CN111261355B - 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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CN111261355B
CN111261355B CN202010121476.6A CN202010121476A CN111261355B CN 111261355 B CN111261355 B CN 111261355B CN 202010121476 A CN202010121476 A CN 202010121476A CN 111261355 B CN111261355 B CN 111261355B
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magnet material
mass percentage
raw material
neodymium
iron
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CN111261355A (en
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骆溁
黄佳莹
廖宗博
蓝琴
林玉麟
师大伟
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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    • 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
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
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    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
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    • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
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    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
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    • 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 discloses a neodymium iron boron magnet material, a raw material composition, a preparation method and an application, wherein the raw material composition 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: 60-70.5 wt%; co: less than 0.5wt% and not 0 wt%; RH is heavy rare earth element. 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 material2Fel4The 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 the scheme of low content of Co and no addition of heavy rare earth metal 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 the remanence B and the coercive force Hcj of the magnet are improved.
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：60～70.5wt％；
co: less than 0.5wt% and not 0 wt%;
the RH is a heavy rare earth element;
the wt% is the mass percentage of each element in the raw material composition.
In the present invention, the content of R is preferably 29.5 to 31.5wt%, or 29.8 to 32.8 wt%, for example 31.2 wt%, 32.2 wt%, or 30.9 wt%, where 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 0.5wt%, 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 0.94 wt%, 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 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 0.1 to 0.32 wt%, for example, 0.25 wt%, 0.32 wt%, 0.22 wt%, 0.32 wt%, or 0.2wt%, and the 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 the present invention, the content range of Co is preferably 0.4wt% or less and is not 0, for example, 0.1wt%, 0.2wt%, 0.3wt%, or 0.15wt%, and wt% is a mass percentage of the element 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 27.5 wt%; in R2: 0.5wt% of Tb; 0.9 wt% of B, 0.15wt% of Cu, 0.35wt% of Ti, 0.1wt% of Co, 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%, Co 0.2wt%, 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 0.5wt% of Tb; 0.98 wt% of B, 0.07wt% of Cu, 0.12 wt% of Ti, 0.1wt% of Nb, 0.1wt% of Ga, 0.3wt% of Co, 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 0.5wt% 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%, Co 0.15wt%, and the balance of Fe and inevitable impurities, wherein the wt% is the mass percentage of the 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; 1.1 wt% of B, 0.03wt% of Cu, 0.05 wt% of Ti, 0.1wt% of Ga, 0.15wt% of Co, 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; 1.03 wt% of B, 0.05 wt% of Cu, 0.3wt% of Ti, 0.02 wt% of Ga, 0.2wt% of Co, 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, 0.4wt% of Co, 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%, Co 0.1wt%, 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;
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;
co in the neodymium iron boron magnet material: less than 0.5wt% and not 0 wt%;
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 1.45-2.9%; the grain boundary continuity of the neodymium iron boron magnet material is more than 97.5%.
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 0.3 to 0.4%, for example, 0.32%, 0.39%, 0.34%, 0.36%, or 0.38%. The ratio of C to O in the grain boundary triangle is preferably 0.42 to 0.50% by mass, for example, 0.44%, 0.45%, 0.49%, 0.43%, 0.47%, or 0.48%.
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 two hetero phases of the rare earth oxide and the rare earth carbide, preferably, a new phase having a chemical composition R is detected in the two-particle grain boundary24.09～29.88M0.24～0.48Cu1.7～2.84(Fe+Co)67.35～73.24A 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.
In preferred embodiments of the present application, the structure of the novel phase is, for example, R26.91(Fe+Co)69.93Cu2.68M0.48、R24.60(Fe+Co)72.73Cu2.34M0.33、R25.35(Fe+Co)72.54Cu1.70M0.41、R29.49(Fe+Co)67.35Cu2.81M0.35、R24.37(Fe+Co)73.24Cu2.08M0.31、R29.88(Fe+Co)67.43Cu2.31M0.38、R24.09(Fe+Co)73.18Cu2.49M0.24、R26.11(Fe+Co)70.73Cu2.84M0.32。
Wherein, R is24.09～29.88M0.24～0.48Cu1.7～2.84(Fe+Co)67.35～73.24The area ratio of the phase in the two-particle grain boundary is preferably 1 to 3.2%, for example, 3.12%, 0.53%, 1.03%, 1.22%, 1.14%, 2.09%, 1.66%, and 2.35%. 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 the present invention, the area ratio of the grain boundary triangle is preferably 1.49 to 2.4% or 2.15 to 2.9%, for example, 1.84%, 2.38%, 2.16%, 2.47%, 1.91%, 1.49%, 1.98% or 2.86%.
