CN111223627B - Neodymium-iron-boron magnet material, raw material composition, preparation method and application - Google Patents

Neodymium-iron-boron magnet material, raw material composition, preparation method and application Download PDF

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CN111223627B
CN111223627B CN202010121486.XA CN202010121486A CN111223627B CN 111223627 B CN111223627 B CN 111223627B CN 202010121486 A CN202010121486 A CN 202010121486A CN 111223627 B CN111223627 B CN 111223627B
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magnet material
composition
mass percentage
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CN111223627A (en
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骆溁
廖宗博
蓝琴
黄佳莹
师大伟
林玉麟
谢菊华
龙严清
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Fujian Jinlong Rare Earth Co ltd
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Xiamen Tungsten Co Ltd
Fujian Changting Jinlong Rare Earth Co Ltd
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H01F41/0266—Moulding; Pressing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • 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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  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

The invention discloses a neodymium iron boron magnet material, a raw material composition, a preparation method and an application, wherein the neodymium iron boron magnet material comprises the following components: r: 28 to 33 wt%; r is a rare earth element and comprises rare earth metal R1 for smelting and rare earth metal R2 for grain boundary diffusion, wherein the content of R2 is 0.2-1 wt%; r1 includes Nd and does not contain RH; r2 includes Tb; b: 0.9-1.1 wt%; cu: 0.15wt% or less and not 0 wt%; m: 0.4wt% or less and not 0 wt%; m comprises one or more of Ti, Ni, V, Nb, Ta, Cr, Mo, W, Mn, Zr, Hf, Zn and Ag; fe: 60-70.6 wt%; RH is heavy rare earth element; the raw material composition does not contain Co. The magnet material has the advantages of high remanence, high coercivity and good high-temperature performance.

Description

Neodymium-iron-boron magnet material, raw material composition, preparation method and application
Technical Field
The invention relates to a neodymium iron boron magnet material, a raw material composition, a preparation method and application.
Background
Nd-Fe-B permanent magnetic materialNd2Fel4The B compound is used as a matrix, has the advantages of high magnetic property, small thermal expansion coefficient, easy processing, low price and the like, is increased at the speed of 20-30 percent per year on average since the coming of the world, and becomes a permanent magnetic material with the most wide application. According to the preparation method, the Nd-Fe-B permanent magnet can be divided into three types of sintering, bonding and hot pressing, wherein the sintered magnet accounts for more than 80% of the total production and is most widely applied.
With the continuous optimization of the preparation process and the magnet components, the maximum magnetic energy product of the sintered Nd-Fe-B magnet is close to the theoretical value. With the rapid development of new industries such as wind power generation, hybrid electric vehicles, variable frequency air conditioners and the like in recent years, the demand of high-performance Nd-Fe-B magnets is more and more large, and meanwhile, the application in the high-temperature field also puts higher requirements on the performance, especially the coercive force, of sintered Nd-Fe-B magnets.
U.S. patent application No. US5645651A shows from fig. 1 that the curie temperature of Nd-Fe-B magnets increases with increasing Co content, and in addition, table 1 shows from a comparison of sample 9 and sample 2 that adding 20 at% Co to Nd-Fe-B magnets increases the coercivity while maintaining the remanence substantially constant compared to the solution without Co.
Therefore, Co is widely applied to high-tech fields such as neodymium-iron-boron rare earth permanent magnet, samarium-cobalt rare earth permanent magnet, battery and the like, but Co is an important strategic resource and is expensive.
Disclosure of Invention
The invention aims to overcome the technical problems that the Curie temperature and the coercive force of a neodymium iron boron magnet in the prior art are improved by adding Co, and the Co faces the defect of high price, and provides a neodymium iron boron magnet material, a raw material composition, a preparation method and application. The magnet material of the invention has the advantages of high remanence and high coercivity.
The neodymium iron boron magnet material provided by the invention adopts a scheme of no Co and no heavy rare earth metal added in the smelting metal, and simultaneously reasonably controls the total rare earth content and the content range of Cu, B and M (Ti, Nb, Zr and the like) elements, so that more impurity phases are distributed in two-particle crystal boundaries, the continuity of the crystal boundaries is improved, and meanwhile, the area of a crystal boundary triangular region is reduced, thereby being beneficial to obtaining higher density, and further improving the residual magnetism Br and the coercive force Hcj of the magnet.
The invention solves the technical problems through the following technical scheme:
a raw material composition of a neodymium iron boron magnet material comprises the following components in percentage by weight:
r: 28 to 33 wt%; the R is a rare earth element and comprises rare earth metal R1 for smelting and rare earth metal R2 for grain boundary diffusion, and the content of R2 is 0.2-1 wt%;
the R1 includes Nd and does not contain RH;
said R2 comprises Tb;
B：0.9～1.1wt％；
cu: 0.15wt% or less and not 0 wt%;
m: 0.4wt% or less and not 0 wt%;
m comprises one or more of Ti, Ni, V, Nb, Ta, Cr, Mo, W, Mn, Zr, Hf, Zn and Ag;
Fe：60～70.6wt％；
the RH is a heavy rare earth element;
the wt% is the mass percentage of the element in the raw material composition;
the raw material composition does not contain Co.
In the present invention, the content of R is preferably 29.5 to 31.6wt% or 29.8 to 32.5 wt%, for example 31.2 wt%, 32.2 wt%, 30.9 wt% or 31.5 wt%, and the wt% is the mass percentage of the element in the raw material composition.
In the invention, the R1 can also comprise one or more of Pr, La and Ce; preferably comprising Pr.
Wherein, when the R1 contains Pr, the addition form of Pr may be conventional in the art, for example, in the form of PrNd, or in the form of a pure mixture of Pr and Nd, or in the form of a mixture of PrNd, pure Pr and Nd. When added as PrNd, Pr: nd 25:75 or 20: 80; when the pure Pr and Nd are added in the form of a mixture, the Pr content is preferably 0.1-2 wt%, such as 0.2wt% or 0.5 wt%, and the wt% is the mass percentage of the element in the raw material composition. When PrNd, pure Pr and Nd are added as a mixture, the Pr content is preferably 0.1-2 wt%.
In the present invention, the content of R2 is preferably 0.2 to 0.8wt%, or 0.5 to 1wt%, for example 0.6wt%, 0.9 wt%, or 0.7wt%, where wt% is the mass percentage of the element in the raw material composition.
In the present invention, the content of Tb is preferably in the range of 0.5 to 1wt%, for example, 0.8wt%, 0.6wt%, 0.75 wt%, 0.9 wt%, or 0.7wt%, where wt% is the mass percentage of the element in the raw material composition.
In the invention, the R2 may further comprise one or more of Pr, Dy, Ho and Gd. The rare earth elements can form a shell layer for diffusing the rare earth elements by a grain boundary diffusion principle.
Wherein, when the R2 includes Pr, the content range of Pr is preferably 0.2wt% or less and not 0wt%, for example 0.2wt% or 0.1wt%, wt% being the mass percentage of the element in the raw material composition.
Wherein, when R2 includes Dy, the content range of Dy is preferably 0.3wt% or less and not 0wt%, for example, 0.1wt%, 0.05 wt% or 0.12 wt%, wt% being the mass percentage of element in the raw material composition.
Wherein, when the R2 includes Ho, the content range of Ho is preferably 0.15wt% or less and not 0wt%, for example, 0.1wt% or 0.02 wt%, wt% being the mass percentage of the element in the raw material composition.
Wherein, when the R2 includes Gd, the content range of Gd is preferably 0.15wt% or less and not 0wt%, for example 0.1wt% or 0.06 wt%, wt% being the mass percentage of the element in the raw material composition.
In the present invention, the content of B is preferably in the range of 0.9 to 0.99wt% or 0.98 to 1.05 wt%, for example 1wt%, 1.02 wt% or 1.03 wt%, wt% being the mass percentage of the element in the raw material composition.
In the present invention, the Cu content is preferably in a range of 0.07 to 0.15wt% or 0.08wt% or less and is not 0wt%, for example, 0.12 wt%, 0.13 wt%, 0.03wt%, 0.05 wt%, 0.09 wt%, 0.1wt%, or 0.07wt%, with wt% being a mass percentage of an element in the raw material composition.
The addition mode of the Cu can be the addition during smelting and/or grain boundary diffusion.
When the Cu is added in the grain boundary diffusion, the Cu is added in the form of PrCu alloy, the content of the Cu is preferably 0.03-0.15 wt%, and the wt% is the mass percentage of elements in the raw material composition, wherein the Cu accounts for 0.1-17 wt% of the PrCu.
