CN113223849A - High-performance and high-abundance rare earth iron boron permanent magnet material and preparation method thereof - Google Patents
High-performance and high-abundance rare earth iron boron permanent magnet material and preparation method thereof Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 84
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 80
- ZDVYABSQRRRIOJ-UHFFFAOYSA-N boron;iron Chemical compound [Fe]#B ZDVYABSQRRRIOJ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- RZJQYRCNDBMIAG-UHFFFAOYSA-N [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] Chemical class [Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Cu].[Zn].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Ag].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn].[Sn] RZJQYRCNDBMIAG-UHFFFAOYSA-N 0.000 claims abstract description 90
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 40
- 230000005291 magnetic effect Effects 0.000 claims abstract description 36
- 239000006247 magnetic powder Substances 0.000 claims abstract description 24
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 20
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 9
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 8
- 230000005294 ferromagnetic effect Effects 0.000 claims abstract description 7
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 6
- 238000005496 tempering Methods 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 31
- 238000005245 sintering Methods 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 20
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 15
- 239000000696 magnetic material Substances 0.000 claims description 15
- 238000003723 Smelting Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 239000001257 hydrogen Substances 0.000 claims description 11
- 238000009694 cold isostatic pressing Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 238000000748 compression moulding Methods 0.000 claims description 5
- 230000006835 compression Effects 0.000 claims description 3
- 238000007906 compression Methods 0.000 claims description 3
- 238000003801 milling Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 abstract description 7
- 230000005307 ferromagnetism Effects 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 4
- 230000002708 enhancing effect Effects 0.000 abstract description 3
- 239000000843 powder Substances 0.000 description 42
- 238000006356 dehydrogenation reaction Methods 0.000 description 12
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000956 alloy Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 238000010902 jet-milling Methods 0.000 description 5
- 238000004321 preservation Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000001965 increasing effect Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 230000002238 attenuated effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 229910001172 neodymium magnet Inorganic materials 0.000 description 2
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 description 1
- JSQFSWNWYZNVSY-UHFFFAOYSA-N [B].[Fe].[Nd].[Ce] Chemical compound [B].[Fe].[Nd].[Ce] JSQFSWNWYZNVSY-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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- 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
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- H01F41/0293—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 diffusion of rare earth elements, e.g. Tb, Dy or Ho, into permanent magnets
Abstract
The invention provides a high-performance and high-abundance rare earth iron boron permanent magnet material and a preparation method thereof. The preparation method comprises the following steps: the two kinds of main phase magnetic powder and auxiliary phase alloy are mixed to be pressed, sintered and tempered. The two main phase magnetic powders are respectively RExFe(98.56‑x‑y)ByM1.44、[RE(100‑a)LREa]xFe(98.56‑x‑y)ByM1.44The auxiliary phase alloy is RE(100‑i‑j)FeiM’jRE is Nd and Pr, LRE is La, Ce and Y, and M' is Ga, Al and Cu. According to the invention, RE elements in the auxiliary phase are preferentially diffused into the main phase rich in LRE, so that the magnetocrystalline anisotropy field of the main phase rich in LRE is enhanced, and a continuous non-ferromagnetic grain boundary phase consisting of RE, Fe and M' is formed, thereby reducing the ferromagnetism of the grain boundary, effectively improving the distribution of the grain boundary of the magnet, enhancing the magnetic decoupling capacity and greatly improving the coercive force.
Description
Technical Field
The invention relates to a rare earth iron boron permanent magnetic material, in particular to a high-performance and high-abundance rare earth iron boron permanent magnetic material and a preparation method thereof, belonging to the technical field of rare earth permanent magnetic materials.
Background
The neodymium iron boron is used as a third-generation rare earth permanent magnet material and has extremely high magnetic energy and coercive force. The preparation method mainly consumes medium and heavy rare earth such as Pr, Nd, Dy, Tb and the like. In recent years, as the price of heavy rare earth is continuously increased, the cost of a magnet is greatly increased, and the worry of the rare earth permanent magnet industry is caused, so that the reduction of the use of the heavy rare earth and the development of high-abundance rare earth permanent magnets become the focus of attention of the industry.
The La/Ce/Y element has high abundance and low raw material price, can form a 2:14:1 main phase with certain hard magnetic property, but has far lower intrinsic magnetism than Nd2Fe14B, at present, the La/Ce/Y is mainly used for partially replacing Nd and Pr to prepare the magnet with high cost performance. The loss of comprehensive magnetic property of the highly doped La/Ce/Y rare earth ferroboron magnet is serious, which is a key factor for restricting the large-scale production of the highly doped La/Ce/Y rare earth ferroboron magnet with high cost performance. The comprehensive magnetic performance of the magnet is equal to 2:14:1, the hard magnetic performance of the main phase is closely related to the microstructure, and the coercive force of the magnet can be effectively improved by adjusting the components and the distribution of the grain boundary.
