CN111223625B - 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 PDFInfo
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- 239000002994 raw material Substances 0.000 title claims abstract description 109
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 116
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 110
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 32
- 238000005324 grain boundary diffusion Methods 0.000 claims abstract description 31
- 238000003723 Smelting Methods 0.000 claims abstract description 19
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 11
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 10
- 229910052735 hafnium Inorganic materials 0.000 claims abstract description 10
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- 229910052709 silver Inorganic materials 0.000 claims abstract description 10
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 10
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 10
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 10
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 106
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- 239000002245 particle Substances 0.000 claims description 76
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- 238000001816 cooling Methods 0.000 claims description 4
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- 229910052737 gold Inorganic materials 0.000 claims description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
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- 229910001117 Tb alloy Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical group [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- 229910001004 magnetic alloy Inorganic materials 0.000 description 1
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- 238000001000 micrograph Methods 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
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- 229910000938 samarium–cobalt magnet Inorganic materials 0.000 description 1
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- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
Classifications
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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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
- H01F41/0293—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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/70—Wind energy
- Y02E10/72—Wind turbines with rotation axis in wind direction
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Hard Magnetic Materials (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Heat Treatment Of Articles (AREA)
- Manufacturing Cores, Coils, And Magnets (AREA)
Abstract
The invention provides a neodymium iron boron magnet material, a raw material composition, a preparation method and application. The raw material composition comprises: r: 28 to 33 wt%; r comprises R1 and R2, R1 is a rare earth element added during smelting, and R1 comprises Nd and Dy; the R2 is a rare earth element added during grain boundary diffusion, the R2 comprises Tb, and the content of R2 is 0.2-1 wt%; m: less than or equal to 0.4 wt% and not less than 0 wt%, the species of M including one or more of Ti, Ni, V, Nb, Ta, Cr, Mo, W, Mn, Zr, Hf and Ag; cu: less than or equal to 0.15 wt% and less than 0 wt%; b: 0.9-1.1 wt%; fe: 60 to 70.88 weight percent; 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
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 material 2 Fe l4 The 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 the most widely used permanent magnetA magnetic material. 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 has the advantages of high remanence, high coercivity and good high-temperature performance.
The invention relates to a raw material composition of a neodymium iron boron magnet material, which comprises the following components in percentage by mass: r: 28 to 33 wt%;
r is rare earth elements including R1 and R2, R1 is rare earth element added during smelting, and R1 includes Nd and Dy; the R2 is a rare earth element added during grain boundary diffusion, the R2 comprises Tb, and the content of R2 is 0.2-1 wt%;
m: less than or equal to 0.4 wt% and not less than 0 wt%, the species of M comprises one or more of Ti, Ni, V, Nb, Ta, Cr, Mo, W, Mn, Zr, Hf and Ag;
cu: less than or equal to 0.15 wt% and less than 0 wt%;
B：0.9～1.1wt％；
Fe：60wt％～70.88wt％；
the wt% is the mass percentage of each element content in the total mass of the raw material composition;
the raw material composition does not contain Co.
In the present invention, the amount of R in the raw material composition is preferably 29 to 31% by weight.
In the present invention, in the raw material composition, the content of Nd in R1 may be conventional in the art, and is preferably 28 to 32.5 wt%, with the percentage being mass percentage of the total mass of the raw material composition.
In the present invention, the content of Dy in R1 in the raw material composition is preferably 0.2 wt% or less, for example, 0.1 to 0.2 wt%.
In the present invention, the R1 may further include other rare earth elements conventional in the art, including, for example, one or more of Pr, Ho, Tb, Gd, and Y.
Wherein, when said R1 contains Pr, the addition form of Pr is 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 combination of PrNd, pure Pr and Nd. When added as PrNd, Pr: nd 25:75 or 20: 80; when the raw material composition is added in the form of a pure mixture of Pr and Nd or a combination of PrNd, pure mixture of Pr and Nd, the content of Pr is preferably 0.1 to 2 wt%, such as 0.1 wt%, 0.2 wt%, wherein the percentage is the mass percentage of the total mass of the raw material composition. The pure Pr or Nd in the present invention generally means a purity of more than 99.5%.
When the R1 contains Ho, the content of Ho is preferably 0.1-0.2 wt%, and the percentage is the mass percentage of each component in the total mass of the raw material composition.
When the R1 contains Gd, the content of Gd is preferably 0.1 to 0.2 wt%, and the percentage is the mass percentage of each component in the total mass of the raw material composition.
When the R1 contains Y, the content of Y is preferably 0.1-0.2 wt%, and the percentage is the mass percentage of each component in the total mass of the raw material composition.
In the invention, the content of the R2 is preferably 0.2 wt% to 0.8 wt%, and the percentage is the mass percentage of each component in the total mass of the raw material composition.