In the present invention, the content of M is preferably 0.1 to 0.15wt%, or 0.1 to 0.32 wt%, for example 0.25 wt%, 0.32 wt%, 0.22 wt%, or 0.2wt%, where wt% is the mass percentage of the element in the raw material composition.
In the present invention, the M may further include one or more of Bi, Sn, Zn, Ga, In, Au, and Pb.
Preferably, the M comprises one or more of Ga, Ti and Nb.
Wherein, when the M comprises Ga, the content of the Ga may be in the range of 0.02 to 0.3wt%, preferably 0.02 to 0.1wt% or 0.08 to 0.2wt%, for example 0.07wt%, the wt% being the mass percentage of the element in the raw material composition.
Wherein, when the M includes Ti, the content of Ti may be in a range of 0 to 0.35wt%, preferably 0.05 to 0.3wt% or 0.1 to 0.15wt%, for example 0.12 wt%, 0.05 wt% or 0.2wt%, and wt% is the mass percentage of element in the raw material composition.
When the M comprises Nb, the content of Nb is preferably 0.05-0.1 wt%, and the wt% is the mass percentage of the element in the raw material composition.
In the present invention, preferably, the raw material composition further contains Al; the content range of Al is preferably 0.03wt% or less and not 0wt%, for example 0.01wt%, wt% being the mass percentage of the element in the raw material composition.
When the M comprises Ga and Ga is 0.01wt% or less, Al + Ga + Cu may be 0.15wt% or less and not 0wt%, for example 0.12 wt%; preferably, Al + Ga + Cu is 0.11wt% or less and not 0wt%, for example 0.07wt%, wt% being the mass percentage of the element in the raw material composition.
When the M element includes Ga, and Ga is 0.2wt% or more and not 0.35wt%, it is preferable that Ti + Nb in the composition of the M element is 0.07wt% or less and not 0wt%, for example, 0.05 wt%, and wt% is the mass percentage of the element in the raw material composition. In addition, when Ti + Nb is excessive, remanence may be reduced.
In a preferred embodiment of the present invention, the raw material composition comprises the following components in percentage by weight: in R1: nd 27.5 wt%; in R2: 0.5 wt% of Tb; 0.9 wt% of B, 0.15wt% of Cu, 0.35wt% of Ti, and the balance of Fe and inevitable impurities, wherein the wt% is the mass percentage of elements in the raw material composition.
In a preferred embodiment of the present invention, the raw material composition comprises the following components in percentage by weight: in R1: nd 32 wt%; in R2: 0.8wt% of Tb; b1 wt%, Cu 0.12 wt%, Ti 0.15wt%, Nb 0.1wt%, and the balance of Fe and inevitable impurities, wherein the wt% is the mass percentage of elements in the raw material composition.
In a preferred embodiment of the present invention, the raw material composition comprises the following components in percentage by weight: in R1: 30.4 wt% of Nd, 0.2wt% of Pr; in R2: 0.1wt% of Dy and 0.5 wt% of Tb; 0.98 wt% of B, 0.07wt% of Cu, 0.12 wt% of Ti, 0.1wt% of Nb, 0.1wt% of Ga, and the balance of Fe and inevitable impurities, wherein the wt% is the mass percentage of elements in the raw material composition.
In a preferred embodiment of the present invention, the raw material composition comprises the following components in percentage by weight: in R1: 30.8 wt% of Nd and 0.5 wt% of Pr; in R2: 0.1wt% of Dy, 0.6wt% of Tb and 0.2wt% of Pr; b1.02wt%, Cu 0.13 wt%, Ti 0.15wt%, Ga 0.07wt%, and the balance of Fe and inevitable impurities, wherein the wt% is the mass percentage of elements in the raw material composition.
In a preferred embodiment of the present invention, the raw material composition comprises the following components in percentage by weight: in R1: nd 29.9 wt%; in R2: 0.05 wt% of Dy, 0.75 wt% of Tb, 0.1wt% of Ho and 0.1wt% of Gd; b1.1 wt%, Cu 0.03wt%, Ti 0.05 wt%, Ga 0.1wt%, and the balance of Fe and inevitable impurities, wherein the wt% is the mass percentage of elements in the raw material composition.
In a preferred embodiment of the present invention, the raw material composition comprises the following components in percentage by weight: in R1: nd 28.5 wt%; in R2: 0.12 wt% of Dy, 0.7wt% of Tb, 0.1wt% of Pr, 0.02 wt% of Ho and 0.06 wt% of Gd; b1.03 wt%, Cu 0.05 wt%, Ti 0.3wt%, Ga 0.02 wt%, and the balance of Fe and inevitable impurities, wherein the wt% is the mass percentage of elements in the raw material composition.
In a preferred embodiment of the present invention, the raw material composition comprises the following components in percentage by weight: in R1: nd 29 wt%; in R2: 0.8wt% of Tb; 0.99wt% of B, 0.09 wt% of Cu, 0.2wt% of Ti, 0.03wt% of Al, and the balance of Fe and inevitable impurities, wherein the wt% is the mass percentage of elements in the raw material composition.
In a preferred embodiment of the present invention, the raw material composition comprises the following components in percentage by weight: in R1: 30.5 wt% of Nd; in R2: 0.1wt% of Dy and 0.9 wt% of Tb; b1 wt%, Cu 0.1wt%, Nb 0.05 wt%, Ga 0.3wt%, Al 0.01wt%, and the balance of Fe and inevitable impurities, wherein the wt% is the mass percentage of elements in the raw material composition.
In a preferred embodiment of the present invention, the raw material composition comprises the following components in percentage by weight: in R1: nd 29.9 wt%; in R2: 0.7wt% of Tb; 0.99wt% of B, 0.07wt% of Cu, 0.15wt% of Ti, and the balance of Fe and inevitable impurities, wherein the wt% is the mass percentage of elements in the raw material composition.
The invention also provides a neodymium iron boron magnet material, R: 28 to 33 wt%; the R comprises R1 and R2, and the content of the R2 is 0.2-1 wt%; the R1 includes Nd and does not contain RH;
said R2 comprises Tb;
B：0.9～1.1wt％；
cu: 0.15wt% or less and not 0 wt%;
m: 0.4wt% or less and not 0 wt%;
m comprises one or more of Ti, Ni, V, Nb, Ta, Cr, Mo, W, Mn, Zr, Hf, Zn and Ag;
Fe：60～70.6wt％；
the wt% is the mass percentage of the element in the neodymium iron boron magnet material;
the neodymium iron boron magnet material does not contain Co;
the neodymium-iron-boron magnet material comprises Nd2Fel4B crystal grains and shell layer thereof, adjacent to the Nd2Fel4Two-grain boundaries and grain boundary trigones of B grains, in which Nd in R1 is distributed2Fel4B crystal grains, the two-particle grain boundary and the grain boundary triangular region, wherein R2 is mainly distributed in the shell layer, the two-particle grain boundary and the grain boundary triangular region; the area percentage of the grain boundary triangular region is 2-3.5%; the grain boundary continuity of the neodymium iron boron magnet material is more than 96%.
In the present invention, "R2 is mainly distributed in the shell layer, the two-particle grain boundary and the grain boundary triangle" means that R2 caused by the conventional grain boundary diffusion process in the art is mainly distributed (generally, 95% or more) in the shell layer and the grain boundary of the main phase grains, and a small part of R2 is also diffused into the main phase grains, for example, at the outer edges of the main phase grains.
As known to those skilled in the art, since rare earth elements are usually lost in the smelting and sintering processes, in order to ensure the quality of the final product, 0.3wt% of Nd is generally additionally added to the raw material composition, and the wt% of the additionally added rare earth elements accounts for the mass ratio of the neodymium iron boron raw material composition, not counting the component content of the raw material composition.
In the invention, the grain boundary triangular region generally refers to a place where three or more grain boundaries intersect, and a B-rich phase, a rare earth oxide, a rare earth carbide and a cavity are distributed. The calculation mode of the area ratio of the grain boundary triangular region refers to the ratio of the area of the grain boundary triangular region to the total area (the total area of grains and the grain boundary).
In the present invention, the calculation mode of the grain boundary continuity refers to the ratio of the length occupied by the phase other than the void in the grain boundary (for example, B-rich phase, rare earth-rich phase, etc.) to the total grain boundary length. If the continuity of the grain boundary exceeds 96%, the channel is called a continuous channel.