In the present invention, the grain boundary continuity is preferably 98% or more, for example, 99.21%, 98.34%, 99.24%, 98.02%, 97.94%, or 98.13%.
In the present invention, the content of R is preferably 29.5 to 31.5wt%, or 29.8 to 32.8 wt%, for example, 31.2 wt%, 32.2 wt%, or 30.9 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 additive is in the form of a mixture of pure Pr and Nd, the content of Pr is preferably 0.1 to 2wt%, for example 0.2wt% or 0.5wt%, wt% being the mass percentage of the element in the neodymium iron boron magnet material. When the Nd is added in the form of a mixture of PrNd, pure Pr and Nd, the Pr content is preferably 0.1-2 wt%, and wt% is the mass percentage of elements in the Nd-Fe-B magnet material.
In the present invention, the content range of R2 is preferably 0.2 to 0.8wt%, or 0.5 to 1wt%, for example, 0.6wt%, 0.9 wt%, or 0.94 wt%, where wt% is the mass percentage of the element in the neodymium iron boron magnet material.
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 neodymium iron boron magnet material.
Wherein, when R2 includes Dy, the content range of Dy is preferably 0.3wt% or less and not 0wt%, such as 0.1wt%, 0.05 wt% or 0.12 wt%, wt% being the mass percentage of the element in the neodymium iron boron magnet material.
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 neodymium iron boron magnet material.
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 neodymium iron boron magnet material.
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 0.1 to 0.32 wt%, for example, 0.25 wt%, 0.32 wt%, 0.22 wt%, 0.32 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 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 the present invention, the Co content is preferably in a range of 0.4wt% or less and not 0, for example, 0.1wt%, 0.2wt%, 0.3wt%, or 0.15wt%, with wt% being the mass percentage of the element in the neodymium iron boron magnet material.
In a preferred embodiment of the present invention, the neodymium iron boron material comprises the following components by weight percentage: in R1: nd 27.5 wt%; in R2: 0.5wt% of Tb; 0.9 wt% of B, 0.15wt% of Cu, 0.35wt% of Ti, 0.1wt% of Co, 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 1.84%; the continuity of the grain boundary is 97.51 percent, and the new phase in the two-particle grain boundary is R26.91(Fe+Co)69.93Cu2.68M0.48。
In a preferred embodiment of the present invention, the neodymium iron boron material comprises the following components by weight percentage: in R1: nd 32 wt%; in R2: 0.8wt% of Tb; b1 wt%, Cu 0.12 wt%, Ti 0.15wt%, Nb 0.1wt%, Co 0.2wt%, 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 2.38%; the continuity of the grain boundary is 99.21 percent, and the new phase in the two-particle grain boundary is R24.60(Fe+Co)72.73Cu2.34M0.33。
In a preferred embodiment of the present invention, the neodymium iron boron material comprises the following components by weight percentage: in R1: 30.4 wt% of Nd, 0.2wt% of Pr; in R2: 0.1wt% of Dy and 0.5wt% of Tb; 0.98 wt% of B, 0.07wt% of Cu, 0.12 wt% of Ti, 0.1wt% of Nb, 0.1wt% of Ga, 0.3wt% of Co, 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 2.16 percent; the continuity of the grain boundary is 98.34 percent, and the new phase in the two-particle grain boundary is R25.35(Fe+Co)72.54Cu1.70M0.41。
In a preferred embodiment of the present invention, the neodymium iron boron material comprises the following components by weight percentage: in R1: 30.8 wt% of Nd and 0.5wt% 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%, Co 0.15wt%, 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 2.47 percent; the continuity of the grain boundary is 99.24 percent, and the new phase in the two-particle grain boundary is R29.49(Fe+Co)67.35Cu2.81M0.35。
In a preferred embodiment of the present invention, the neodymium iron boron material comprises the following components by weight percentage: 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; 1.1 wt% of B, 0.03wt% of Cu, 0.05 wt% of Ti, 0.1wt% of Ga, 0.15wt% of Co, 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 1.91%; the continuity of the grain boundary is 98.02 percent, and the new phase in the two-particle grain boundary is R24.37(Fe+Co)73.24Cu2.08M0.31。
In a preferred embodiment of the present invention, the neodymium iron boron material comprises the following components by weight percentage: 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; 1.03 wt% of B, 0.05 wt% of Cu, 0.3wt% of Ti, 0.02 wt% of Ga, 0.2wt% of Co, 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 1.49%; the continuity of the grain boundary is 97.94 percent, and the new phase in the two-particle grain boundary is R29.88(Fe+Co)67.43Cu2.31M0.38。