In the present invention, the content of Tb in R2 is preferably 0.2 wt% to 0.8 wt%, for example, 0.6 wt%.
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.
When R2 contains Pr, the content of Pr is preferably 0.2 wt% or less, and is not 0 wt%, for example 0.2 wt%, where wt% is the mass percentage of element in the raw material composition.
Wherein, when R2 contains Dy, the content of Dy is preferably 0.3 wt% or less, and not 0 wt%, for example 0.3 wt%, wt% being the mass percentage of elements in the raw material composition.
Wherein, when the R2 includes Ho, the content of Ho is preferably 0.15 wt% or less and not 0 wt%, wt% being the mass percentage of the element in the raw material composition.
Wherein, when the R2 includes Gd, the content of Gd is preferably 0.15 wt% or less and not 0 wt%, wt% being the mass percentage of the element in the raw material composition.
In the present invention, the content of M is preferably 0.1 wt% to 0.15 wt%, or 0.25 wt% to 0.4 wt%, for example 0.15 wt%, 0.25 wt%, 0.3 wt%, 0.35 wt%, 0.4 wt%.
In the present invention, the kind of M is preferably one or more of Ti, Zr, Nb, Ni, V, Ta, Cr, Mo, W, Mn, Hf and Ag.
Wherein, when the M includes Ti, the content of Ti is preferably 0.05 wt% to 0.3 wt%, for example, 0.05 wt%, 0.15 wt%, 0.3 wt%, and more preferably 0.1 wt% to 0.15 wt%.
Wherein, when said M contains Nb, the content of Nb is preferably 0.05 wt% to 0.15 wt%, such as 0.05 wt%, 0.15 wt%, more preferably 0.05 wt% to 0.1 wt%.
Wherein, the M preferably also comprises one or more of Bi, Sn, Zn, Ga, In, Au and Pb.
Wherein, when the M comprises Ga, the content of the Ga is preferably in the range of 0.1 to 0.3 wt%, such as 0.1 wt%, 0.15 wt%, 0.3 wt%, and the wt% is the mass percentage of the element in the raw material composition.
When the M element includes Ga, and Ga is 0.2 wt% or more and not 0.35 wt%, it is preferable that Ti + Nb in the composition of the M element is 0.07 wt% or less and not 0 wt%, 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 raw material composition of the present application preferably further contains Al; the content thereof is preferably 0.15 wt% or less, but not 0 wt%, for example 0.15 wt%.
When the M comprises Ga and Ga is 0.01 wt% or less, Al + Ga + Cu may be 0.15 wt% or less and not 0 wt%, for example 0.12 wt%; preferably, Al + Ga + Cu is 0.11 wt% or less and not 0 wt%, for example 0.07 wt%, wt% being the mass percentage of the element in the raw material composition.
In the present invention, the Cu content is preferably 0.08 wt% or less but not 0 wt%, or 0.1 wt% to 0.15 wt%, for example 0.07 wt%, 0.15 wt%.
In the present invention, the content of B is preferably 0.9 to 1.1% by weight, more preferably 0.97 to 1.05% by weight.
In the present invention, the content of Fe is preferably 65.65 wt% to 70.88 wt%, for example 67.99 wt%, 68.19 wt%.
In the present invention, preferably, the raw material composition comprises:
r: 29-31 wt%; the R1 comprises Nd and Dy, wherein the Dy is used in an amount of 0.1-0.2 wt%; r2 comprises Tb, the dosage of Tb is 0.2 wt% -0.8 wt%;
B：0.9wt％～1.1wt％；
cu: 0.15 wt% or less but not 0 wt%;
ti: 0.3 wt% or less but not 0 wt%;
the balance of Fe and inevitable impurities;
wherein the percentage is the mass percentage of each element in the raw material composition.
In a preferred embodiment of the present invention, the raw material composition comprises the following components:
r: 30.6 wt%; wherein R1 is Nd and Dy, Nd is 29.90 wt%, Dy is 0.10 wt%; r2 is Tb, Tb is 0.60 wt%;
B：0.99wt％；
Cu：0.07wt％；
Ti：0.15wt％；
Fe:68.19wt％；
wherein the percentage is the mass percentage of each element in the raw material composition.
In the present invention, preferably, the raw material composition comprises:
r: 29-31 wt%; the R1 comprises Nd and Dy, wherein the Dy is used in an amount of 0.1-0.2 wt%; r2 comprises Tb, the dosage of Tb is 0.2 wt% -0.8 wt%;
B：0.9wt％～1.1wt％；
cu: 0.15 wt% or less but not 0 wt%;
nb: 0.3 wt% or less but not 0 wt%;
the balance of Fe and inevitable impurities;
wherein the percentage is the mass percentage of each element in the raw material composition.