In the present invention, it can be presumed that the impurity phase migrates from the triangular region to the two-particle grain boundary by "the ratio of the mass of carbon to the mass of oxygen at the two-particle grain boundary" and "the ratio of the mass of carbon to the mass of oxygen at the triangular region of the grain boundary", and the area of the triangular region of the grain boundary is reduced. C. O is typically present in magnets in the form of rare earth carbides and oxides.
Wherein the mass ratio of C to O in the two-particle grain boundary is preferably 0.34 to 0.40%, for example, 0.36%, 0.38%, 0.39%, 0.34%, or 0.35%. The ratio of C to O in the grain boundary triangle is preferably 0.4 to 0.5% by mass, for example, 0.46%, 0.45%, 0.41%, 0.44%, 0.43%, 0.48%, or 0.47%.
Wherein the mass ratio of C to O in the grain boundary triangular region refers to: the ratio of the mass of C and O in the trigones of the grain boundaries to the total mass of all elements in the grain boundaries. The mass ratio of C to O in the two-particle grain boundary refers to: the ratio of the mass of C and O in the grain boundaries of the two particles to the total mass of all elements in the grain boundaries.
In the invention, C, O element in rare earth oxide and rare earth carbide is introduced in a conventional mode in the field, generally introduced as impurities or introduced in an atmosphere, specifically, for example, in the process of jet milling and pressing, lubricant is introduced, and during sintering, the additives are removed by heating, but a small amount of C, O element residue is inevitable; for another example, a small amount of O element is inevitably introduced by the atmosphere during the preparation process. In the application, the content of C, O in the finally obtained neodymium iron boron magnet material product is only below 1000 ppm and 1200ppm respectively through detection, and the product belongs to the conventionally acceptable impurity category in the field, so that the product element statistical table is not included.
In the two-particle grain boundary of the magnet material of the present invention, in addition to the rare earth oxide and rare earth carbide hetero-phase, preferably, a new phase having a chemical composition of R is detected in the two-particle grain boundary29.8～32.14Fe65.89～67.25M0.12～0.18B1.75～1.88A phase, wherein R comprises Nd and Tb, and M comprises one or more of Ti, Ni, V, Nb, Ta, Cr, Mo, W, Mn, Zr, Hf, Zn and Ag. The phase is well dissolved in a grain boundary, and is beneficial to improving the continuity of the grain boundary and improving the demagnetization coupling effect, thereby improving the Hcj of the magnet.
Wherein, R is29.8～32.14Fe65.89～67.25M0.12～0.18B1.75～1.88The area ratio of the phase to the grain boundary of the two grains is preferably 0.7 to 2.5%, for example, 0.73%, 0.97%, 1.03%, 1.12%, 0.86%, 0.77%, 0.95%, 2.49%, or 1.01%. The area ratio of the new phase in the grain boundary of the two particles refers to: the ratio of the area of the new phase in the grain boundary of the second particle to the total area of the grain boundary of the second particle.
In preferred embodiments of the present application, the structure of the novel phase is, for example, R30.52Fe67.54M0.15B1.79、
R30.23Fe67.77M0.16B1.84、R29.85Fe68.28M0.09B1.78、R31.19Fe66.83M0.12B1.86、R32.14Fe65.89M0.13B1.84、R31.50Fe66.59M0.16B1.75、R31.87Fe66.07M0.18B1.88、R30.75Fe67.25M0.15B1.85Or R31.22Fe66.82M0.12B1.84。
In the present invention, the area ratio of the grain boundary triangle is preferably 2.2 to 2.9% or 2.4 to 3.2%, for example, 2.42%, 2.78%, 2.83%, 3.12%, 2.84%, 2.23%, 2.32%, 2.65%, or 2.89%.
In the present invention, the grain boundary continuity is preferably 97.5% or more, for example, 97.92%, 98.46%, 98.33%, 98.24%, 98.13%, 97.96%, 97.93%, 98.57% or 98.67%.
In the present invention, the content of R is preferably 29.5 to 31.6wt% or 29.8 to 32.5 wt%, for example, 31.2 wt%, 32.2 wt%, 30.9 wt% or 31.5 wt%, where wt% is the mass percentage of the element in the neodymium iron boron magnet material.
In the invention, the R1 can also comprise one or more of Pr, La and Ce; preferably comprising Pr.
Wherein, when the R1 contains Pr, the addition form of Pr may be conventional in the art, for example, in the form of PrNd, or in the form of a pure mixture of Pr and Nd, or in the form of a mixture of PrNd, pure Pr and Nd. When added as PrNd, Pr: nd 25:75 or 20: 80; when the pure Pr and Nd are added in the form of a mixture, the Pr content is preferably 0.1-2 wt%, such as 0.2wt% or 0.5 wt%, and the wt% is the mass percentage of the element in the raw material composition. When PrNd, pure Pr and Nd are added as a mixture, the Pr content is preferably 0.1-2 wt%.
In the present invention, the content of R2 is preferably 0.2 to 0.8wt%, or 0.5 to 1wt%, for example 0.6wt%, 0.9 wt%, or 0.7wt%, where wt% is the mass percentage of the element in the raw material composition.
In the present invention, the content of Tb is preferably 0.5 to 1wt%, for example, 0.8wt%, 0.6wt%, 0.75 wt%, 0.9 wt%, or 0.7wt%, where wt% is the mass percentage of the element in the neodymium iron boron magnet material.
In the invention, the R2 may further comprise one or more of Pr, Dy, Ho and Gd. The rare earth elements can form a shell layer for diffusing the rare earth elements by a grain boundary diffusion principle.
Wherein, when the R2 includes Pr, the content range of Pr is preferably 0.2wt% or less and not 0wt%, for example 0.2wt% or 0.1wt%, wt% being the mass percentage of the element in the raw material composition.
Wherein, when R2 includes Dy, the content range of Dy is preferably 0.3wt% or less and not 0wt%, for example, 0.1wt%, 0.05 wt% or 0.12 wt%, wt% being the mass percentage of element in the raw material composition.
Wherein, when the R2 includes Ho, the content range of Ho is preferably 0.15wt% or less and not 0wt%, for example, 0.1wt% or 0.02 wt%, wt% being the mass percentage of the element in the raw material composition.
Wherein, when the R2 includes Gd, the content range of Gd is preferably 0.15wt% or less and not 0wt%, for example 0.1wt% or 0.06 wt%, wt% being the mass percentage of the element in the raw material composition.
In the present invention, the content range of B is preferably 0.9 to 0.99wt% or 0.98 to 1.05 wt%, for example, 1wt%, 1.02 wt% or 1.03 wt%, where wt% is the mass percentage of the element in the neodymium iron boron magnet material.
In the present invention, the Cu content is preferably in a range of 0.07 to 0.15wt% or less than 0.08wt% and not 0wt%, for example, 0.12 wt%, 0.13 wt%, 0.03wt%, 0.05 wt%, 0.09 wt%, 0.1wt%, or 0.07wt%, where wt% is a mass percentage of an element in the neodymium iron boron magnet material.
The addition mode of the Cu can be the addition during smelting and/or grain boundary diffusion.
When the Cu is added in the grain boundary diffusion, the Cu is added in the form of a PrCu alloy, the content of the Cu is preferably 0.03-0.15 wt%, and the wt% is the mass percentage of elements in the raw material composition; wherein the percentage of Cu in PrCu is 0.1-17 wt%.
In the present invention, the content of M is preferably 0.1 to 0.15wt%, or 0.15 to 0.32 wt%, for example, 0.25 wt%, 0.32 wt%, 0.22 wt%, or 0.2wt%, where wt% is the mass percentage of the element in the neodymium iron boron magnet material.
In the present invention, the M may further include one or more of Bi, Sn, Zn, Ga, In, Au, and Pb.
Preferably, the M comprises one or more of Ga, Ti and Nb.
Wherein, when the M includes Ga, the content of the Ga may be in a range of 0.02 to 0.3wt%, preferably 0.02 to 0.1wt% or 0.08 to 0.2wt%, for example 0.07wt%, the wt% being a mass percentage of the element in the neodymium iron boron magnet material.
Wherein, when the M includes Ti, the content of Ti may be in a range of 0 to 0.35wt%, preferably 0.05 to 0.3wt% or 0.1 to 0.15wt%, for example 0.12 wt%, 0.05 wt% or 0.2wt%, wt% being a mass percentage of an element in the neodymium iron boron magnet material.
