CN116844812A - Rare earth permanent magnet alloy and preparation method thereof - Google Patents

Rare earth permanent magnet alloy and preparation method thereof Download PDF

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CN116844812A
CN116844812A CN202310745614.1A CN202310745614A CN116844812A CN 116844812 A CN116844812 A CN 116844812A CN 202310745614 A CN202310745614 A CN 202310745614A CN 116844812 A CN116844812 A CN 116844812A
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rare earth
equal
permanent magnet
earth permanent
magnet alloy
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岳明
秦渊
刘卫强
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Beijing University of Technology
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Beijing University of Technology
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    • H—ELECTRICITY
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
    • H—ELECTRICITY
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    • 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
    • H01F1/0576—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 pressed, e.g. hot working
    • 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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    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H01F41/0266—Moulding; Pressing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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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
    • H01F41/0293—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

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Abstract

The invention belongs to the technical field of rare earth magnetic materials, and in particular relates to a rare earth permanent magnet alloy and a preparation method thereof, wherein the rare earth permanent magnet alloy has Nd x (La a Ce 1‑a ) y Fe 100‑x‑y‑w‑t‑e‑z Ga t Cu e M z B w The composition is represented by the formula, wherein M is one or more of Al, nb, ti, co, zr; x is more than or equal to 16.0 and less than or equal to 33.0,0.05, a is more than or equal to 0.20,1.0, y is more than or equal to 12.0,0.3, t is more than or equal to 1.0,0.3, e is more than or equal to 1.0,0.1, z is more than or equal to 1.0,0.8 and w is more than or equal to 3552Less than or equal to 1.0. The rare earth permanent magnet alloy macroscopically regulates and controls the inter-crystalline phase components by introducing La element and regulating the Ga and Cu proportion, promotes the diffusion between the rare earth elements, ensures that a large amount of the rare earth elements are gathered at the grain boundaries, is favorable for forming uniform and continuous rare earth-rich phase thin layers between adjacent main phase grains, inhibits the exchange coupling effect between the main phase grains, and remarkably improves the magnetic performance.

Description

Rare earth permanent magnet alloy and preparation method thereof
Technical Field
The invention belongs to the technical field of rare earth magnetic materials, and particularly relates to a rare earth permanent magnet alloy and a preparation method thereof.
Background
The Nd-Fe-B magnet has excellent magnetic performance and is widely applied to the fields of wind motors, new energy automobiles, intelligent electronic equipment and the like. However, with the increasing demand of the society for Nd-Fe-B magnets, excessive use of rare earth element Nd, pr, dy, tb is caused, so that abundant and cheap La and Ce elements are backlogged in a large amount, and the rare earth resource utilization is unbalanced. Therefore, la and Ce elements are used for preparing the high-performance sintered magnet, which has very important significance for saving production cost and balancing utilization of rare earth resources.