For example, in CN106710768A, a method for increasing the coercivity of a neodymium-cerium-iron-boron sintered magnet by adding a hydride is disclosed, and the coercivity increases linearly with the addition of the hydride.
However, the conventional grain boundary addition method only increases the rare earth content in the magnet, the auxiliary phase RE uniformly enters the two main phases, and the difference of the magnetic anisotropy fields of the two main phases is still large from the whole view. Meanwhile, the conventional grain boundary adding method mainly focuses on improving the main phase, and the adjusting effect on the grain boundary is not obvious.
Therefore, it is needed to provide an auxiliary phase alloy that is significantly optimized for both grain boundaries and main phase, and a high-cost-performance high-doping high-abundance rare earth ferroboron magnet.
Disclosure of Invention
The invention mainly aims to provide a high-performance and high-abundance rare-earth iron-boron permanent magnet material and a preparation method thereof, so as to overcome the defects of 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 high-performance high-abundance rare earth iron boron permanent magnet material, which adopts a multi-alloy process, mechanically and uniformly mixes two main-phase alloy powders and an auxiliary-phase alloy powder according to a proportion, and obtains the high-performance high-abundance rare earth iron boron magnet through compression molding, sintering and tempering treatment, and the preparation method comprises the following specific steps:
respectively providing a first main phase alloy, a second main phase alloy and an auxiliary phase alloy, wherein the chemical formula of the first main phase alloy is RExFe(98.56-x-y)ByM1.44(LRE-free for short), and the chemical formula of the second main phase alloy is [ RE(100-a)LREa]xFe(98.56-x-y)ByM1.44(LRE is rich), wherein RE comprises any one or two combinations of Pr and Nd, LRE comprises any one or more combinations of La, Ce and Y, M comprises any one or more combinations of Al, Cu, Zr and Co, and a, x and Y respectively satisfy the following relations: a is more than or equal to 40 and less than or equal to 100, x is more than or equal to 29 and less than or equal to 34, and y is more than or equal to 0.9 and less than or equal to 0.93; the chemical formula of the auxiliary phase alloy is RE(100-i-j)FeiM’jRE comprises any one or two of Nd and Pr, M' comprises any one or more of Ga, Al and Cu, and i and j respectively satisfy the following relations: i is more than or equal to 6 and less than or equal to 6.5, and j is more than or equal to 11.5 and less than or equal to 12;
mechanically mixing the first main phase alloy, the second main phase alloy and the auxiliary phase alloy to obtain uniform mixed magnetic powder;
and sequentially carrying out compression molding, sintering and tempering on the mixed magnetic powder to obtain the high-performance and high-abundance rare earth iron boron permanent magnetic material.
The embodiment of the invention also provides a high-performance high-abundance rare earth iron boron permanent magnet material prepared by the method, which comprises an LRE-rich main phase, an LRE-free main phase and a continuous grain boundary phase, wherein the LRE-rich main phase has an LRE-rich shell layer, and the LRE-free main phase has an LRE-poor shell layer.
Further, the high-performance high-abundance rare-earth ferroboron permanent magnet material has a continuous thin-layer grain boundary structure comprising 6: 13: 1 non-ferromagnetic intergranular phase.