In a preferred embodiment of the present invention, the neodymium iron boron material comprises the following components by weight percentage: 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, 0.4wt% of Co, 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 1.98 percent; the continuity of the grain boundary is 97.88 percent, and the new phase in the two-particle grain boundary is R24.09(Fe+Co)73.18Cu2.49M0.24。
In a preferred embodiment of the present invention, the neodymium iron boron material comprises the following components by weight percentage: 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%, Co 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 2.86 percent; the continuity of the grain boundary is 98.13 percent, and the new phase in the two-particle grain boundary is R26.11(Fe+Co)70.73Cu2.84M0.32。
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 during grain boundary diffusion, 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%.
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 14.3kGs, and Hcj is more than or equal to 24.5 kOe; the Br temperature coefficient is more than or equal to-0.104%/DEG C at the temperature of 20-120 ℃; grain boundary continuity is more than 97.5%, and triangular area is less than 2.9%;
(2) the magnet material of the invention can be used for manufacturing 54SH and/or 52UH high-performance magnetic steel, and the production cost is reduced because only low content of Co is needed.
Drawings
Fig. 1 is an EPMA micrograph 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 BDA0002393103590000151
Figure BDA0002393103590000161
Note: "/" means that the element is not included.
The preparation method of the neodymium iron boron magnet material in examples 1 to 8 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 1-8 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 BDA0002393103590000171
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 BDA0002393103590000172
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 R24.09～29.88M0.24～0.48Cu1.7～2.84(Fe+Co)67.35～73.24According to the FE-EPMA test.
TABLE 3
Figure BDA0002393103590000173
Figure BDA0002393103590000181
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 1-8); 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 condition of the same low content of Co, 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 application24.09～29.88M0.24～0.48Cu1.7～2.84(Fe+Co)67.35～73.24In 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 application24.09～29.88M0.24～0.48Cu1.7～2.84(Fe+Co)67.35～73.24In 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 application24.09～29.88M0.24～0.48Cu1.7～2.84(Fe+Co)67.35～73.24In 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 application24.09～29.88M0.24～0.48Cu1.7～2.84(Fe+Co)67.35～73.24In 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 continuity of the grain boundary was reduced and the triangular region area was large (comparative example 5).
Effect example 2
As shown in fig. 1, which is a scanning photograph of the microstructure of the ndfeb magnet prepared in example 1, in fig. 1, the black area structure is that when a sample observed by a scanning electron microscope is prepared, the neodymium-rich phase brought by grinding and polishing falls off, so that a black void appears in the figure. 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 boundary24.09～29.88M0.24～0.48Cu1.7～2.84(Fe+Co)67.35～73.24. The results show that: the area of the grain boundary triangle is smaller than that of the conventional magnet.

Claims (80)

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%; said R2 comprises Tb; the R1 includes Nd and does not contain RH;
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;
co in the neodymium iron boron magnet material: less than 0.5wt% and not 0 wt%;
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, and R2 is mainly distributed in the shell layer,The two grain boundaries and the grain boundary triangular region; the area percentage of the grain boundary triangular region is 1.45-2.9%; the grain boundary continuity of the neodymium iron boron magnet material is more than 97.5%;
the grain boundary of the two particles also contains a chemical composition R24.09~29.88M0.24~0.48Cu1.7~2.84（Fe+Co)67.35~73.24A 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.
