic powder to obtain mixed magnetic powder, wherein the AlCoFeB alloy magnetic powder in the mixed magnetic powder accounts for more than or equal to 0.1wt% and less than or equal to 1.5 wt%;
(3) sequentially carrying out orientation compression, pre-sintering, hot pressing and tempering on the mixed magnetic powder to obtain a neodymium iron boron permanent magnet material;
wherein, the orientation die comprises: pressing the mixed magnetic powder into a shape under a magnetic field of 1.5T-2.5T, and then pressing under isostatic pressure of 100 MPa-300 MPa to obtain a blank magnet;
the pre-sintering treatment specifically comprises: after the mixed magnetic powder is subjected to orientation compression, placing the mixed magnetic powder in a vacuum environment, and sintering the mixed magnetic powder at the temperature of 700-950 ℃ for 0.5-6 h to obtain a pre-sintered magnet;
the hot pressing treatment specifically comprises: pre-sintering the mixed magnetic powder, and then preserving heat and pressurizing for 1-15 min at the temperature of 700-900 ℃ and the pressure of 1-5 Mpa to obtain a prefabricated body;
the tempering treatment specifically comprises: sequentially carrying out primary tempering and secondary tempering in a vacuum environment or a protective atmosphere, wherein the temperature of the primary tempering is 800-950 ℃, the time of the primary tempering is 0.5-6 h, the temperature of the secondary tempering is 450-650 ℃, and the time of the secondary tempering is 0.5-6 h.
2. The method according to claim 1, wherein the step (1) specifically comprises:
mixing the materials according to the proportion of each element in the main-phase alloy magnetic powder;
mixing the prepared raw materials and smelting in an inert atmosphere to obtain a master alloy;
rapidly solidifying the master alloy to prepare an alloy sheet; and
and crushing the alloy sheet by hydrogen crushing and jet milling to obtain the main-phase alloy magnetic powder.
3. The method of claim 1, wherein: the grain size of the main phase alloy magnetic powder is 1.0-4.0 mu m.
4. The method of claim 1, wherein: a is more than or equal to 32 percent and less than or equal to 38 percent, b is more than or equal to 42.5 percent and less than or equal to 49 percent, and c is more than or equal to 16.5 percent and less than or equal to 18.5 percent.
5. The method according to claim 1, wherein the step (2) specifically comprises: and mixing the main-phase alloy magnetic powder and the AlCoFeB alloy magnetic powder in a mixer according to the mass ratio of 99.9: 0.1-98.5: 1.5 for 0.5-5 h to obtain mixed magnetic powder.
6. The preparation method according to claim 1, wherein in the step (3), the hot pressing specifically comprises: the temperature is 790-820 ℃, and the pressure is 2.5-3.5 MPa.
7. The neodymium iron boron permanent magnet material prepared by the preparation method of any one of claims 1-6.
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