Compared with the prior art, the invention has the following beneficial effects:
1) the preparation method of the high-performance and high-abundance rare earth iron boron permanent magnet material provided by the invention can obviously improve the coercive force of the rare earth iron boron permanent magnet material under the condition of using highly doped La/Ce rare earth;
2) the preparation method of the high-performance high-abundance rare earth iron boron permanent magnet material provided by the invention has the advantages that RE elements contained in the auxiliary phase are preferentially diffused to the LRE-rich main phase, and the magnetocrystalline anisotropy field H of the auxiliary phase is improvedAThe magnetic dilution effect by LRE substitution was attenuated while not changing 2:14: stability of 1-phase structure, thereby improving the overall H of the magnetAThereby obviously improving the coercive force of the rare earth iron boron permanent magnetic material;
3) the preparation method of the high-performance high-abundance rare earth iron boron permanent magnet material provided by the invention can effectively reduce grain boundary REFE2The phase volume fraction effectively improves the magnetic performance deterioration caused by high doping LRE, simultaneously, because of the replacement of rare earth elements, the rare earth elements in the original LRE-rich main phase enter a crystal boundary, and the crystal boundary generates continuous RE consisting of RE, Fe and M6Fe13M '(M' is one or combination of Al, Ga or Cu) non-ferromagnetic grain boundary phase, reduces the ferromagnetism of the grain boundary, effectively improves the grain boundary distribution of the high-abundance rare earth ferroboron magnet, enhances the magnetic decoupling capacity, reduces the ferromagnetism of the grain boundary, and improves the grain boundaryThe wettability with the main phase, thereby obviously improving the coercive force of the rare earth iron boron permanent magnetic material;
4) after sintering and tempering are carried out on the high-performance high-abundance rare earth iron boron permanent magnet material, RE elements of auxiliary phase components are preferentially diffused into the main phase rich in LRE to form a (La, Ce, Pr, Nd) -Fe-B hard magnetic shell layer, so that a magnetocrystalline anisotropy field of the main phase rich in LRE is enhanced, and the coercive force of the high-abundance rare earth iron boron magnet is obviously improved;
5) the preparation method of the high-performance and high-abundance rare earth iron boron permanent magnet material provided by the invention has the advantages of low raw material price and simple and easy operation, and can be used for industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings needed to be used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a back-scattered scanning electron microscope photograph of a rare-earth ferroboron permanent magnetic material obtained in comparative example 1;
FIG. 2 is a scanning electron microscope photomicrograph of the back scattering of the high-performance and high-abundance rare-earth Fe-B permanent magnet material obtained in example 1 of the present invention;
FIG. 3 is a scanning electron microscope photomicrograph of the back scattering of the high-performance and high-abundance rare-earth Fe-B permanent magnet material obtained in example 1 of the present invention;
FIG. 4 is a back-scattering scanning electron microscope photograph of the high-performance and high-abundance rare-earth Fe-B permanent magnetic material obtained in example 1 of the present invention.
Detailed Description
In view of the defects in the prior art, the inventor of the present invention finds through long-term research and a large amount of practice that the technical scheme of the present invention is provided, and mainly provides a high-performance and high-abundance rare earth iron boron permanent magnet material and a preparation method thereof. The technical solution, its implementation and principles, etc. will be further explained as follows.
One aspect of the embodiment of the invention provides a high-performance high-abundance rare earth iron boron permanent magnet material which is prepared from two main phase alloys and an auxiliary phase alloy, wherein the general formulas of the two main phase alloys are respectively RE according to mass percentagexFe(98.56-x-y)ByM1.44And [ RE ](100-a)LREa]xFe(98.56-x-y)ByM1.44RE is one or two of Pr and Nd, LRE is any one or two of La, Ce and Y, M comprises any one or two of Al, Cu, Zr and Co, Fe is iron element, B is boron element; a. x and y respectively satisfy the following relations: a is more than or equal to 40 and less than or equal to 100, x is more than or equal to 29 and less than or equal to 34, and y is more than or equal to 0.9 and less than or equal to 0.93; the general formula of the auxiliary phase alloy is RE by mass percent(100-i-j)FeiM’jRE is any one or the combination of two of Nd and Pr, and M' is any one or the combination of two of Ga, Al and Cu; i and j satisfy the following relationships, respectively: i is more than or equal to 6 and less than or equal to 6.5, and j is more than or equal to 11.5 and less than or equal to 12.
In another aspect, the embodiment of the invention provides a multi-alloy process, which comprises the following steps of mechanically and uniformly mixing two main-phase alloy powders and an auxiliary-phase alloy powder in proportion, and performing compression molding, sintering and tempering to obtain a high-performance and high-abundance rare earth ferroboron magnet, wherein the specific steps comprise:
respectively providing a first main phase alloy, a second main phase alloy and an auxiliary phase alloy, wherein the chemical formula of the first main phase alloy is RExFe(98.56-x-y)ByM1.44The chemical formula of the second main phase alloy is [ RE(100-a)LREa]xFe(98.56-x-y)ByM1.44Wherein RE includes any one or two of Pr, Nd, etc., LRE includes any one or more of La, Ce, Y, etc., M includes any one or more of Al, Cu, Zr, Co, etc., a, x, Y areThe following relationships are satisfied: a is more than or equal to 40 and less than or equal to 100, x is more than or equal to 29 and less than or equal to 34, and y is more than or equal to 0.9 and less than or equal to 0.93; the chemical formula of the auxiliary phase alloy is RE(100-i-j)FeiM’jRE includes any one or a combination of two of Nd, Pr and the like, M' includes any one or a combination of two or more of Ga, Al, Cu and the like, and i and j satisfy the following relationships, respectively: i is more than or equal to 6 and less than or equal to 6.5, and j is more than or equal to 11.5 and less than or equal to 12;
mechanically mixing the first main phase alloy, the second main phase alloy and the auxiliary phase alloy to obtain uniform mixed magnetic powder;
and sequentially carrying out compression molding, sintering and tempering on the mixed magnetic powder to obtain the high-performance and high-abundance rare earth iron boron permanent magnetic material.