When the M comprises Nb, the content range of Nb is preferably 0.05-0.1 wt%, and the wt% is the mass percentage of elements in the neodymium iron boron magnet material.
In the invention, preferably, the neodymium iron boron magnet material further contains Al; the content range of Al is preferably 0.03wt% or less, and is not 0wt%, for example 0.01wt%, wt% being the mass percentage of the element in the neodymium iron boron magnet material.
When the M comprises Ga and Ga is 0.01wt% or less, Al + Ga + Cu may be 0.15wt% or less and not 0wt%, for example 0.12 wt%; preferably, Al + Ga + Cu is 0.11wt% or less and not 0wt%, for example 0.07wt%, wt% being the mass percentage of the element in the neodymium iron boron magnet material.
When the M element includes Ga, and Ga is 0.2wt% or more and is not 0.35wt%, preferably, Ti + Nb in the composition of the M element is 0.07wt% or less and is not 0wt%, for example, 0.05 wt%, and wt% is the mass percentage of the element in the neodymium iron boron magnet material. In addition, when Ti + Nb is excessive, remanence may be reduced.
In a preferred embodiment of the present invention, the neodymium-iron-boron magnet material comprises the following components in percentage by weight: nd 27.5 wt%, Tb 0.5 wt%; 0.9 wt% of B, 0.15wt% of Cu, 0.35wt% of Ti, and the balance of Fe and inevitable impurities, wherein the wt% is the mass percentage of elements in the neodymium iron boron magnet material;
the area percentage of the grain boundary triangular region is 2.42 percent; the continuity of the grain boundary is 97.92 percent, and the new phase in the two-particle grain boundary is R30.52Fe67.54M0.15B1.79。
In a preferred embodiment of the present invention, the neodymium-iron-boron magnet material comprises the following components in percentage by weight: nd 32 wt%, Tb 0.8 wt%; b1 wt%, Cu 0.12 wt%, Ti 0.15wt%, Nb 0.1wt%, and the balance of Fe and inevitable impurities, wherein the wt% is the mass percentage of elements in the neodymium iron boron magnet material;
the area percentage of the grain boundary triangular region is 2.78%; the continuity of the grain boundary is 98.46 percent, and the new phase in the two-particle grain boundary is R30.23Fe67.77M0.16B1.84。
In a preferred embodiment of the present invention, the neodymium-iron-boron magnet material comprises the following components in percentage by weight: 30.4 wt% of Nd, 0.2wt% of Pr, 0.1wt% of Dy and 0.5 wt% of Tb; 0.98 wt% of B, 0.07wt% of Cu, 0.12 wt% of Ti, 0.1wt% of Nb, 0.1wt% of Ga, and the balance of Fe and inevitable impurities, wherein the wt% is the mass percentage of elements in the neodymium iron boron magnet material;
the area percentage of the grain boundary triangular region is 2.83 percent; the continuity of the grain boundary is 98.33 percent, and the new phase in the two-particle grain boundary is R29.85Fe68.28M0.09B1.78。
In a preferred embodiment of the present invention, the neodymium-iron-boron magnet material comprises the following components in percentage by weight: 30.8 wt% of Nd, 0.7wt% of Pr, 0.1wt% of Dy, 0.6wt% of Tb, 1.02wt% of B, 0.13 wt% of Cu, 0.15wt% of Ti, 0.07wt% of Ga, and the balance of Fe and inevitable impurities, wherein the wt% is the mass percentage of elements in the neodymium iron boron magnet material;
the area percentage of the grain boundary triangular region is 3.12%; the continuity of the grain boundary is 98.24 percent, and the new phase in the two-particle grain boundary is R31.19Fe66.83M0.12B1.86。
In a preferred embodiment of the present invention, the neodymium-iron-boron magnet material comprises the following components in percentage by weight: 29.9 wt% of Nd, 0.05 wt% of Dy, 0.75 wt% of Tb, 0.1wt% of Ho, 0.1wt% of Gd0.1 wt%, 1.1 wt% of B, 0.03wt% of Cu, 0.05 wt% of Ti, 0.1wt% of Ga, and the balance of Fe and inevitable impurities, wherein the wt% is the mass percentage of elements in the neodymium iron boron magnet material;
the area percentage of the grain boundary triangular region is 2.84%; the continuity of the grain boundary is 98.13 percent, and a new matter phase in the two-particle grain boundaryIs R32.14Fe65.89M0.13B1.84。
In a preferred embodiment of the present invention, the neodymium-iron-boron magnet material comprises the following components in percentage by weight: 28.5 wt% of Nd, 0.12 wt% of Dy, 0.7wt% of Tb, 0.1wt% of Pr, 0.02 wt% of Ho, 0.06 wt% of Gd, 1.03 wt% of B, 0.05 wt% of Cu, 0.3wt% of Ti, 0.02 wt% of Ga, and the balance of Fe and inevitable impurities, wherein the wt% is the mass percentage of elements in the neodymium iron boron magnet material;
the area percentage of the grain boundary triangular region is 2.23%; the continuity of the grain boundary is 97.96 percent, and the new phase in the two-particle grain boundary is R31.50Fe66.59M0.16B1.75。
In a preferred embodiment of the present invention, the neodymium-iron-boron magnet material comprises the following components in percentage by weight: nd 29 wt%, Tb 0.8 wt%; 0.99wt% of B, 0.09 wt% of Cu, 0.2wt% of Ti, 0.03wt% of Al, and the balance of Fe and inevitable impurities, wherein the wt% is the mass percentage of elements in the neodymium iron boron magnet material;
the area percentage of the grain boundary triangular region is 2.32 percent; the continuity of the grain boundary is 97.93 percent, and the new phase in the two-particle grain boundary is R31.87Fe66.07M0.18B1.88。
In a preferred embodiment of the present invention, the neodymium-iron-boron magnet material comprises the following components in percentage by weight: 30.5 wt% of Nd, 0.1wt% of Dy and 0.9 wt% of Tb; b1 wt%, Cu 0.1wt%, Nb 0.05 wt%, Ga 0.3wt%, Al 0.01wt%, and the balance of Fe and inevitable impurities, wherein the wt% is the mass percentage of elements in the neodymium iron boron magnet material;
the area percentage of the grain boundary triangular region is 2.65%; the continuity of the grain boundary is 98.57 percent, and the new phase in the two-particle grain boundary is R30.75Fe67.25M0.15B1.85。
In a preferred embodiment of the present invention, the neodymium-iron-boron magnet material comprises the following components in percentage by weight: nd 29.9 wt%, Tb 0.7 wt%; 0.99wt% of B, 0.07wt% of Cu, 0.15wt% of Ti, and the balance of Fe and inevitable impurities, wherein the wt% is the mass percentage of elements in the neodymium iron boron magnet material;
the area percentage of the grain boundary triangular region is 2.89%; the continuity of the grain boundary is 98.67 percent, and the new phase in the two-particle grain boundary is R31.22Fe66.82M0.12B1.84。
The invention also provides a preparation method of the neodymium iron boron magnet material, which is carried out by adopting the raw material composition, the preparation method is a diffusion preparation method, the R1 element is added in the smelting step, and the R2 element is added in the grain boundary diffusion step.
In the present invention, the preparation method preferably comprises the steps of: the elements except for R2 in the raw material composition of the neodymium iron boron magnet material are smelted, pulverized, molded and sintered to obtain a sintered body, and then the mixture of the sintered body and the R2 is subjected to grain boundary diffusion treatment.
The smelting operation and conditions can be conventional smelting processes in the field, and elements except for R2 in the neodymium iron boron magnet material are generally smelted and cast by adopting an ingot casting process and a rapid hardening sheet process to obtain alloy sheets.
The temperature of the smelting can be 1300-1700 ℃, preferably 1450-1550 ℃, for example 1500 ℃. The vacuum degree of the smelting furnace can be 5 multiplied by 10-2Pa。
The smelting equipment is generally a high-frequency vacuum smelting furnace, such as a high-frequency vacuum induction smelting furnace.
The operation and conditions of the powder preparation can be conventional powder preparation process in the field, and generally comprise two processes of hydrogen powder preparation and airflow powder preparation.
The hydrogen pulverized powder generally comprises hydrogen absorption, dehydrogenation and cooling treatment. The temperature of the hydrogen absorption is generally 20 to 200 ℃, for example, 25 ℃. The dehydrogenation temperature is generally 400 to 650 ℃, and may be 500 to 550 ℃, for example 550 ℃. The pressure of the hydrogen absorption is generally 50 to 600kPa, for example 90 kPa.