From the viewpoints of balanced utilization of resources and economical applicability, substitution of La and Ce for Nd and Pr has become a preferred choice for manufacturing Nd-Fe-B magnets, but addition of a large amount of La and Ce causes a sharp decrease in magnetic properties, particularly serious deterioration in coercive force, due to poor intrinsic properties of La and Ce. In order to improve the magnetic properties of the magnet, researchers have conducted a great deal of research mainly from the following two aspects: first, the anisotropic field of the main phase grains is increased to increase the coercive force, such as CN201210315684.5 and CN201911156116.3; secondly, a uniform and continuous rare earth-rich phase thin layer is formed through grain boundary optimization to weaken the exchange coupling effect, and the grain inversion in the magnetizing process is restrained to improve the coercive force, such as CN201310035673.6. The prior research work is focused on improving the anisotropic field and grain boundary optimization of main phase grains by improving the preparation method, and the prior art mainly uses a double alloy method and a grain boundary diffusion method, but the mutual diffusion behavior of rare earth elements in a LaCe-based magnet prepared by adopting the double alloy method is difficult to accurately control, and elements with higher diffusion speed such as Ce and the like are easy to form thicker high-abundance rare earth element-rich shells in a long-time high-temperature sintering process, so that the rare earth element-rich shells have lower magnetic crystal anisotropic field and are easy to become nucleation sites in a reverse magnetization process, and the coercive force is reduced. The grain boundary diffusion method is only suitable for thin magnets, and cannot prepare thicker large-block magnets due to the influence of diffusion depth.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a rare earth permanent magnet alloy and a preparation method thereof, wherein the rare earth permanent magnet alloy is single main phase (Nd, la, ce) -Ga-Cu-M-Fe-B permanent magnet alloy, la replaces Ce element and adjusts the proportion of trace elements Ga and Cu to macroscopically regulate and control inter-crystalline phase components, promote the diffusion between Nd/La/Ce rare earth elements, enable a large amount of rare earth elements to gather at grain boundaries, optimize rare earth-rich phase components and form uniform and continuous rare earth-rich phase thin layers between adjacent main phase grains, inhibit the exchange coupling effect between the main phase grains and remarkably improve magnetic properties (remanence, coercive force and maximum magnetic energy product).
Specifically, the invention provides the following technical scheme:
rare earth permanent magnet alloy having Nd x (La a Ce 1-a ) y Fe 100-x-y-w-t-e- z Ga t Cu e M z B w The composition of the representation, wherein:
m is one or more than one of Al, nb, ti, co, zr;
x, y, t, e, z, w is the weight percent (wt.%) of each element, and the range is that x is more than or equal to 16.0 and less than or equal to 33.0,1.0, y is more than or equal to 12.0,0.3 and less than or equal to 1.0,0.3 and less than or equal to e and less than or equal to 1.0,0.1, z is more than or equal to 1.0,0.8 and less than or equal to w is more than or equal to 1.0;
a is the weight percentage content of La in the whole of La and Ce, and the range of the weight percentage content of the La is more than or equal to 0.05 and less than or equal to 0.20.
Preferably, 28.0.ltoreq.x+y.ltoreq.34.0.
Preferably, y/(x+y) =5.0 to 40.0wt.%.
The invention discovers that the total amount of rare earth is controlled to be 28.0-34.0 wt%, and the total amount of La and Ce accounts for 5.0-40.0 wt% of the total amount of rare earth, so that the remanence, coercive force and maximum magnetic energy product are further improved.
Preferably, M is Co and Zr in a mass ratio of 0.1 to 0.6:0.12.
The invention also provides a preparation method of the rare earth permanent magnet alloy, which comprises the following steps:
obtaining rare earth permanent magnet alloy magnetic powder by means of air flow grinding; the rare earth permanent magnet alloy magnetic powder has Nd x (La a Ce 1-a ) y Fe 100-x-y-w-t-e-z Ga t Cu e M z B w The composition of the representation, wherein:
m is one or more than one of Al, nb, ti, co, zr;
x, y, t, e, z, w is the weight percent (wt.%) of each element, and the range is that x is more than or equal to 16.0 and less than or equal to 33.0,1.0, y is more than or equal to 12.0,0.3 and less than or equal to 1.0,0.3 and less than or equal to e and less than or equal to 1.0,0.1, z is more than or equal to 1.0,0.8 and less than or equal to w is more than or equal to 1.0; a is the weight percentage content of La in the whole of La and Ce, and the range of a is more than or equal to 0.05 and less than or equal to 0.20;
and sequentially carrying out magnetic field orientation molding, cold isostatic pressing, vacuum sintering and secondary tempering heat treatment on the rare earth permanent magnet alloy magnetic powder to obtain the rare earth permanent magnet alloy.
Preferably, x+y is 28.0 or less and 34.0 or less;
and/or y/(x+y) =5.0 to 40.0wt.%;
and/or M is Co and Zr with the mass ratio of 0.2-0.5:0.12.