In a preferred embodiment of the present invention, the raw material composition comprises the following components:
r: 30.6 wt%; wherein R1 is Nd and Dy, Nd is 29.90 wt%, Dy is 0.10 wt%, R2 is Tb, Tb is 0.60 wt%;
B：0.99wt％；
Cu：0.07wt％；
Nb：0.15wt％；
Fe:68.19wt％；
wherein the percentage is the mass percentage of each element in the raw material composition.
In the present invention, preferably, the raw material composition comprises:
r: 29-31 wt%; the R1 comprises Nd and Dy, wherein the Dy is used in an amount of 0.1-0.2 wt%; r2 comprises Tb, the dosage of Tb is 0.2 wt% -0.8 wt%;
B：0.9wt％～1.1wt％；
cu: 0.15 wt% or less but not 0 wt%;
nb: 0.3 wt% or less but not 0 wt%;
Ga：0.05wt％-0.3wt％；
the balance of Fe and inevitable impurities;
wherein the percentage is the mass percentage of each element in the raw material composition.
In a preferred embodiment of the present invention, the raw material composition comprises the following components:
r: 30.6 wt%; wherein R1 is Nd and Dy, Nd is 29.90 wt%, Dy is 0.10 wt%, R2 is Tb, Tb is 0.60 wt%;
B：0.99wt％；
Cu：0.07wt％；
Nb：0.05wt％；
Ga：0.3wt％；
Fe:67.99wt％；
wherein, the percentage is the mass percentage of each element in the raw material composition.
In another preferred embodiment of the present invention, the raw material composition comprises the following components:
r: 29 wt%; wherein R1 is Nd and Dy, Nd is 28.6 wt%, Dy is 0.10 wt%, R2 is Tb, Tb is 0.30 wt%;
B：1.01wt％；
Cu：0.07wt％；
Ti：0.15wt％；
Ga：0.15wt％；
Fe:69.62wt％；
wherein the percentage is the mass percentage of each element in the raw material composition.
In another preferred embodiment of the present invention, the raw material composition comprises the following components:
r: 31 wt%; wherein R1 is Nd and Dy, Nd is 30.4 wt%, Dy is 0.10 wt%, R2 is Tb, Tb is 0.50 wt%;
B：0.98wt％；
Cu：0.07wt％；
Ti：0.15wt％；
Ga：0.1wt％；
Fe:67.7wt％；
wherein the percentage is the mass percentage of each element in the raw material composition.
In another preferred embodiment of the present invention, the raw material composition comprises the following components:
r: 30.6 wt%; wherein R1 is Nd and Dy, Nd is 29.9 wt%, Dy is 0.10 wt%, R2 is Tb, Tb is 0.60 wt%;
B：0.99wt％；
Cu：0.07wt％；
Ti：0.05wt％；
Ga：0.1wt％；
Fe:68.19wt％；
wherein the percentage is the mass percentage of each element in the raw material composition.
In another preferred embodiment of the present invention, the raw material composition comprises the following components:
r: 30.6 wt%; wherein R1 is Nd and Dy, Nd is 29.90 wt%, Dy is 0.10 wt%, R2 is Tb, Tb is 0.60 wt%;
B：0.99wt％；
Cu：0.07wt％；
Ti：0.3wt％；
Ga：0.1wt％；
Fe:67.94wt％；
wherein the percentage is the mass percentage of each element in the raw material composition.
In another preferred embodiment of the present invention, the raw material composition comprises the following components:
r: 28 wt%; wherein R1 is Nd and Dy, Nd is 27.3 wt%, Dy is 0.10 wt%, R2 is Tb, Tb is 0.2 wt%;
B：1.1wt％；
Cu：0.07wt％；
Ti：0.15wt％；
Nb：0.05wt％；
Ga：0.15wt％；
Fe:70.88wt％；
wherein the percentage is the mass percentage of each element in the raw material composition.
In another preferred embodiment of the present invention, the raw material composition comprises the following components:
r: 33 wt%; wherein R1 is Nd, Dy and Pr, Nd is 31.7 wt%, Dy is 0.20 wt%, Pr is 0.1 wt%, R2 is Tb, Tb is 1 wt%;
B：0.9wt％；
Cu：0.15wt％；
Ti：0.15wt％；
Al：0.15wt％；
Fe:65.65wt％；
wherein the percentage is the mass percentage of each element in the raw material composition.
In another preferred embodiment of the present invention, the raw material composition comprises the following components:
r: 31 wt%; wherein R1 is Nd and Dy, Nd is 29.9 wt%, Dy is 0.10 wt%, R2 is Tb, Dy and Pr, wherein Tb is 0.5 wt%, Dy is 0.30 wt%, and Pr is 0.20 wt%;
B：0.97wt％；
Cu：0.07wt％；
Ti：0.15wt％；
Fe:67.81wt％；
wherein the percentage is the mass percentage of each element in the raw material composition.