The jet milling powder is generally carried out under the condition of 0.1-2 MPa, preferably 0.5-0.7 MPa (such as 0.6 MPa). The gas stream in the gas stream milled powder may be, for example, nitrogen. The time of the airflow milling powder can be 2-4 h, such as 3 h.
The molding operation and conditions may be those conventional in the art. Such as magnetic field molding. The magnetic field intensity of the magnetic field forming method is generally 1.5T or more.
Wherein, the sintering operation and conditions can be sintering process conventional in the field.
The sintering can be carried out under the condition that the vacuum degree is lower than 0.5 Pa.
The sintering temperature can be 1000-1200 ℃, such as 1030-1090 ℃, and further such as 1040 ℃.
The sintering time may be 0.5 to 10, for example 2 to 5, and further for example 2 hours.
Wherein the grain boundary diffusion treatment may be performed according to a process conventional in the art, such as an R2 coating operation. The R2 is typically coated in the form of a fluoride or low melting point alloy, such as an alloy of Tb or fluoride. When the R2 further contains Dy, it is preferable that Dy is coated in the form of an alloy or fluoride of Dy. When the R2 further comprises Pr, preferably Pr is added in the form of a PrCu alloy.
When the R2 contains Pr, and the Pr participates in grain boundary diffusion in the form of a PrCu alloy, the Cu can be added in a smelting and/or grain boundary diffusion mode.
When the Cu is added in the grain boundary diffusion, the Cu is added in the form of PrCu alloy, the content of the Cu is preferably 0.03-0.15 wt%, and the wt% is the mass percentage of elements in the raw material composition, wherein the Cu accounts for 0.1-17 wt% of the PrCu.
The temperature of the grain boundary diffusion can be 800-1000 ℃, such as 850 ℃.
The time of the grain boundary diffusion can be 5 to 20 hours, such as 5 to 15 hours, and further such as 18 hours.
After the grain boundary diffusion, low temperature tempering treatment is also performed as conventional in the art. The temperature of the low-temperature tempering treatment is generally 460-560 ℃, for example 550 ℃. The time of the low-temperature tempering treatment can be 1-3 h.
The invention also provides the neodymium iron boron magnet material prepared by the preparation method.
The invention also provides application of the neodymium iron boron magnet material in preparation of magnetic steel.
Wherein, the magnetic steel is preferably 54SH and/or 52UH high-performance magnetic steel.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
(1) the magnet material has excellent magnet performance, wherein Br is more than or equal to 14.4kGs, and Hcj is more than or equal to 24.5 kOe; the Br temperature coefficient is more than or equal to-0.108%/DEG C at the temperature of 20-120 ℃; the grain boundary continuity is more than 96%, and the triangular area is less than 3.12%;
(2) the magnet material can be used for manufacturing 54SH and/or 52UH high-performance magnetic steel, and the production cost is reduced because the magnet material does not contain Co.
Drawings
Fig. 1 is an EPMA micrograph of the neodymium iron boron magnet material prepared in example 1.
Fig. 2 is an EPMA spectrum of the neodymium iron boron magnet material prepared in example 1.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
TABLE 1 formulation and content (wt%) of raw material composition of NdFeB magnet Material
Figure BDA0002393097850000151
Figure BDA0002393097850000161
Note: "/" means that the element is not included.
The preparation method of the neodymium iron boron magnet material in examples 1 to 9 and comparative examples 1 to 5 is as follows:
(1) smelting and casting processes: according to the formulation shown in Table 1, the prepared raw materials except for R2 (Pr was added as PrCu in R2 of examples 4 and 6, and the contents of Cu added in the grain boundary diffusion step in examples 4 and 6 were 0.05 wt% and 0.03wt%, respectively) were put into a crucible of alumina, and vacuum melting was performed in a high-frequency vacuum melting furnace under a vacuum of 0.05Pa and at 1500 ℃. Introducing argon into the intermediate frequency vacuum induction rapid hardening melt-spun furnace, casting, and rapidly cooling the alloy to obtain an alloy sheet.
(2) Hydrogen crushing powder preparation process: and (3) vacuumizing the hydrogen breaking furnace in which the quenching alloy is placed at room temperature, introducing hydrogen with the purity of 99.9% into the hydrogen breaking furnace, maintaining the pressure of the hydrogen at 90kPa, fully absorbing the hydrogen, vacuumizing while heating, fully dehydrogenating, cooling, and taking out the powder after hydrogen breaking and crushing. Wherein the temperature for hydrogen absorption is 25 ℃ and the temperature for dehydrogenation is 550 ℃.
(3) And (3) airflow milling powder preparation process: the powder after hydrogen crushing was subjected to jet milling for 3 hours under a nitrogen atmosphere at a pressure in the milling chamber of 0.6MPa to obtain a fine powder.
(4) And (3) forming: and forming the powder after passing through the airflow film in a magnetic field intensity of more than 1.5T.
(5) And (3) sintering: the molded bodies were transferred to a sintering furnace and sintered at 1040 ℃ for 2 hours under a vacuum of less than 0.5Pa to obtain sintered bodies.
(6) And (3) a grain boundary diffusion process: after the surface of the sintered body is cleaned, R2 (such as Tb alloy or fluoride, Dy alloy or one or more of fluoride and PrCu alloy) is coated on the surface of the sintered body, and is diffused for 18h at the temperature of 850 ℃, then is cooled to the room temperature, and is subjected to low-temperature tempering treatment for 3h at the temperature of 550 ℃.
Effect example 1
The neodymium iron boron magnet materials in examples 1-9 and comparative examples 1-5 are respectively taken, the magnetic property and the components are measured, and the phase composition of the magnet is observed by FE-EPMA.
(1) The components of the neodymium-iron-boron magnet material were measured using a high-frequency inductively coupled plasma emission spectrometer (ICP-OES). The following table 2 shows the results of component detection.
TABLE 2 composition and content (wt%) of NdFeB Material
Figure BDA0002393097850000171
Note: "/" means that the element is not included.
(3) Evaluation of magnetic Properties: the neodymium iron boron magnet material is subjected to magnetic property detection by using a PFM-14 magnetic property measuring instrument of Hirst company in UK; the following Table 3 shows the results of magnetic property measurements.
(4) Testing high-temperature performance: the formula for calculating the temperature coefficient is:
Figure BDA0002393097850000172
the calculation results are shown in table 3.
(5) Determination of microstructure: the results of the triangular area, grain boundary continuity, etc. are shown in Table 3, wherein R29.8～32.14Fe65.89～67.25M0.12～0.18B1.75～1.88The phases were obtained according to the FE-EPMA test.
TABLE 3
Figure BDA0002393097850000173
Figure BDA0002393097850000181
1) The temperature coefficient of remanence of the neodymium iron boron magnet material is equivalent to that of a comparative example, and even better; the coercive force is obviously higher than that of a comparative example (examples 1-9); the reason is that: according to the embodiment that the difference between the "mass ratio of C and O in the grain boundary triangular region" minus the "mass ratio (%) of C and O in the two-grain boundary" is smaller than that in the comparative example, it can be concluded that the hetero-phase migrates from the grain boundary triangular region to the two-grain boundary, which explains the improvement of the continuity of the grain boundary and the reason of the improvement of the magnetic property from the mechanism. The results show that under the same Co-free condition, the effect is poor if the formula of the application is not cooperated synergistically (comparative examples 1-5).
2) Based on the formulation of the present application, even if the contents of Cu and TRE are adjusted, R cannot be generated if the contents of other components are not within the range defined in the present application29.8～32.14Fe65.89～67.25M0.12～0.18B1.75～1.88In the phase, Br and Hcj of the R-T-B based permanent magnetic material cannot be simultaneously maintained at high values, and grain boundaries are continuously reduced and the triangular region area is large (comparative example 1 and comparative example 3).
3) Based on the formulation of the present application, even if the contents of Cu and M are adjusted, R cannot be generated unless the contents of other components are within the ranges defined in the present application29.8～32.14Fe65.89～67.25M0.12～0.18B1.75～1.88In the phase, Br and Hcj of the R-T-B permanent magnet material could not be maintained at high values at the same time, and the grain boundary was continuously decreased and the triangular region area was large (comparative example 2).
4) Based on the formulation of the present application, even if the TRE and M contents are adjusted, R cannot be generated if the contents of other components are not within the range defined in the present application29.8～32.14Fe65.89～67.25M0.12～0.18B1.75～1.88In the phase, Br and Hcj of the R-T-B permanent magnet material could not be maintained at high values at the same time, and the grain boundary was continuously decreased and the triangular region area was large (comparative example 4).