Preferably, the preparation method of the rare earth permanent magnet alloy magnetic powder specifically comprises the following steps:
(1) Proportioning according to the proportion of each element in the rare earth permanent magnet alloy magnetic powder;
(2) Mixing the prepared raw materials containing the elements, smelting, and then preparing quick-setting tablets;
(3) Carrying out hydrogen breaking treatment on the rapid hardening sheet, and obtaining coarse magnetic powder after dehydrogenation;
(4) Uniformly mixing the coarse magnetic powder, a first lubricant and a first antioxidant, and performing air flow grinding to obtain rare earth permanent magnet alloy magnetic powder, wherein the average particle size of the rare earth permanent magnet alloy magnetic powder is 2.5-3.0 mu m.
Further preferably, the thickness of the rapid hardening sheet is 200-350 μm;
and/or the first lubricant is used in an amount of 0.01 to 3% and the first antioxidant is used in an amount of 0.01 to 3% based on the weight of the coarse magnetic powder.
Preferably, the rare earth permanent magnet alloy magnetic powder is sequentially subjected to magnetic field orientation molding and cold isostatic pressing, and the method specifically comprises the following steps:
uniformly mixing the rare earth permanent magnet alloy magnetic powder, a second lubricant and a second antioxidant, and then carrying out orientation profiling in a magnetic field with the magnetic field strength of 1.5-1.8T under the protection of inert atmosphere to obtain a coarse blank;
and (3) carrying out cold isostatic pressing after vacuum packaging on the coarse embryo, wherein the pressure of the cold isostatic pressing is 210-230 MPa, and the pressure maintaining time is 120-240 s.
Further preferably, the second lubricant is used in an amount of 0.01 to 3% and the second antioxidant is used in an amount of 0.01 to 3% based on the weight of the coarse magnetic powder.
Preferably, the sintering temperature of the vacuum sintering is 1040-1080 ℃, and the heat preservation time is 3-5 h.
Preferably, the secondary tempering heat treatment specifically comprises: firstly, heat treatment is carried out for 3-5 hours at 800-900 ℃, and then heat treatment is carried out for 3-5 hours at 400-500 ℃.
The invention is not particularly limited to any one of the lubricants and any one of the antioxidants, and the lubricants and the antioxidants which are conventional in the art can be adopted.
Compared with the prior art, the invention has the following advantages:
according to the rare earth permanent magnet alloy provided by the invention, the inter-crystalline phase components are macroscopically regulated and controlled by introducing La elements and regulating Ga and Cu proportions, so that diffusion among Nd/La/Ce rare earth elements is promoted, a large amount of rare earth elements are gathered at grain boundaries, rare earth-rich phase components are optimized, uniform and continuous rare earth-rich phase thin layers are formed among adjacent main phase grains, exchange coupling effect among the main phase grains is inhibited, and magnetic performance is remarkably improved;
the existing high-abundance rare earth permanent magnet material mainly comprises a Ce-containing magnet, and La element is less in application due to poor intrinsic magnetic property. According to the rare earth permanent magnet alloy provided by the invention, la element is introduced into the Ce-containing magnet, and compared with a magnet prepared by not adding La element, the obtained magnet has the advantages that the remanence, the coercive force and the maximum magnetic energy product are greatly improved, the efficient utilization of La element is realized, and the rare earth permanent magnet alloy has important significance in promoting the balance utilization of rare earth resources and reducing the production cost.
Drawings
Fig. 1 is a comparison of coercive force effects of example 2 and comparative example 1, in which the abscissa is coercive force and the ordinate is remanence.