2. The neodymium-iron-boron magnet material of claim 1,
the area percentage of the grain boundary triangular region is 1.49-2.4% or 2.15-2.9%;
and/or the grain boundary continuity is more than 98%;
and/or the content range of the R is 29.5-31.5 wt% or 29.8-32.8 wt%, and the wt% is the mass percentage of elements in the neodymium iron boron magnet material;
and/or, the R1 further comprises one or more of Pr, La and Ce;
and/or the content range of the R2 is 0.2-0.8 wt% or 0.5-1 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% or 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 0.07-0.15 wt% or less than 0.08wt% and not 0wt%, 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 content of M is 0.1-0.15 wt% or 0.1-0.32 wt%, and the wt% is the mass percentage of elements in the neodymium iron boron magnet material;
and/or, the M also comprises one or more of Bi, Sn, Zn, Ga, In, Au and Pb;
and/or the content range of Co is less than 0.4wt% and not 0, and the wt% is the mass percentage of elements in the neodymium iron boron magnet material.
3. The neodymium-iron-boron magnet material according to claim 2, wherein the grain boundary trigonal area percentage is 1.84%, 2.38%, 2.16%, 2.47%, 1.91%, 1.49%, 1.98%, or 2.86%.
4. The neodymium-iron-boron magnet material according to claim 2, characterized in that the grain boundary continuity is 99.21%, 98.34%, 99.24%, 98.02%, 97.94% or 98.13%.
5. The ndfeb magnet material according to claim 2, wherein the amount of R is in the range of 31.2 wt%, 32.2 wt% or 30.9 wt%, wt% being the mass percentage of the element in the ndfeb magnet material.
6. The neodymium-iron-boron magnet material of claim 2, wherein the R1 further includes Pr.
7. The ndfeb magnet material according to claim 2, wherein the amount of R2 is in the range 0.6wt%, 0.9 wt% or 0.94 wt%, wt% being the mass percentage of the element in the ndfeb magnet material.
8. The ndfeb magnet material according to claim 2, 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.
9. The ndfeb magnet material according to claim 2, 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.
10. The ndfeb magnet material according to claim 2, 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.
11. The neodymium-iron-boron magnet material according to claim 2, wherein when the Cu is added during grain boundary diffusion, the Cu is added in the form of PrCu alloy, the content of the Cu is 0.03-0.15 wt%, and wt% is the mass percentage of elements in the raw material composition, wherein the percentage of the Cu in the PrCu is 0.1-17 wt%.
12. The ndfeb magnet material according to claim 2, wherein the content of M is 0.25 wt%, 0.32 wt%, 0.22 wt%, 0.32 wt% or 0.2wt%, wt% being the mass percentage of the element in the ndfeb magnet material.
13. The neodymium-iron-boron magnet material of claim 2, wherein the M includes one or more of Ga, Ti, and Nb.
14. The ndfeb magnet material according to claim 2, wherein the Co content is in the range of 0.1wt%, 0.2wt%, 0.3wt% or 0.15wt%, wt% being the mass percentage of the element in the ndfeb magnet material.
15. 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 Ti, the content range of the Ti is 0-0.35 wt%, and the wt% is the mass percentage of elements 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, when the M comprises Ga, the content of the Ga ranges from 0.02 to 0.3 wt%;
and/or the neodymium iron boron magnet material also contains Al;
and/or, said R24.09~29.88M0.24~0.48Cu1.7~2.84（Fe+Co)67.35~73.24The area ratio of the phase in the two-particle grain boundary is 1-3.2%.
16. The ndfeb magnet material according to claim 15, wherein when R1 contains Pr, the addition of Pr in the form of PrNd, Pr: nd =25:75 or 20: 80.
17. the ndfeb magnet material according to claim 15, wherein when R1 is added in the form of a mixture of pure Pr and Nd or a mixture of PrNd, pure Pr and Nd, the content of Pr is 0.1 to 2wt%, wt% being the mass percentage of the element in the ndfeb magnet material.