In some embodiments, the preparation method comprises: the first main phase alloy or the second main phase alloy is prepared by adopting a smelting sheet-hydrogen dehydrogenation breaking-airflow milling process, wherein the casting temperature is 1200-1400 ℃, and the hydrogen dehydrogenation breaking temperature is 320-580 ℃.
In some embodiments, the preparation method comprises: the auxiliary phase alloy is prepared by adopting a smelting sheet-hydrogen dehydrogenation breaking-airflow milling process, wherein the casting temperature is 1000-1100 ℃, and the hydrogen dehydrogenation breaking temperature is 320-580 ℃.
In some embodiments, the content of the auxiliary alloy in the mixed magnetic powder is 1 wt% to 8 wt%.
In some embodiments, the preparation method comprises: and carrying out magnetic field orientation compression on the mixed magnetic powder to obtain a green body, wherein the size of the magnetic field is 2.0T-2.5T.
In some embodiments, the preparation method comprises: and carrying out cold isostatic pressing treatment on the green body under the pressure of 150-200 MPa, and then carrying out sintering treatment at 1000-1090 ℃ for 2-6 h to obtain the sintered magnet.
In some embodiments, the preparation method comprises: and (3) carrying out primary tempering treatment on the sintered magnet at 890-930 ℃ for 2-4 h, then carrying out secondary tempering treatment at 460-580 ℃, keeping the temperature for 2-8 h, and then rapidly carrying out air cooling to room temperature under an inert atmosphere to obtain the high-performance and high-abundance rare earth iron boron permanent magnet.
In some specific embodiments, the preparation method of the high-performance and high-abundance rare-earth iron boron permanent magnet material comprises the following steps:
1) preparing two main-phase alloy powder and auxiliary-phase alloy powder by adopting SC, HD and JM processes;
2) uniformly mixing two main-phase alloy powder and auxiliary-phase alloy powder according to a certain proportion to obtain mixed magnetic powder, and carrying out magnetic field orientation compression on the mixed magnetic powder to obtain a green body, wherein the auxiliary-phase alloy powder accounts for 1-8 wt% of the mixed magnetic powder;
3) carrying out cold isostatic pressing treatment on the obtained green body under the pressure of 150-200 MPa;
4) putting the green body treated in the step 3) into a vacuum sintering furnace, and preserving heat for 2-6 hours at 1000-1090 ℃ to obtain a sintered magnet;
5) tempering the sintered magnet obtained in the step 4), performing primary tempering at 890-930 ℃, performing secondary tempering at 460-580 ℃, keeping the temperature for 2-8 hours, and then rapidly performing air cooling to room temperature under Ar atmosphere to obtain the high-performance and high-abundance rare earth iron boron permanent magnet.
Further, in some specific embodiments, the preparation method of the high-performance and high-abundance rare-earth-iron-boron permanent magnet material comprises the following specific steps:
(1) providing two main phase alloy powders prepared by smelting sheet-hydrogen breaking dehydrogenation-jet milling process, wherein the general formula is respectively RE according to mass percentagexFe(98.56-x-y)ByM1.44And [ RE ](100-a)LREa]xFe(98.56-x-y)ByM1.44RE is one or combination of Pr and Nd, LRE is one or combination of La, Ce and Y, M comprises any one or more of Al, Cu, Zr and Co, Fe is iron element, and B is boron element; a. x and y respectively satisfy the following relations: a is more than or equal to 40 and less than or equal to 100, x is more than or equal to 29 and less than or equal to 34, and y is more than or equal to 0.9 and less than or equal to 0.93.
(2) Provides an auxiliary phase alloy powder prepared by smelting sheet-hydrogen breaking dehydrogenation-jet milling process, the general formula of which is RE according to the mass percentage(100-i-j)FeiM’jRE is one or a combination of Nd and Pr, and M' is one or more of Ga, Al and Cu; i and j satisfy the following relationships, respectively: i is more than or equal to 6 and less than or equal to 6.5, and j is more than or equal to 11.5 and less than or equal to 12.
(3) And mechanically mixing the two main-phase alloy powders and the auxiliary-phase alloy powder to obtain uniform mixed magnetic powder, wherein the auxiliary-phase alloy powder accounts for 1-8 wt% of the mixed magnetic powder.