5) Based on the formulation of the present application, even if the content range of M is adjusted, Tb is not contained in R2, and R cannot be generated if the content of other components is not within the range defined in the present application29.8～32.14Fe65.89～67.25M0.12～0.18B1.75～1.88In the phase, Br and Hcj of the R-T-B permanent magnet material could not be maintained at high values at the same time, and the grain boundary was continuously decreased and the triangular region area was large (comparative example 5).
Effect example 2
As shown in figure 1 of the drawings, in which,in fig. 1, the black area structure is that when a sample is observed by a scanning electron microscope, neodymium-rich phases brought by grinding and polishing fall off, so that black holes appear in the picture. Wherein point 3 is Nd2Fe14B main phase (dark gray region), point 2 is the grain boundary triangle region (silver white region), and point 1 is the new phase R contained in the two-particle grain boundary29.8～32.14Fe65.89～67.25M0.12～0.18B1.75～1.88A phase. The results show that: the area of the grain boundary triangle is smaller than that of the conventional magnet. In addition, the EPMA spectrum of fig. 2 indicates that "Tb element is uniformly distributed in the grain boundary and the primary phase shell layer".

Claims (91)

1. A neodymium iron boron magnet material is characterized in that R: 28 to 33 wt%; the R comprises R1 and R2, and the content of the R2 is 0.2-1 wt%; the R1 includes Nd and does not contain RH;
said R2 comprises Tb;
B：0.9~1.1wt%；
cu: 0.15wt% or less and not 0 wt%;
m: 0.4wt% or less and not 0 wt%;
m comprises one or more of Ti, Ni, V, Nb, Ta, Cr, Mo, W, Mn, Zr, Hf, Zn and Ag;
Fe：60~70.6wt%；
the wt% is the mass percentage of the element in the neodymium iron boron magnet material;
the neodymium iron boron magnet material does not contain Co;
the neodymium-iron-boron magnet material comprises Nd2Fel4B crystal grains and shell layer thereof, adjacent to the Nd2Fel4Two-grain boundaries and grain boundary trigones of B grains, in which Nd in R1 is distributed2Fel4B crystal grains, the two-particle grain boundary and the grain boundary triangular region, wherein R2 is mainly distributed in the shell layer, the two-particle grain boundary and the grain boundary triangular region; the area percentage of the grain boundary triangular region is 2-3.5%; the grain boundary continuity of the neodymium iron boron magnet material is more than 96%;
the grain boundary of the two particles also contains chemical groupsTo be R29.8~32.14Fe65.89~67.25M0.12~0.18B1.75~1.88A phase, wherein R comprises Nd and Tb, and M comprises one or more of Ti, Ni, V, Nb, Ta, Cr, Mo, W, Mn, Zr, Hf, Zn and Ag;
the R is29.8~32.14Fe65.89~67.25M0.12~0.18B1.75~1.88The area ratio of the phase in the grain boundary of the two particles is 0.7-2.5%.
2. The neodymium-iron-boron magnet material as claimed in claim 1, wherein the area proportion of the grain boundary triangular region is 2.2-2.9%;
and/or the grain boundary continuity is 97.5% or more;
and/or the content range of the R is 29.5-31.6 wt%, and the wt% is the mass percentage of elements in the neodymium iron boron magnet material;
and/or, the R1 includes one or more of Pr, La and Ce;
and/or the content range of the R2 is 0.2-0.8 wt%, and the wt% is the mass percentage of elements in the neodymium iron boron magnet material;
and/or the Tb accounts for 0.5-1 wt%, and the wt% is the mass percentage of elements in the neodymium iron boron magnet material;
and/or, the R2 also comprises one or more of Pr, Dy, Ho and Gd;
and/or the content range of B is 0.9-0.99 wt%, and the wt% is the mass percentage of elements in the neodymium iron boron magnet material;
and/or the content range of the Cu is 0.07-0.15 wt%, and the wt% is the mass percentage of elements in the neodymium iron boron magnet material;
and/or the Cu is added in a smelting and/or grain boundary diffusion mode;
and/or, the M also comprises one or more of Bi, Sn, Zn, Ga, In, Au and Pb.
3. The ndfeb magnet material according to claim 1, wherein the content of M is 0.1 to 0.32 wt%, wt% being the mass percentage of elements in the ndfeb magnet material.
4. The neodymium-iron-boron magnet material as claimed in claim 1, wherein the area proportion of the grain boundary triangular region is 2.4-3.2%;
and/or the content range of R is 29.8-32.5 wt%, and the wt% is the mass percentage of elements in the neodymium iron boron magnet material;
and/or the content range of the R2 is 0.5-1 wt%, and the wt% is the mass percentage of elements in the neodymium iron boron magnet material;
and/or the content range of B is 0.98-1.05 wt%, and the wt% is the mass percentage of elements in the neodymium iron boron magnet material;
and/or the content range of the Cu is less than 0.08wt% and not 0wt%, and the wt% is the mass percentage of elements in the neodymium iron boron magnet material.
5. The neodymium-iron-boron magnet material according to claim 1, wherein the grain boundary trigonal area fraction is 2.42%, 2.78%, 2.83%, 3.12%, 2.84%, 2.23%, 2.32%, 2.65%, or 2.89%.
6. The neodymium-iron-boron magnet material of claim 1, wherein the grain boundary continuity is 97.92%, 98.46%, 98.33%, 98.24%, 98.13%, 97.96%, 97.93%, 98.57% or 98.67%.
7. The ndfeb magnet material according to claim 1, wherein the amount of R is in the range of 31.2 wt%, 32.2 wt%, 30.9 wt% or 31.5 wt%, wt% being the mass percentage of the element in the ndfeb magnet material.
8. The neodymium-iron-boron magnet material of claim 1, wherein the R1 includes Pr.
9. The ndfeb magnet material according to claim 1, wherein the amount of R2 is in the range 0.6wt%, 0.9 wt% or 0.7wt%, wt% being the mass percentage of the element in the ndfeb magnet material.
10. The ndfeb magnet material according to claim 1, wherein the Tb content is in the range 0.8wt%, 0.6wt%, 0.75 wt%, 0.9 wt% or 0.7wt%, wt% being the mass percentage of the element in the ndfeb magnet material.
11. The ndfeb magnet material according to claim 1, wherein the B content is in the range of 1wt%, 1.02 wt% or 1.03 wt%, wt% being the mass percentage of the element in the ndfeb magnet material.
12. The ndfeb magnet material according to claim 1, wherein the Cu is present in a range of 0.12 wt%, 0.13 wt%, 0.03wt%, 0.05 wt%, 0.09 wt%, 0.1wt% or 0.07wt%, wt% being the mass percentage of the element in the ndfeb magnet material.
13. The ndfeb magnet material according to claim 1, wherein when the Cu is added at grain boundary diffusion, the Cu is added in the form of a PrCu alloy, the content of Cu is 0.03 to 0.15wt%, wt% is the mass percentage of elements in the ndfeb magnet material, and the percentage of Cu in the PrCu is 0.1 to 17 wt%.
14. The ndfeb magnet material according to claim 1, wherein the content of M is 0.1 to 0.15wt%, wt% being the mass percentage of elements in the ndfeb magnet material.
15. The ndfeb magnet material according to claim 1, wherein the content of M is 0.25 wt%, 0.32 wt%, 0.22 wt% or 0.2wt%, wt% being the mass percentage of elements in the ndfeb magnet material.
16. The neodymium-iron-boron magnet material of claim 2, wherein the M includes one or more of Ga, Ti, and Nb.
17. The ndfeb magnet material according to claim 2, wherein when R1 contains Pr, Pr is added in the form of PrNd, or in the form of a mixture of pure Pr and Nd, or in the form of a mixture of PrNd, pure Pr and Nd;
and/or, when the R2 includes Pr, the content range of the Pr is less than 0.2wt% and is not 0wt%, and the wt% is the mass percentage of elements in the neodymium iron boron magnet material;
and/or, when R2 includes Dy, the content of Dy is in the range of 0.3wt% or less and not 0wt%, wt% being the mass percentage of the element in the neodymium iron boron magnet material;
and/or, when the R2 includes Ho, the content range of Ho is 0.15wt% or less and is not 0wt%, wt% being the mass percentage of the element in the neodymium iron boron magnet material;
and/or, when the R2 includes Gd, the content range of Gd is 0.15wt% or less and is not 0wt%, wt% being the mass percentage of the element in the neodymium iron boron magnet material;
and/or when the M comprises Nb, the content range of Nb is 0.05-0.1 wt%, and the wt% is the mass percentage of elements in the neodymium iron boron magnet material;
and/or the neodymium iron boron magnet material also contains Al.