18. The ndfeb magnet material of claim 15, wherein when R1 is 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 0.5wt%, wt% being the mass percentage of the element in the ndfeb magnet material.
19. The ndfeb magnet material of claim 15, 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.
20. The ndfeb magnet material as claimed in claim 15, 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.
21. The ndfeb magnet material of claim 15, 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.
22. The ndfeb magnet material of claim 15, 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.
23. The ndfeb magnet material as claimed in claim 15, wherein when the M comprises Ti, the Ti content is in the range 0.05 to 0.3wt% or 0.1 to 0.15wt%, wt% being the mass percentage of the element in the ndfeb magnet material.
24. The ndfeb magnet material as claimed in claim 15, wherein when the M comprises Ti, 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.
25. The ndfeb magnet material of claim 15, wherein when the M comprises Ga, the Ga is present in the range of 0.02 to 0.1wt% or 0.08 to 0.2wt% as the mass percentage of elements in the ndfeb magnet material.
26. The ndfeb magnet material of claim 15, wherein when the M comprises Ga, the Ga is present in the range of 0.07wt%, wt% being the mass percentage of the element in the ndfeb magnet material.
27. The ndfeb magnet material according to claim 15, 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%, the wt% being the mass percentage of the element in the ndfeb magnet material.
28. The ndfeb magnet material according to claim 15, 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 0.05 wt%, and wt% is the mass percentage of the element in the ndfeb magnet material.
29. The ndfeb magnet material as claimed in claim 15, further comprising Al; the content range of the Al is less than 0.03wt% and not 0wt%, and the wt% is the mass percentage of elements in the neodymium iron boron magnet material.
30. The ndfeb magnet material as claimed in claim 15, further comprising Al; the content range of the Al is 0.01wt%, and the wt% is the mass percentage of elements in the neodymium iron boron magnet material.
31. The ndfeb magnet material of claim 29, 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.
32. The neodymium-iron-boron magnet material of claim 29, wherein when M includes Ga, and Ga is 0.01wt% or less, Al + Ga + Cu is 0.12 wt%; and the wt% is the mass percentage of the element in the neodymium iron boron magnet material.
33. The neodymium-iron-boron magnet material according to claim 29, wherein when M includes Ga and Ga is 0.01wt% or less, Al + Ga + Cu is 0.11wt% or less and is not 0 wt%; and the wt% is the mass percentage of the element in the neodymium iron boron magnet material.
34. The neodymium-iron-boron magnet material of claim 29, wherein when M includes Ga, and Ga is 0.01wt% or less, Al + Ga + Cu is 0.07 wt%; and the wt% is the mass percentage of the element in the neodymium iron boron magnet material.
35. The neodymium-iron-boron magnet material of claim 15, wherein R is24.09~29.88M0.24~0.48Cu1.7~2.84（Fe+Co)67.35~73.24The area fraction of the phase in the two-grain boundary is 3.12%, 0.53%, 1.03%, 1.22%, 1.14%, 2.09%, 1.66%, or 2.35%.
36. The raw material composition of neodymium iron boron magnet material according to any one of claims 1 to 35, characterized by comprising, in weight percent:
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：60~70.5 wt%；
co: less than 0.5wt% and not 0 wt%;
the RH is a heavy rare earth element;
the wt% is the mass percentage of each element in the raw material composition.
37. The raw material composition of a neodymium-iron-boron magnet material as claimed in claim 36, wherein the content of R is in a range of 29.5 to 31.5wt% or 29.8 to 32.8 wt%, wt% being a mass percentage of elements 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% or 0.5-1 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% or 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 0.07-0.15 wt% or 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 Cu is added in a smelting and/or grain boundary diffusion mode;
and/or the content of M is 0.1-0.15 wt% or 0.1-0.32 wt%, and the wt% is the mass percentage of elements in the raw material composition;
and/or, the M also comprises one or more of Bi, Sn, Zn, Ga, In, Au and Pb;
and/or the content range of the Co is less than 0.4wt% and is not 0, and the wt% is the mass percentage of elements in the raw material composition.