(4) And respectively carrying out orientation molding, cold isostatic pressing, sintering and secondary tempering on the mixed magnetic powder in a magnetic field to obtain the high-abundance rare earth ferroboron magnet.
Further, in the process of smelting the two main phase alloys into the sheet in the step (1), the pouring temperature is 1200-1400 ℃, the hydrogen dehydrogenation temperature is 320-580 ℃, and the particle size of the main phase alloy (the first main phase alloy or the second main phase alloy) powder is 2-3 μm. In the general formula of the main phase alloy, x is more than or equal to 30 and less than or equal to 30.5, y is more than or equal to 0.9 and less than or equal to 0.93, and M comprises any one or the combination of more than two of Al, Cu, Zr and Co.
Further, in the process of smelting the auxiliary phase alloy into the sheet in the step (2), the casting temperature is 1000-1100 ℃, the dehydrogenation temperature is 320-580 ℃, and the particle size of the auxiliary phase alloy powder is 0.5-2 μm. In the general formula of the auxiliary phase alloy, i is more than or equal to 6 and less than or equal to 6.5, j is more than or equal to 11.5 and less than or equal to 12, and M' is one or a combination of Ga, Al and Cu.
Further, the time for mixing the powder (i.e. mechanically mixing) in the step (3) is 1-3 h.
Further, the step (4) comprises: orienting and molding the mixed magnetic powder in a 2.0T-2.5T magnetic field; the cold isostatic pressure is 150 MPa-200 MPa; the sintering temperature is 1000-1090 ℃, and the temperature is kept for 2-6 h; the tempering treatment is carried out at a primary tempering temperature of 890-930 ℃, preferably 890-900 ℃, and the temperature is kept for 2-4 hours and then air cooling is carried out to the room temperature; and the secondary tempering temperature is 460-580 ℃, the temperature is kept for 2-8 h, and preferably 2-6 h, and then the air is cooled to the room temperature.
In conclusion, after sintering and tempering, RE elements of the auxiliary phase components are preferentially diffused into the main phase rich in LRE to form a (La, Ce, Pr, Nd) -Fe-B hard magnetic shell layer, so that the magnetocrystalline anisotropy field of the main phase rich in LRE is enhanced, and the coercive force of the high-abundance rare earth iron boron magnet is obviously improved. Due to the replacement of the rare earth element, the rare earth element in the original LRE-rich main phase enters a grain boundary to form a continuous non-ferromagnetic grain boundary phase consisting of RE, Fe and M', so that the grain boundary ferromagnetism is reduced, the grain boundary distribution of the high-abundance rare earth ferroboron magnet is effectively improved, the magnetic decoupling capacity is enhanced, and the coercive force of the high-abundance rare earth ferroboron magnet is greatly improved.
The invention can effectively improve the magnetic performance deterioration caused by high doping LRE, and simultaneously, the grain boundary generates continuous non-ferromagnetic phase formed by RE, Fe and Ga, thereby enhancing the magnetic decoupling capability and effectively improving the coercive force of the magnet.
In another aspect, the present invention provides a high performance and high abundance rare earth iron boron permanent magnetic material prepared by the foregoing method, which includes an LRE-rich main phase, an LRE-free main phase and a continuous grain boundary phase, wherein the LRE-rich main phase has an LRE-rich shell and the LRE-free main phase has an LRE-poor shell.
Furthermore, the high-performance high-abundance rare earth iron boron permanent magnet material has an (LRE, Pr, Nd) -Fe-B hard magnetic shell layer, and in the microstructure of the high-abundance rare earth iron boron permanent magnet material, the ratio of the content of RE in the auxiliary phase alloy contained in the LRE-rich shell layer to the content of RE in the auxiliary phase alloy contained in the LRE-poor shell layer is more than 1.5 at%, namely the ratio of the content of RE in the auxiliary phase RE contained in the LRE-rich shell layer to the content of RE in the auxiliary phase alloy contained in the LRE-poor shell layer is more than 1.5 at%, which indicates that the auxiliary phase RE preferentially enters the LRE-rich main phase to form the (LRE, Pr, Nd) -Fe-B hard magnetic shell layer, enhances the magnetocrystalline anisotropy field of the LRE-rich main phase, and greatly improves the coercive force of the magnet.
The RE element contained in the auxiliary phase of the high-performance high-abundance rare earth iron boron permanent magnetic material provided by the invention is preferentially diffused to the LRE-rich main phase, so that the magnetocrystalline anisotropy field H of the rare earth iron boron permanent magnetic material is improvedAThe magnetic dilution effect by LRE substitution was attenuated while not changing 2:14: stability of 1-phase structure, thereby improving the overall H of the magnetAThereby obviously improving the coercive force of the rare earth iron boron permanent magnetic material.