Detailed Description
The invention provides a rare earth permanent magnet alloy, the nominal component of which is Nd x (La a Ce 1-a ) y Fe 100-x-y-w-t-e-z Ga t Cu e M z B w (wt.%) M is one or several of Al, nb, ti, co, zr, wherein x, a, y, t, e, z, w satisfies the following relationship: x is more than or equal to 16.0 and less than or equal to 33.0,0.05, a is more than or equal to 0.20,1.0, y is more than or equal to 12.0,0.3, t is more than or equal to 1.0,0.3, e is more than or equal to 1.0,0.1, z is more than or equal to 1.0,0.8, and w is more than or equal to 1.0. The La element is used for replacing Ce element and regulating the proportion of trace elements Ga and Cu to macroscopically regulate the inter-crystalline phase components, promote the diffusion between Nd/La/Ce rare earth elements, enable a large amount of rare earth elements to be gathered at the grain boundaries, optimize the rare earth-rich phase components and form a uniform continuous rare earth-rich phase thin layer between adjacent main phase grains, inhibit the exchange coupling effect between the main phase grains, and simultaneously improve the remanence, coercive force and maximum magnetic energy product of the single main phase (Nd, la, ce) -Ga-Cu-M-Fe-B sintered permanent magnet material.
In a preferred embodiment, 28.0.ltoreq.x+y.ltoreq.34.0, y/(x+y) =5.0 to 40.0wt.%, M is Co and Zr in a mass ratio of 0.2 to 0.5:0.12.
The invention also provides a preparation method of the rare earth permanent magnet alloy, which comprises the following steps:
obtaining rare earth permanent magnet alloy magnetic powder by means of air flow grinding;
and sequentially carrying out magnetic field orientation molding, cold isostatic pressing, vacuum sintering and secondary tempering heat treatment on the rare earth permanent magnet alloy magnetic powder to obtain the rare earth permanent magnet alloy.
In a preferred embodiment, the preparation method specifically comprises the following steps:
(1) Based on the nominal composition of the alloy, nd x (La a Ce 1-a ) y Fe 100-x-y-w-t-e-z Ga t Cu e M z B w Respectively selecting corresponding neodymium, lanthanum, cerium, iron-boron alloy and other elements M, putting into a crucible, and under argonSmelting under protection, and then pouring the molten steel onto a rotating water-cooled copper roller, wherein the rotating speed of the copper roller is 1-4 m/s, so as to obtain a rapid hardening sheet with the thickness of about 200-350 mu m;
(2) Hydrogen crushing the rapid hardening sheet obtained in the step (1), and dehydrogenating to obtain coarse powder;
(3) Adding 0.01-3% of lubricant and antioxidant into the hydrogen crushing coarse powder obtained in the step (2) respectively, uniformly mixing, and performing air flow grinding to obtain fine powder with an average particle size of 2.5-3.0 mu m;
(4) Respectively adding 0.01-3% of lubricant and antioxidant into the air flow fine powder in the step (3), uniformly mixing, and carrying out orientation compression molding on the fine powder in a magnetic field with the magnetic field strength of 1.5-1.8T under the protection of inert gas to obtain a coarse blank;
(5) Vacuum packaging the rough blank obtained in the step (4), and then carrying out cold isostatic pressing, wherein the pressure is 225MPa, and the pressure maintaining time is 180s;
(6) Placing the rough blank obtained in the step (5) into a vacuum sintering furnace for high-temperature sintering (under a vacuum environment) to obtain a sintered magnet, wherein the sintering temperature is 1040-1080 ℃, and the heat preservation time is 3-5 h;
(7) Placing the sintered magnet obtained in the step (6) into a vacuum sintering furnace for two-stage heat treatment (under a vacuum environment), wherein the primary heat treatment temperature is 800-900 ℃, and the heat preservation time is 3-5 h; the temperature of the secondary heat treatment is 400-500 ℃ and the time is 3-5 h.
The following describes in further detail the embodiments of the present invention with reference to the drawings and examples.
The following examples are only for illustrating the present invention and are not intended to limit the scope of the present invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified. Wherein the lubricant is special NdFeB lubricant, and the product number is YSH-06; the antioxidant is special for NdFeB, and the product number is YSH-05.