38. The raw material composition of a neodymium-iron-boron magnet material as claimed in claim 37, wherein the content of R is within a range of 31.2 wt%, 32.2 wt% or 30.9 wt%, wt% being a mass percentage of element in the raw material composition.
39. The raw material composition of neodymium-iron-boron magnet material according to claim 37, wherein R1 includes Pr.
40. The raw material composition of neodymium-iron-boron magnet material according to claim 37, wherein the content of R2 is in the range of 0.6wt%, 0.9 wt% or 0.94 wt%, wt% being the mass percentage of element in the raw material composition.
41. The raw material composition of neodymium-iron-boron magnet material as claimed in claim 37, wherein the content of Tb is in a range of 0.8wt%, 0.6wt%, 0.75 wt%, 0.9 wt% or 0.7wt%, wt% being the mass percentage of element in the raw material composition.
42. The raw material composition of a neodymium-iron-boron magnet material as claimed in claim 37, wherein the content range of B is 1wt%, 1.02 wt% or 1.03 wt%, wt% being the mass percentage of element in the raw material composition.
43. The raw material composition of neodymium-iron-boron magnet material according to claim 37, wherein the content of Cu is 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 a mass percentage of element in the raw material composition.
44. The raw material composition of a neodymium-iron-boron magnet material according to claim 37, wherein when the Cu is added at the time of grain boundary diffusion, the Cu is added in the form of PrCu, the content of the Cu is 0.03 to 0.15wt%, wt% is the mass percentage of element in the raw material composition, and the percentage of the Cu in the PrCu is 0.1 to 17 wt%.
45. The raw material composition of a neodymium-iron-boron magnet material as claimed in claim 37, wherein the content of M is 0.25 wt%, 0.32 wt%, 0.22 wt%, 0.32 wt% or 0.2wt%, wt% being a mass percentage of an element in the raw material composition.
46. The raw material composition of neodymium-iron-boron magnet material as claimed in claim 37, wherein the M includes one or more of Ga, Ti and Nb.
47. The raw material composition of a neodymium-iron-boron magnet material as claimed in claim 37, wherein the content of Co is in a range of 0.1wt%, 0.2wt%, 0.3wt% or 0.15wt%, wt% being a mass percentage of element in the raw material composition.
48. The raw material composition of neodymium-iron-boron magnet material according to claim 37, characterized in that 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 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 Ti, the content range of the Ti is 0-0.35 wt%, and the wt% is the mass percentage 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 when the M comprises Ga, the content range of the Ga is 0.02-0.3 wt%, and the wt% is the mass percentage of elements in the raw material composition;
and/or, the raw material composition also contains Al.
49. The raw material composition of neodymium-iron-boron magnet material according to claim 48, wherein when R1 contains Pr, the addition form of Pr is in the form of PrNd, and Pr: nd =25:75 or 20: 80.
50. the raw material composition of neodymium-iron-boron magnet material according to claim 48, wherein when R1 is 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 0.1-2 wt%, and the wt% is the mass percentage of element in the raw material composition.
51. The raw material composition of neodymium-iron-boron magnet material according to claim 48, characterized in that when R1 is 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 0.2wt% or 0.5wt%, wt% being the mass percentage of the element in the raw material composition.
52. The raw material composition of neodymium-iron-boron magnet material as claimed in claim 48, wherein when R2 includes Pr, the content of Pr is in the range of 0.2wt% or 0.1wt%, wt% being the mass percentage of element in the raw material composition.
53. The raw material composition of neodymium-iron-boron magnet material as claimed in claim 48, wherein when R2 includes Dy, the Dy is contained in an amount ranging from 0.1wt%, 0.05 wt% or 0.12 wt%, wt% being a mass percentage of element in the raw material composition.
54. The raw material composition of neodymium-iron-boron magnet material according to claim 48, characterized in that when the R2 includes Ho, the content range of Ho is 0.1wt% or 0.02 wt%, wt% being the mass percentage of element in the raw material composition.
55. The raw material composition of neodymium-iron-boron magnet material according to claim 48, characterized in that when R2 includes Gd, the Gd content ranges from 0.1wt% or 0.06 wt%, wt% being the mass percentage of the element in the raw material composition.