Further, the high-performance high-abundance rare-earth iron boron permanent magnet material has a continuous thin-layer grain boundary structure, which comprises 6: 13: 1 non-ferromagnetic intergranular phase, which can enhance the magnetic decoupling capacity, reduce the ferromagnetism of the grain boundary, and improve the wettability of the grain boundary and the main phase, thereby obviously improving the coercive force of the rare earth iron boron permanent magnetic material.
In order to make the objects, technical solutions and advantages of the present invention more clearly apparent, the technical solutions in the embodiments of the present invention will be described in detail below with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Comparative example 1
And 3, respectively carrying out hydrogen breaking and dehydrogenation treatment on the main phase alloy and the auxiliary phase alloy, wherein the dehydrogenation temperature is 320-580 ℃, and the time is 6 hours.
And 4, respectively preparing the main phase alloy and the auxiliary phase alloy into powder by a jet milling process, wherein the particle size of the powder is 2.0-2.5 microns and 1.1-1.9 microns.
And 6, sintering the magnet blank in vacuum, and performing secondary tempering treatment to obtain the high-abundance iron-boron magnet. Wherein the sintering temperature is 1090 ℃, and the temperature is kept for 4 hours; the primary tempering temperature is 900 ℃, and the temperature is kept for 2 hours; the secondary tempering temperature is 500 ℃, and the temperature is kept for 2 hours; and after the heat preservation is finished, air cooling is carried out to room temperature in Ar atmosphere, and the rare earth iron boron magnet is obtained and is defined as an initial magnet-1.
Comparative example 2
Except that two main phase chemical formulas in the step 1 are changed into Nd30Al0.2Cu0.2Zr0.1Co0.94FebalB0.9And [ Nd ]60(La35Ce65)40]30Al0.2Cu0.2Zr0.1Co0.94FebalB0.9The alloy powder uniformly mixed in step 5 is called as LaCe-30', other steps and process conditions are the same as those of example 1, and the obtained magnet is defined as an initial magnet-2.
Example 1
And 3, respectively carrying out hydrogen breaking and dehydrogenation treatment on the main phase alloy and the auxiliary phase alloy, wherein the dehydrogenation temperature is 320-580 ℃, and the time is 6 hours.
And 4, respectively preparing the main phase alloy and the auxiliary phase alloy into powder by a jet milling process, wherein the particle size of the powder is 2.0-2.5 microns and 1.1-1.9 microns.
And 6, sintering the magnet blank in vacuum, and performing secondary tempering treatment to obtain the high-performance and high-abundance rare earth iron boron permanent magnet material. Wherein the sintering temperature is 1090 ℃, and the temperature is kept for 4 hours; the primary tempering temperature is 900 ℃, and the temperature is kept for 2 hours; the secondary tempering temperature is 500 ℃, and the temperature is kept for 2 hours; and after the heat preservation is finished, air cooling to room temperature in Ar atmosphere to obtain the rare earth iron boron magnet, wherein the obtained magnets are respectively defined as 2 wt% -1, 4 wt% -1 and 6 wt% -1.
Example 2
And 3, respectively carrying out hydrogen breaking and dehydrogenation treatment on the main phase alloy and the auxiliary phase alloy, wherein the dehydrogenation temperature is 320-580 ℃, and the time is 6 hours.
And 4, respectively preparing the main phase alloy and the auxiliary phase alloy into powder by a jet milling process, wherein the particle size of the powder is 2.0-2.5 microns and 1.1-1.9 microns.
And 6, sintering the magnet blank in vacuum, and performing secondary tempering treatment to obtain the high-performance and high-abundance rare earth iron boron permanent magnet material. Wherein the sintering temperature is 1090 ℃, and the temperature is kept for 4 hours; the primary tempering temperature is 900 ℃, and the temperature is kept for 2 hours; the secondary tempering temperature is 500 ℃, and the temperature is kept for 2 hours; and after the heat preservation is finished, air cooling to room temperature in Ar atmosphere to obtain the rare earth iron boron magnet, wherein the obtained magnets are respectively defined as 2 wt% -2, 4 wt% -2 and 6 wt% -2.
Example 3
Removing stepIn step 2, the chemical formula of the auxiliary phase alloy is changed into Pr82Fe6Ga9Al3Other steps and process conditions were the same as in example 1, and the obtained magnets were defined as 2 wt% to 3, 4 wt% to 3 and 6 wt% to 3, respectively.