Example 1
Single main phase (Nd, la, ce) -Ga-Cu-M-Fe-B magnet prepared by single alloy method according to nominal component Nd of alloy A2 26.5 (La 0.1 Ce 0.9 ) 3 Fe bal Cu 0.3 Co 0.5 Ga 0.3 Zr 0.12 B 0.94 (wt.%) a copper roller rotation speed of 1.3m/s was used to obtain a rapid hardening sheet A1 having a thickness of 260. Mu.m.
Crushing the quick-setting tablet A1 with hydrogen, dehydrogenating to obtain coarse powder, adding 0.05% lubricant and 0.1% antioxidant, mixing, and air-flow grinding to obtain average particle size X 50 Fine powder A1 of 2.8 μm.
The fine powder A1 was added with 0.1% by mass of a lubricant and 0.2% by mass of an antioxidant, respectively, and mixed uniformly in a vacuum glove box.
Under the protection of inert gas, carrying out orientation molding on air-flow ground powder A1 in a magnetic field with the magnetic field strength of 2.0T to obtain a coarse blank, vacuum packaging the coarse blank, carrying out cold isostatic pressing, then placing the coarse blank into a vacuum sintering furnace for sintering, keeping the sintering temperature at 1040 ℃, introducing argon gas for air cooling after the heat preservation time is 3h, and then carrying out primary heat treatment and secondary heat treatment, wherein the primary heat treatment temperature is 850 ℃ and the time is 3h; the temperature of the secondary heat treatment is 450 ℃ and the time is 4 hours. The single main phase magnet A1 is obtained, and the single main phase magnet A1 is put into a BH tester to test magnetic properties, and the result is as follows:
magnet A1: b (B) r ＝14.41kG，H cj ＝10.21kOe，(BH) max ＝49.83MGOe，H k /H cj ＝97.40％
Example 2
Single main phase (Nd, la, ce) -Ga-Cu-M-Fe-B magnet prepared by single alloy method according to nominal component Nd of alloy A2 26.5 (La 0.1 Ce 0.9 ) 3 Fe bal Cu 0.8 Co 0.5 Ga 0.6 Zr 0.12 B 0.94 (wt.%) a copper roller rotation speed of 1.3m/s was used to obtain a rapid hardening sheet A2 having a thickness of 260. Mu.m.
Crushing the quick-setting tablet A2 with hydrogen, dehydrogenating to obtain coarse powder, adding 0.05% lubricant and 0.1% antioxidant, and mixingThen carrying out air flow grinding to obtain the average grain diameter X 50 Fine powder A2 of 2.8 μm.
The fine powder A2 was added with 0.1% by mass of a lubricant and 0.2% by mass of an antioxidant, respectively, and mixed uniformly in a vacuum glove box.
Under the protection of inert gas, carrying out orientation molding on air-flow ground powder A2 in a magnetic field with the magnetic field strength of 2.0T to obtain a coarse blank, vacuum packaging the coarse blank, carrying out cold isostatic pressing, then placing the coarse blank into a vacuum sintering furnace for sintering, keeping the sintering temperature at 1030 ℃ for 3 hours, introducing argon for air cooling, and then carrying out primary heat treatment and secondary heat treatment, wherein the primary heat treatment temperature is 850 ℃ for 3 hours; the temperature of the secondary heat treatment is 450 ℃ and the time is 4 hours. The single main phase magnet A2 is obtained, and the single main phase magnet A2 is put into a BH tester to test magnetic properties, and the result is as follows:
magnet A2: b (B) r ＝14.40kG，H cj ＝10.75kOe，(BH) max ＝50.14MGOe，H k /H cj ＝97.40％
Comparative example 1
Single main phase (Nd, ce) -Ga-Cu-M-Fe-B magnet prepared by single alloy method according to nominal component Nd of alloy A3 26.5 Ce 3 Fe bal Cu 0.3 Co 0.5 Ga 0.3 Zr 0.12 B 0.94 (wt.%) ("bal" stands for the balance), a copper roll rotation speed of 1.3m/s was used to obtain a rapid hardening sheet A3 having a thickness of 260. Mu.m.