18. The ndfeb magnet material according to claim 2, wherein when M comprises Ti, the Ti content is in the range of 0 to 0.35wt%, wt% being the mass percentage of the element in the ndfeb magnet material.
19. The ndfeb magnet material according to claim 3, wherein when M comprises Ga, the content of Ga is in the range of 0.02 to 0.3wt%, wt% being the mass percentage of the element in the ndfeb magnet material.
20. The neodymium-iron-boron magnet material of claim 17, wherein when added in the form of PrNd, Pr: nd =25:75 or 20: 80.
21. the ndfeb magnet material according to claim 17, wherein when added as a mixture of pure Pr and Nd or as a mixture of PrNd, pure Pr and Nd, the content of Pr is 0.1-2 wt%, wt% being the mass percentage of elements in the ndfeb magnet material.
22. The ndfeb magnet material according to claim 17, wherein when added as a mixture of pure Pr and Nd or as a mixture of PrNd, pure Pr and Nd, the content of Pr is 0.2wt% or 0.5 wt%, wt% being the mass percentage of the element in the ndfeb magnet material.
23. The ndfeb magnet material of claim 17, wherein when R2 includes Pr, the Pr is present in the range of 0.2wt% or 0.1wt%, wt% being the mass percentage of elements in the ndfeb magnet material.
24. The ndfeb magnet material as claimed in claim 17, wherein when R2 includes Dy, the Dy is present in an amount in the range of 0.1wt%, 0.05 wt% or 0.12 wt%, wt% being the mass percentage of the element in the ndfeb magnet material.
25. The ndfeb magnet material of claim 17, wherein when the R2 includes Ho, the Ho is present in an amount in the range of 0.1wt% or 0.02 wt%, wt% being the mass percent of the element in the ndfeb magnet material.
26. The ndfeb magnet material of claim 17, wherein when R2 includes Gd, the Gd is present in the range of 0.1wt% or 0.06 wt%, wt% being the mass percentage of the element in the ndfeb magnet material.
27. The ndfeb magnet material as claimed in claim 18, wherein when M comprises Ti, the Ti content is in the range of 0.05 to 0.3wt%, wt% being the mass percentage of the element in the ndfeb magnet material.
28. The ndfeb magnet material according to claim 27, wherein the Ti content is in the range of 0.1 to 0.15wt%, wt% being the mass percentage of the element in the ndfeb magnet material.
29. The ndfeb magnet material as claimed in claim 27, wherein the Ti content is in the range 0.12 wt%, 0.05 wt% or 0.2wt%, wt% being the mass percentage of the element in the ndfeb magnet material.
30. The ndfeb magnet material according to claim 19, wherein the Ga content is in the range of 0.02 to 0.1wt%, wt% being the mass percentage of elements in the ndfeb magnet material.
31. The ndfeb magnet material according to claim 19, wherein the Ga content is in the range of 0.08 to 0.2wt%, wt% being the mass percentage of elements in the ndfeb magnet material.
32. The ndfeb magnet material of claim 30, wherein the Ga content is in the range of 0.07wt%, wt% being the mass percentage of elements in the ndfeb magnet material.
33. The ndfeb magnet material according to claim 2, wherein when the M element includes Ga, and Ga is 0.2wt% or more and is not 0.35wt%, Ti + Nb in the composition of the M element is 0.07wt% or less and is not 0wt%, and wt% is the mass percentage of the element in the ndfeb magnet material.
34. The ndfeb magnet material according to claim 33, wherein the composition of the M element is 0.05 wt% Ti + Nb, wt% being the mass percentage of the element in the ndfeb magnet material.
35. The ndfeb magnet material according to claim 17, wherein the Al content is in the range of 0.03wt% or less and not 0wt%, wt% being the mass percentage of the element in the ndfeb magnet material.
36. The ndfeb magnet material as claimed in claim 35, wherein the Al content is in the range of 0.01wt%, wt% being the mass percentage of the element in the ndfeb magnet material.
37. The ndfeb magnet material of claim 17, wherein when M comprises Ga and Ga is 0.01wt% or less, Al + Ga + Cu is 0.15wt% or less and not 0wt%, wt% being the mass percentage of elements in the ndfeb magnet material.
38. The ndfeb magnet material of claim 37, wherein Al + Ga + Cu is 0.12 wt%, wt% being the mass percentage of elements in the ndfeb magnet material.
39. The ndfeb magnet material of claim 37, wherein Al + Ga + Cu is 0.11wt% or less and not 0wt%, wt% being the mass percentage of elements in the ndfeb magnet material.
40. The ndfeb magnet material of claim 39, wherein Al + Ga + Cu is 0.07wt%, wt% being the mass percentage of elements in the ndfeb magnet material.
41. The neodymium-iron-boron magnet material of claim 17, wherein R is29.8~32.14Fe65.89~ 67.25M0.12~0.18B1.75~1.88The area of the phase in the two-particle grain boundary is 0.73%, 0.97%, 1.03%, 1.12%0.86%, 0.77%, 0.95%, 2.49% or 1.01%.
42. A raw material composition for preparing the neodymium-iron-boron magnet material as claimed in any one of claims 1 to 41, characterized by comprising the following components in percentage by weight:
r: 28 to 33 wt%; the R is a rare earth element and comprises rare earth metal R1 for smelting and rare earth metal R2 for grain boundary diffusion, and the content of R2 is 0.2-1 wt%;
the R1 includes Nd and does not contain RH;
said R2 comprises Tb;
B：0.9~1.1wt%；
cu: 0.15wt% or less and not 0 wt%;
m: 0.4wt% or less and not 0 wt%;
m comprises one or more of Ti, Ni, V, Nb, Ta, Cr, Mo, W, Mn, Zr, Hf, Zn and Ag;
Fe：60~70.6 wt%；
the RH is a heavy rare earth element;
the wt% is the mass percentage of the element in the raw material composition;
the raw material composition does not contain Co.
43. The raw material composition as claimed in claim 42, wherein the content of R is in the range of 29.5 to 31.6wt%, and the wt% is the mass percentage of the element in the raw material composition;
and/or, the R1 includes one or more of Pr, La and Ce;
and/or the content range of the R2 is 0.2-0.8 wt%, and the wt% is the mass percentage of elements in the raw material composition;
and/or the Tb accounts for 0.5-1 wt%, and the wt% is the mass percentage of the element in the raw material composition;
and/or, the R2 also comprises one or more of Pr, Dy, Ho and Gd;
and/or the content range of the B is 0.9-0.99 wt%, and the wt% is the mass percentage of elements in the raw material composition;
and/or the content range of the Cu is 0.07-0.15 wt%, and the wt% is the mass percentage of the element in the raw material composition;
and/or the Cu is added in a smelting and/or grain boundary diffusion mode;
and/or, the M also comprises one or more of Bi, Sn, Zn, Ga, In, Au and Pb.
44. A feedstock composition according to claim 42, wherein the M is present in an amount of 0.1 to 0.15wt%, wt% being the mass percentage of the element in the feedstock composition.
45. The raw material composition as claimed in claim 42, wherein the content of R is in the range of 29.8 to 32.5 wt%, and wt% is the mass percentage of element in the raw material composition;
and/or the content range of the R2 is 0.5-1 wt%, and the wt% is the mass percentage of elements in the raw material composition;
and/or the content range of the B is 0.98-1.05 wt%, and the wt% is the mass percentage of elements in the raw material composition;
and/or the content range of the Cu is less than 0.08wt% and not 0wt%, and the wt% is the mass percentage of the element in the raw material composition;
and/or the content of M is 0.1-0.32 wt%, and the wt% is the mass percentage of elements in the raw material composition.
46. The feedstock composition of claim 42, wherein R is present in an amount ranging from 31.2 wt%, 32.2 wt%, 30.9 wt%, or 31.5 wt%, wt% being the mass percent of the element in the feedstock composition.
47. A feedstock composition according to claim 42, wherein said R1 comprises Pr.
48. The feed composition of claim 42, wherein R2 is present in an amount ranging from 0.6wt%, 0.9 wt%, or 0.7wt%, with wt% being the mass percent of element in the feed composition.