Comparative example 3
Except that two main phase chemical formulas in the step 1 are changed into Nd30.5Al0.2Cu0.2Zr0.1Co0.94FebalB0.93And Nd18.87Y7.7 5Al0.2Cu0.2Zr0.1Co0.98B0.94Fe70.96And in the step 5, the two main phase alloy powders are mixed according to the atomic ratio of 25: 75 (no LRE: rich LRE) ratio (hereinafter, referred to as Y-30 magnetic powder), and the other steps and process conditions were the same as in comparative example 1, and the obtained magnet was defined as an initial magnet-3.
Example 4
Except that two main phase chemical formulas in the step 1 are changed into Nd30.5Al0.2Cu0.2Zr0.1Co0.94FebalB0.93And Nd18.87Y7.7 5Al0.2Cu0.2Zr0.1Co0.98B0.94Fe70.96And in the step 5, the two main phase alloy powders are mixed according to the atomic ratio of 25: 75 (no LRE: LRE-rich) ratio (hereinafter, Y-30 magnetic powder), and the other steps and process conditions were the same as in example 1, and the obtained magnets were defined as 2 wt% -4, 4 wt% -4, and 6 wt% -4, respectively.
The magnetic properties of the high-abundance rare-earth ferroboron magnets prepared by the methods shown in the comparative examples and examples were tested, and the test results are shown in table 1.
TABLE 1 magnetic Properties of the magnets of each comparative example and example
As can be seen from table 1, the high-abundance rare earth iron boron permanent magnet prepared in embodiment 1 of the present invention has the best performance, and particularly, the coercivity of the magnet is significantly improved.
Microstructure tests of the high-abundance rare earth ferroboron magnets prepared by the methods of comparative example 1 and example 1 were performed to obtain corresponding back scattering scanning pictures, please refer to fig. 1, fig. 2 to fig. 4, and the content of elements in different main phases and grain boundaries was determined by an EDS spectrometer, and the test results are shown in tables 2 and 3.
Table 2 elemental content (at.%) of the different main phases
TABLE 3 elemental content (at.%) of different iron-rich grain boundaries
It can be seen from table 2 that the high-abundance rare-earth ferroboron permanent magnet prepared by the methods of comparative example 1 and example 1 of the present invention has two main phase structures, and after the addition of the auxiliary phase, RE in the auxiliary phase preferentially diffuses to the LRE-rich main phase, thereby enhancing the magnetocrystalline anisotropy field of the LRE-rich main phase, reducing the magnetic dilution caused by LRE substitution, and significantly improving the coercive force of the magnet.
As can be seen from Table 3, the high-abundance rare earth iron boron permanent magnet prepared by the method of example 1 of the invention has RE6Fe13Ga nonferromagnetic grain boundary phase while reducing the amount of REFE in the grain boundary of the magnet prepared in comparative example 12The content of the phase reduces the ferromagnetism of the magnet grain boundary, and is beneficial to the magnetic decoupling of adjacent main phases, thereby improving the coercivity.
Example 5
The present embodiment is different from embodiment 1 in that:
in the two main phase alloy powders, the LRE adopts La, and a is 40;
and 5, adding the two main phase alloy powders and the auxiliary phase alloy powder according to the mass ratio of 99: 1, performing orientation forming in a 2.5T magnetic field, and performing cold isostatic pressing under the pressure of 180MPa to prepare a magnet blank.
And 6, sintering the magnet blank in vacuum, and performing secondary tempering treatment to obtain the high-performance and high-abundance rare earth iron boron permanent magnet material. Wherein the sintering temperature is 1050 ℃, and the temperature is kept for 2 h; the primary tempering temperature is 890 ℃, and the temperature is kept for 4 hours; the secondary tempering temperature is 580 ℃, and the temperature is kept for 2 hours; and after the heat preservation is finished, air cooling is carried out to room temperature under Ar atmosphere, and the rare earth iron boron magnet can be obtained.
Example 6
The present embodiment is different from embodiment 1 in that:
and 5, adding the two main phase alloy powders and the auxiliary phase alloy powder in a mass ratio of 92: and 8, performing orientation forming in a 2.2T magnetic field, and performing cold isostatic pressing under the pressure of 200MPa to prepare a magnet blank.
And 6, sintering the magnet blank in vacuum, and performing secondary tempering treatment to obtain the high-performance and high-abundance rare earth iron boron permanent magnet material. Wherein the sintering temperature is 1000 ℃, and the temperature is kept for 6 h; the primary tempering temperature is 930 ℃, and the temperature is kept for 2 hours; the secondary tempering temperature is 460 ℃, and the temperature is kept for 8 hours; and after the heat preservation is finished, air cooling is carried out to room temperature under Ar atmosphere, and the rare earth iron boron magnet can be obtained.