Crushing the quick-setting tablet A3 with hydrogen, dehydrogenating to obtain coarse powder, adding 0.05% lubricant and 0.1% antioxidant, mixing, and air-flow grinding to obtain average particle size X 50 Fine powder A3 of 2.8 μm.
The fine powder A3 was added with 0.1% by mass of a lubricant and 0.2% by mass of an antioxidant, respectively, and mixed uniformly in a vacuum glove box.
Under the protection of inert gas, carrying out orientation molding on air-flow ground powder A3 in a magnetic field with the magnetic field strength of 2.0T to obtain a coarse blank, vacuum packaging the coarse blank, carrying out cold isostatic pressing, then placing the coarse blank into a vacuum sintering furnace for sintering, keeping the sintering temperature at 1040 ℃, introducing argon gas for air cooling after the heat preservation time is 3h, and then carrying out primary heat treatment and secondary heat treatment, wherein the primary heat treatment temperature is 850 ℃ and the time is 3h; the temperature of the secondary heat treatment is 450 ℃ and the time is 4 hours. The single main phase magnet A3 is obtained, and the single main phase magnet A3 is put into a BH tester to test magnetic properties, and the result is as follows:
magnet A3: b (B) r ＝14.26kG，H cj ＝8.71kOe，(BH) max ＝49.54MGOe，H k /H cj ＝93.60％
Comparative example 2
Single main phase (Nd, la, ce) -Ga-Cu-M-Fe-B magnet prepared by single alloy method according to nominal component Nd of alloy A4 26.5 (La 0.35 Ce 0.65 ) 3 Fe bal Cu 0.3 Co 0.5 Ga 0.3 Zr 0.12 B 0.94 (wt.%) a copper roller rotation speed of 1.3m/s was used to obtain a rapid hardening sheet A4 having a thickness of 260. Mu.m.
Crushing the quick-setting tablet A4 with hydrogen, dehydrogenating to obtain coarse powder, adding 0.05% lubricant and 0.1% antioxidant, mixing, and air-flow grinding to obtain average particle size X 50 Fine powder A4 of 2.8 μm.
The fine powder A4 was added with 0.1% by mass of a lubricant and 0.2% by mass of an antioxidant, respectively, and mixed uniformly in a vacuum glove box.
Under the protection of inert gas, carrying out orientation molding on air-flow ground powder A4 in a magnetic field with the magnetic field strength of 2.0T to obtain a coarse blank, vacuum packaging the coarse blank, carrying out cold isostatic pressing, then placing the coarse blank into a vacuum sintering furnace for sintering, keeping the sintering temperature at 1070 ℃, carrying out air cooling by argon after the heat preservation time is 3h, and then carrying out primary heat treatment and secondary heat treatment, wherein the primary heat treatment temperature is 850 ℃ and the time is 3h; the temperature of the secondary heat treatment is 450 ℃ and the time is 4 hours. The single main phase magnet A4 is obtained, and the single main phase magnet A4 is put into a BH tester to test magnetic properties, and the result is as follows:
magnet A4: b (B) r ＝14.49kG，H cj ＝8.14kOe，(BH) max ＝49.33MGOe，H k /H cj ＝96.40％
Comparative example 3
Single main phase (Nd, la, ce) -Ga-Cu-M-Fe-B magnet prepared by single alloy method according to nominal component Nd of alloy A5 26.5 (La 0.1 Ce 0.9 ) 3 Fe bal Cu 0.1 Co 0.2 Ga 0.1 Zr 0.12 B 0.94 (wt.%) a copper roller rotation speed of 1.3m/s was used to obtain a rapid hardening sheet A5 having a thickness of 260. Mu.m.
Crushing the quick-setting tablet A5 with hydrogen, dehydrogenating to obtain coarse powder, adding 0.05% lubricant and 0.1% antioxidant, mixing, and air-flow grinding to obtain average particle size X 50 Fine powder A5 of 2.8 μm.