56. The raw material composition of neodymium iron boron magnet material according to claim 48, wherein when M includes Ti, the content of Ti is in a range of 0.05 to 0.3wt% or 0.1 to 0.15wt%, wt% being a mass percentage of element in the raw material composition.
57. The raw material composition of neodymium-iron-boron magnet material as claimed in claim 48, wherein when the M includes Ti, the content of Ti is in a range of 0.12 wt%, 0.05 wt% or 0.2wt%, wt% being a mass percentage of element in the raw material composition.
58. The raw material composition of neodymium-iron-boron magnet material as claimed in claim 48, wherein when M includes Ga, the content of Ga is in the range of 0.02-0.1 wt% or 0.08-0.2 wt%, wt% being the mass percentage of element in the raw material composition.
59. The raw material composition of neodymium-iron-boron magnet material as claimed in claim 48, wherein when M includes Ga, the content of Ga is in the range of 0.07wt%, wt% being the mass percentage of element in the raw material composition.
60. The raw material composition of a neodymium-iron-boron magnet material according to claim 48, 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 a mass percentage of the element in the raw material composition.
61. The raw material composition of a neodymium-iron-boron magnet material according to claim 48, 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 0.05 wt%, and wt% is the mass percentage of the element in the raw material composition.
62. The raw material composition of neodymium-iron-boron magnet material as claimed in claim 48, characterized in that the raw material composition further contains Al; the content range of the Al is less than 0.03wt% and not 0wt%, and the wt% is the mass percentage of elements in the raw material composition.
63. The raw material composition of neodymium-iron-boron magnet material as claimed in claim 48, characterized in that the raw material composition further contains Al; the content range of the Al is 0.01wt%, and the wt% is the mass percentage of elements in the raw material composition.
64. The raw material composition of neodymium-iron-boron magnet material as claimed in claim 62, wherein when M includes Ga and Ga is 0.01wt% or less, Al + Ga + Cu is 0.15wt% or less and is not 0wt%, wt% being a mass percentage of element in the raw material composition.
65. The raw material composition of neodymium-iron-boron magnet material as claimed in claim 62, wherein when M includes Ga and Ga is 0.01wt% or less, Al + Ga + Cu is 0.12 wt%, wt% being the mass percentage of element in the raw material composition.
66. The raw material composition of neodymium-iron-boron magnet material as claimed in claim 62, wherein when M includes Ga and Ga is 0.01wt% or less, Al + Ga + Cu is 0.11wt% or less and is not 0wt%, wt% being a mass percentage of element in the raw material composition.
67. The raw material composition of neodymium-iron-boron magnet material as claimed in claim 62, wherein when M includes Ga and Ga is 0.01wt% or less, Al + Ga + Cu is 0.07wt%, wt% being a mass percentage of element in the raw material composition.
68. A preparation method of a neodymium-iron-boron magnet material is characterized by adopting the raw material composition as claimed in any one of claims 36 to 67, 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.
69. The method of claim 68, 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.
70. The preparation method of claim 69, wherein the smelting temperature is 1300-1700 ℃.
71. The method of claim 69, wherein the smelting temperature is 1450-1550 ℃.
72. The method of claim 69, wherein the smelting temperature is 1500 ℃.
73. The method of claim 69, wherein said milling comprises hydrogen milling and/or jet milling.
74. The method of claim 73, wherein the jet milling is performed at 0.1 to 2MPa to produce the powder.
75. The method of claim 73, wherein the jet milled powder is jet milled at 0.5 to 0.7 MPa.
76. The method of claim 69, wherein when R2 further comprises Pr, Pr is added in the form of a PrCu alloy.
77. The method of claim 76, wherein when R2 includes 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.
78. A neodymium iron boron magnet material prepared by the preparation method of any one of claims 69 to 77.
79. Use of a neodymium iron boron magnet material according to any one of claims 1 to 35 and 78 in the preparation of magnetic steel.
80. Use of a neodymium iron boron magnet material of claim 79 in the preparation of magnetic steel; the magnetic steel is 54SH and/or 52UH high-performance magnetic steel.
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Address after: 366300 new industrial zone, Changting Economic Development Zone, Longyan City, Fujian Province

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