In addition, the inventor also carries out corresponding experiments by using other raw materials and other process conditions listed above instead of various raw materials and corresponding process conditions in the examples 1 to 6, and the contents to be verified are similar to the products in the examples 1 to 6. Therefore, the contents of the verification of each example are not described herein one by one, and only examples 1 to 6 are used as representatives to describe the excellent points of the present invention.
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 (10)
1. A preparation method of a high-performance and high-abundance rare earth iron boron permanent magnet material is characterized by comprising the following steps:
respectively providing a first main phase alloy, a second main phase alloy and an auxiliary phase alloy, wherein the chemical formula of the first main phase alloy is RExFe(98.56-x-y)ByM1.44The chemical formula of the second main phase alloy is [ RE(100-a)LREa]xFe(98.56-x-y)ByM1.44Wherein RE comprises any one or two of Pr and Nd, LRE comprises any one or more of La, Ce and Y, M comprises any one or more of Al, Cu, Zr and Co, and a, x and Y respectively satisfy the following relations: a is more than or equal to 40 and less than or equal to 100, x is more than or equal to 29 and less than or equal to 34, and y is more than or equal to 0.9 and less than or equal to 0.93; the chemical formula of the auxiliary phase alloy is RE(100-i-j)FeiM’jRE comprises any one or two of Nd and Pr, M' comprises any one or more of Ga, Al and Cu, and i and j respectively satisfy the following relations: i is more than or equal to 6 and less than or equal to 6.5, and j is more than or equal to 11.5 and less than or equal to 12;
mechanically mixing the first main phase alloy, the second main phase alloy and the auxiliary phase alloy to obtain uniform mixed magnetic powder;
and sequentially carrying out compression molding, sintering and tempering on the mixed magnetic powder to obtain the high-performance and high-abundance rare earth iron boron permanent magnetic material.
2. The method of claim 1, wherein: the grain size of the first main phase alloy or the second main phase alloy is 2-3 μm, preferably, in the chemical formula of the first main phase alloy or the second main phase alloy, x is more than or equal to 30 and less than or equal to 30.5, and y is more than or equal to 0.9 and less than or equal to 0.93.
3. The method of claim 1, wherein: the auxiliary phase alloy is prepared by adopting a smelting sheet-hydrogen breaking dehydrogenation-airflow milling process, and the particle size of the auxiliary phase alloy is 0.5-2 mu m.
4. The method of claim 1, wherein: the content of the auxiliary phase alloy in the mixed magnetic powder is 1 wt% -8 wt%.
5. The method according to claim 1, comprising: and carrying out magnetic field orientation compression on the mixed magnetic powder to obtain a green body, wherein the size of the magnetic field is 2.0T-2.5T.
6. The preparation method according to claim 5, characterized by specifically comprising: and carrying out cold isostatic pressing treatment on the green body under the pressure of 150-200 MPa, and then carrying out sintering treatment at 1000-1090 ℃ for 2-6 h to obtain the sintered magnet.
7. The method according to claim 6, comprising: carrying out primary tempering treatment on the sintered magnet at 890-930 ℃ for 2-4 h, then carrying out secondary tempering treatment at 460-580 ℃, keeping the temperature for 2-8 h, preferably 2-6 h, and then rapidly carrying out air cooling to room temperature under an inert atmosphere to obtain the high-performance and high-abundance rare earth iron boron permanent magnet; preferably, the temperature of the primary tempering treatment is 890-900 ℃.
8. A high-performance high-abundance rare-earth ferroboron permanent magnet material prepared by the method of any one of claims 1 to 7, characterized in that: the high-abundance rare earth iron boron permanent magnet material comprises an LRE-rich main phase, an LRE-free main phase and a continuous grain boundary phase, wherein the LRE-rich main phase is provided with an LRE-rich shell layer, and the LRE-free main phase is provided with an LRE-poor shell layer.
9. The high-performance high-abundance rare-earth ferroboron permanent magnet material of claim 8, wherein: the high-performance high-abundance rare earth iron boron permanent magnet material is provided with a (LRE, Pr, Nd) -Fe-B hard magnetic shell layer; preferably, in the high-performance high-abundance rare-earth iron boron permanent magnet material, the ratio of the content of RE in the auxiliary phase alloy contained in the LRE-rich shell layer to the content of RE in the auxiliary phase alloy contained in the LRE-poor shell layer is more than 1.5.
10. The high-performance high-abundance rare-earth ferroboron permanent magnet material of claim 8, wherein: the high-performance high-abundance rare earth iron boron permanent magnet material has a continuous thin-layer grain boundary structure, and comprises 6: 13: 1 non-ferromagnetic intergranular phase.
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Application publication date: 20210806 |