The fine powder A5 was added with 0.1% by mass of a lubricant and 0.2% by mass of an antioxidant, respectively, and mixed uniformly in a vacuum glove box.
Under the protection of inert gas, carrying out orientation molding on air-flow ground powder A5 in a magnetic field with the magnetic field strength of 2.0T to obtain a coarse blank, vacuum packaging the coarse blank, carrying out cold isostatic pressing, then placing the coarse blank into a vacuum sintering furnace for sintering, keeping the sintering temperature at 1040 ℃, introducing argon gas for air cooling after the heat preservation time is 3h, and then carrying out primary heat treatment and secondary heat treatment, wherein the primary heat treatment temperature is 850 ℃ and the time is 3h; the temperature of the secondary heat treatment is 495 ℃ and the time is 4 hours. The single main phase magnet A5 is obtained, and the single main phase magnet A5 is put into a BH tester to test magnetic properties, and the result is as follows:
magnet A5: b (B) r ＝14.39kG，H cj ＝8.82kOe，(BH) max ＝49.73MGOe，H k /H cj ＝96.60％
Test examples
The magnetic properties of the magnets obtained in examples and comparative examples are shown in Table 1.
As can be seen from table 1, the magnets of example 1 had a La-substituted Ce content of 10wt.%, a remanence increase of about 1.05%, a coercivity increase of about 17.22%, a maximum magnetic energy product increase of about 0.64% as compared with comparative example 1, in which no La was added, a remanence performance of about 25.43%, and a maximum magnetic energy product increase of about 1.01% as compared with comparative example 2, in which La-substituted Ce content of 35 wt.%; the magnet of example 1 had a Cu content of 0.3 and a ga content of 0.3, and the remanence and maximum magnetic energy product performance were substantially unchanged and the coercivity was increased by about 15.76% as compared with comparative example 3 having a Cu content of 0.1 and a ga content of 0.1.
FIG. 1 is a comparison of coercivity effects of example 2 and comparative example 1.
TABLE 1 magnetic Properties of (Nd, la, ce) -Ga-Cu-M-Fe-B magnets of different compositions
Finally, the foregoing is merely a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A rare earth permanent magnet alloy is characterized in that the rare earth permanent magnet alloy has Nd x (La a Ce 1-a ) y Fe 100-x-y-w-t-e-z Ga t Cu e M z B w The composition of the representation, wherein:
m is one or more than one of Al, nb, ti, co, zr;
x, y, t, e, z, w the weight percentage of each element is that x is more than or equal to 16.0 and less than or equal to 33.0,1.0 and y is more than or equal to 12.0,0.3 and less than or equal to 1.0,0.3 and less than or equal to e and less than or equal to 1.0,0.1, z is more than or equal to 1.0,0.8 and less than or equal to w is more than or equal to 1.0;
a is the weight percentage content of La in the whole of La and Ce, and the range of the weight percentage content of the La is more than or equal to 0.05 and less than or equal to 0.20.
2. The rare earth permanent magnet alloy according to claim 1, wherein 28.0.ltoreq.x+y.ltoreq.34.0.
3. Rare earth permanent magnet alloy according to claim 1 or 2, characterized in that y/(x+y) = 5.0-40.0 wt.%.
4. A rare earth permanent magnet alloy according to any one of claims 1-3, wherein M is Co and Zr in a mass ratio of 0.1-0.6:0.12.