49. The feed composition of claim 42, wherein the Tb is present in an amount ranging from 0.8wt%, 0.6wt%, 0.75 wt%, 0.9 wt% or 0.7wt%, wt% being the mass percentage of the element in the feed composition.
50. The feedstock composition of claim 42, wherein B is present in an amount ranging from 1wt%, 1.02 wt%, or 1.03 wt%, with wt% being the mass percent of the element in the feedstock composition.
51. The feedstock composition of claim 42, wherein the Cu is present in a range of 0.12 wt%, 0.13 wt%, 0.03wt%, 0.05 wt%, 0.09 wt%, 0.1wt%, or 0.07wt%, with wt% being the mass percent of the element in the feedstock composition.
52. The raw material composition of claim 42, wherein when the Cu is added during grain boundary diffusion, the Cu is added in the form of a PrCu alloy, the content of the Cu is 0.03-0.15 wt%, and the wt% is the mass percentage of the element in the raw material composition; wherein the percentage of Cu in PrCu is 0.1-17 wt%.
53. The feed composition of claim 42, wherein M is present in an amount of 0.25 wt.%, 0.32 wt.%, 0.22 wt.%, or 0.2 wt.%, wt.% being the mass percent of element in the feed composition.
54. The feed composition of claim 42 or 43, wherein M comprises one or more of Ga, Ti and Nb.
55. The feedstock composition of claim 43, wherein when said R1 comprises Pr, the Pr is added in the form of PrNd, or in the form of a mixture of pure Pr and Nd, or in the form of a mixture of PrNd, pure Pr, and Nd;
and/or, when the R2 comprises Pr, the content range of the Pr is less than 0.2wt% and is not 0wt%, and the wt% is the mass percentage of elements in the raw material composition;
and/or, when R2 includes Dy, the content of Dy is in the range of 0.3wt% or less and not 0wt%, wt% being the mass percentage of elements in the raw material composition;
and/or, when the R2 comprises Ho, the content range of Ho is less than 0.15wt% and is not 0wt%, and wt% is the mass percentage of elements in the raw material composition;
and/or, when the R2 comprises Gd, the content range of the Gd is less than 0.15wt% and is not 0wt%, and the wt% is the mass percent of elements in the raw material composition;
and/or when the M comprises Nb, the content of Nb is in the range of 0.05-0.1 wt%, and the wt% is the mass percentage of elements in the raw material composition;
and/or, the raw material composition also contains Al.
56. The feedstock composition of claim 42, wherein when said M comprises Ti, said Ti is present in an amount ranging from 0 to 0.35wt%, wt% being the mass percent of the element in said feedstock composition.
57. The feedstock composition of claim 43, wherein when M comprises Ga, the Ga is in the range of 0.02 to 0.3wt%, wt% being the mass percent of the element in the feedstock composition.
58. A feedstock composition according to claim 55, wherein when added as PrNd, the ratio of Pr: nd =25:75 or 20: 80.
59. a raw material composition according to claim 55, wherein when added in the form of a mixture of pure Pr and Nd or in the form of a mixture of PrNd, pure Pr and Nd, the Pr content is 0.1 to 2wt%, wt% being the mass percentage of the element in the raw material composition.
60. A feedstock composition according to claim 59, wherein when added as a mixture of pure Pr and Nd, or as a mixture of PrNd, pure Pr and Nd, the Pr content is 0.2wt% or 0.5 wt%, wt% being the mass percentage of the element in the feedstock composition.
61. The feed composition of claim 55, wherein when R2 comprises Pr, the Pr is present in a range of 0.2wt% or 0.1wt%, wt% being the mass percent of element in the feed composition.
62. The raw material composition of claim 55, wherein when R2 includes Dy, the Dy is included in a range of 0.1wt%, 0.05 wt%, or 0.12 wt%, with wt% being the mass percent of element in the raw material composition.
63. The feed composition of claim 55, wherein when said R2 comprises Ho, said Ho is present in an amount ranging from 0.1wt% or 0.02 wt%, with wt% being the mass percent of element in said feed composition.
64. The feedstock composition of claim 55, wherein when R2 comprises Gd, the Gd is present in the range of 0.1wt% or 0.06 wt%, wt% being the mass percent of the element in the feedstock composition.
65. The feedstock composition of claim 55, wherein when said M comprises Ti, said Ti is present in an amount ranging from 0.05 to 0.3wt%, wt% being the mass percent of the element in said feedstock composition.
66. The feedstock composition of claim 65, wherein when said M comprises Ti, said Ti is present in an amount ranging from 0.1 to 0.15wt%, wt% being the mass percent of the element in said feedstock composition.
67. The feedstock composition of claim 65, wherein said Ti is present in an amount in the range of 0.12 wt%, 0.05 wt%, or 0.2wt%, wt% being the mass percent of the element in said feedstock composition.
68. The feedstock composition of claim 57, wherein when said M comprises Ga, said Ga is in the range of 0.02 to 0.1wt%, wt% being the mass percent of the element in said feedstock composition.
69. The feed composition of claim 57, wherein when M comprises Ga, the Ga is in the range of 0.08 to 0.2wt%, wt% being the mass percent of the element in the feed composition.
70. The feed composition of claim 68, wherein Ga is in the range of 0.07 wt.%, with wt.% being the mass percent of the element in the feed composition.
71. The raw material composition according to claim 43, wherein when the M element includes Ga, Ti, and Nb, and Ga is 0.2wt% or more and is not 0.35wt%, Ti + Nb in the composition of the M element is 0.07wt% or less and is not 0wt%, and wt% is a mass percentage of the element in the raw material composition.
72. The feedstock composition of claim 71, wherein the composition of M elements, Ti + Nb, is 0.05 wt%, with wt% being the mass percent of the elements in the feedstock composition.
73. The feedstock composition of claim 55, wherein, when Al is included in the feedstock composition, the Al is present in an amount in the range of 0.03wt% or less and not 0wt%, the wt% being the mass percent of the element in the feedstock composition.
74. The feedstock composition of claim 73, wherein, when Al is present in the feedstock composition, said Al is present in an amount in the range of 0.01wt%, with wt% being the mass percent of the element in said feedstock composition.
75. The feedstock composition of claim 55, wherein when M comprises Ga and Ga is 0.01wt% or less, Al + Ga + Cu is 0.15wt% or less and not 0wt%, wt% being the mass percent of the element in the feedstock composition.
76. The feed composition of claim 75, wherein Al + Ga + Cu is 0.12 wt% and wt% is the mass percent of the element in said feed composition.
77. The raw material composition of claim 75, wherein Al + Ga + Cu is 0.11wt% or less and not 0wt%, and wt% is a mass percentage of an element in the raw material composition.
78. The feed composition of claim 77, wherein Al + Ga + Cu is 0.07wt% and wt% is the mass percent of the element in the feed composition.
79. A preparation method of the neodymium iron boron magnet material according to any one of claims 1 to 41, characterized in that the raw material composition according to any one of claims 42 to 78 is adopted, the preparation method is a diffusion method, the R1 element is added in a smelting step, and the R2 element is added in a grain boundary diffusion step.
80. The method of claim 79, comprising the steps of: the elements except R2 in the raw material composition of the neodymium iron boron magnet material are smelted, milled, molded and sintered to obtain a sintered body, and then the mixture of the sintered body and R2 is subjected to grain boundary diffusion.
81. The preparation method of claim 80, wherein the smelting temperature is 1300-1700 ℃.
82. The method of claim 81, wherein the melting temperature is 1450-1550 ℃.
83. The method of claim 82, wherein the temperature of the smelting is 1500 ℃.
84. The method of claim 80, wherein milling comprises hydrogen milling and/or jet milling.
85. The method of claim 84, wherein the jet milled powder is at 0.1 to 2 MPa.
86. The method of claim 85, wherein the jet milling is performed at 0.5 to 0.7 MPa.
87. The method of claim 80, wherein when R2 further comprises Pr, Pr is added in the form of a PrCu alloy.
88. The method of claim 80, wherein when R2 contains Pr and Pr participates in grain boundary diffusion in the form of a PrCu alloy, the Cu is added during melting and/or grain boundary diffusion.
89. A neodymium iron boron magnet material prepared by the preparation method of any one of claims 79 to 88.
90. Use of a neodymium iron boron magnet material according to any one of claims 1 to 41 and 89 in the preparation of magnetic steel.
91. Use of a neodymium iron boron magnet material according to claim 90 in the preparation of magnetic steel, wherein the magnetic steel is a 54SH and/or 52UH high performance magnetic steel.
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