5. The preparation method of the rare earth permanent magnet alloy is characterized by comprising the following steps of:
obtaining rare earth permanent magnet alloy magnetic powder by means of air flow grinding; the rare earth permanent magnet alloy magnetic powder has Nd x (La a Ce 1-a ) y Fe 100-x-y-w-t-e-z Ga t Cu e M z B w The composition of the representation, wherein:
m is one or more than one of Al, nb, ti, co, zr;
x, y, t, e, z, w the weight percentage of each element is that x is more than or equal to 16.0 and less than or equal to 33.0,1.0 and y is more than or equal to 12.0,0.3 and less than or equal to 1.0,0.3 and less than or equal to e and less than or equal to 1.0,0.1, z is more than or equal to 1.0,0.8 and less than or equal to w is more than or equal to 1.0; a is the weight percentage content of La in the whole of La and Ce, and the range of a is more than or equal to 0.05 and less than or equal to 0.20;
and sequentially carrying out magnetic field orientation molding, cold isostatic pressing, vacuum sintering and secondary tempering heat treatment on the rare earth permanent magnet alloy magnetic powder to obtain the rare earth permanent magnet alloy.
6. The rare earth permanent magnet alloy according to claim 5, wherein 28.0.ltoreq.x+y.ltoreq.34.0;
and/or y/(x+y) =5.0 to 40.0wt.%;
and/or M is Co and Zr with the mass ratio of 0.2-0.5:0.12.
7. A rare earth permanent magnet alloy according to claim 5 or 6, wherein the preparation method of the rare earth permanent magnet alloy magnetic powder comprises the following steps:
(1) Proportioning according to the proportion of each element in the rare earth permanent magnet alloy magnetic powder;
(2) Mixing the prepared raw materials containing the elements, smelting, and then preparing quick-setting tablets;
(3) Carrying out hydrogen breaking treatment on the rapid hardening sheet, and obtaining coarse magnetic powder after dehydrogenation;
(4) Uniformly mixing the coarse magnetic powder, a first lubricant and a first antioxidant, and performing air flow grinding to obtain rare earth permanent magnet alloy magnetic powder, wherein the average particle size of the rare earth permanent magnet alloy magnetic powder is 2.5-3.0 mu m;
preferably, the thickness of the rapid hardening sheet is 200-350 μm;
and/or the first lubricant is used in an amount of 0.01 to 3% and the first antioxidant is used in an amount of 0.01 to 3% based on the weight of the coarse magnetic powder.
8. A rare earth permanent magnet alloy according to any one of claims 5-7, wherein the magnetic powder of the rare earth permanent magnet alloy is subjected to magnetic field orientation forming and cold isostatic pressing in sequence, specifically:
uniformly mixing the rare earth permanent magnet alloy magnetic powder, a second lubricant and a second antioxidant, and then carrying out orientation profiling in a magnetic field with the magnetic field strength of 1.5-1.8T under the protection of inert atmosphere to obtain a coarse blank;
carrying out cold isostatic pressing after vacuum packaging on the coarse embryo, wherein the pressure of the cold isostatic pressing is 210-230 MPa, and the pressure maintaining time is 120-240 s;
preferably, the second lubricant is used in an amount of 0.01 to 3% and the second antioxidant is used in an amount of 0.01 to 3% based on the weight of the coarse magnetic powder.
9. A rare earth permanent magnet alloy according to any one of claims 5-8, wherein the sintering temperature of the vacuum sintering is 1040-1080 ℃ and the holding time is 3-5 h.
10. Rare earth permanent magnet alloy according to any one of claims 5-9, characterized in that the secondary tempering heat treatment specifically is: firstly, heat treatment is carried out for 3-5 hours at 800-900 ℃, and then heat treatment is carried out for 3-5 hours at 400-500 ℃.
CN202310745614.1A 2023-06-21 2023-06-21 Rare earth permanent magnet alloy and preparation method thereof Pending CN116844812A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117747233A (en) * 2023-11-10 2024-03-22 宁波金鸡强磁股份有限公司 Heavy rare earth-free high-performance lanthanum-cerium-containing rare earth permanent magnet and manufacturing method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117747233A (en) * 2023-11-10 2024-03-22 宁波金鸡强磁股份有限公司 Heavy rare earth-free high-performance lanthanum-cerium-containing rare earth permanent magnet and manufacturing method thereof

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