The invention also provides a preparation method of the neodymium iron boron magnet material, which is carried out by adopting the raw material composition, and the preparation method is a conventional diffusion preparation method in the field, wherein the R1 element is added in a smelting step, and the R2 element is added in a 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 diffused through a grain boundary.
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.
As known to those skilled in the art, since rare earth elements are usually lost in the melting and sintering processes, in order to ensure the quality of a final product, 0 to 0.3 wt% of a rare earth element (generally Nd element) is generally additionally added to the formula of a raw material composition in the melting process, wherein the percentage is the mass percentage of the additionally added rare earth element in the total content of the raw material composition; in addition, the content of the additionally added rare earth elements is not included in the category of the raw material composition.
The temperature of the smelting can be 1300-1700 ℃, preferably 1450-1550 ℃, for example 1500 ℃.
The smelting equipment is generally a high-frequency vacuum smelting furnace and/or a medium-frequency vacuum smelting furnace, such as a medium-frequency vacuum induction rapid hardening melt-spinning furnace.
The operation and conditions of the powder preparation can be conventional powder preparation process in the field, and generally comprise hydrogen powder preparation and/or airflow powder preparation.
The hydrogen pulverized powder generally comprises hydrogen absorption, dehydrogenation and cooling treatment. The temperature of the hydrogen absorption is generally 20-200 ℃. The dehydrogenation temperature is generally 400 to 650 ℃, preferably 500 to 550 ℃. The pressure of the hydrogen absorption is generally 50 to 600kPa, for example 90 kPa.
The jet milling powder is generally subjected to jet milling under the condition of 0.1-2 MPa, preferably 0.5-0.7 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.
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 in a vacuum degree of less than 5X 10 -1 Pa, and the like.
The sintering temperature can be 1000-1200 ℃, for example 1030-1090 ℃.
The sintering time can be 0.5-10 h, such as 2-5 h.
In the present invention, it is known to those skilled in the art that the R2 coating operation is generally included before the grain boundary diffusion.
Wherein said R2 is typically coated in the form of a fluoride or low melting point alloy, such as Tb fluoride. When Dy is further contained, Dy is preferably coated in the form of a fluoride of Dy. In addition, when Pr is further included, preferably, Pr is added in the form of a PrCu alloy.
When the R2 contains Pr and Pr participates in grain boundary diffusion in the form of a PrCu alloy, preferably, the addition timing of Cu in the preparation method is a grain boundary diffusion step, or is added at the same time in a smelting step and a grain boundary diffusion step; 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%.
In the present invention, the operation and conditions of the grain boundary diffusion treatment may be a grain boundary diffusion process that is conventional in the art.
The temperature of the grain boundary diffusion can be 800-1000 ℃, such as 850 ℃.
The time of the grain boundary diffusion can be 5-20 h, such as 5-15 h.
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 ℃, and the time is generally 1-3 h.
The invention also provides the neodymium iron boron magnet material prepared by the preparation method.
The invention also provides a neodymium iron boron magnet material, R: 28 to 33 wt%; the R comprises R1 and R2, the R1 comprises Nd and Dy, the R2 comprises Tb; the content of R2 is 0.2 wt% -1 wt%;
B：0.9～1.1wt％；
cu: 0.15 wt% or less and not 0 wt%;
m: 0.35 wt% 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：60wt％～70.88wt％；
the wt% is the mass percentage of each 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 Nd 2 Fe l4 B crystal grains and shell layer thereof, adjacent to the Nd 2 Fe l4 Two-grain boundaries and grain boundary trigones of B grains, in which the heavy rare earth element in R1 is mainly distributed in Nd 2 Fe l4 B, crystal grains, wherein R2 is mainly distributed in the shell layer, the two-particle grain boundary and the grain boundary triangular region, and the area percentage of the grain boundary triangular region is 1.5-3.5%; the grain boundary continuity of the neodymium iron boron magnet material is more than 96%; the mass ratio of C to O in the crystal boundary triangular region is 0.4-0.5%, and the mass ratio of C to O in the two-particle crystal boundary is more than 0.35%.
In the present invention, the heavy rare earth element in "R1 is mainly distributed in Nd 2 Fe l4 B grains "can be understood as that heavy rare earth elements in R1 caused by the conventional smelting sintering process in the art are mainly distributed (generally, more than 95%) in main phase grains, and are distributed in small amount in grain boundaries. "R2 is mainly distributed in the shell layer, the two-particle grain boundary and the grain boundary triangle" can be understood as that R2 mainly distributed (generally, more than 95%) in the shell layer of the main phase grains, the two-particle grain boundary and the grain boundary triangle caused by the grain boundary diffusion process in the prior artThe bounded triangular regions, too, have a small portion diffused into the main phase grains, for example at the outer edges of the main phase grains.
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 oxide, rare earth carbide, 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 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 (grains + grain boundaries).
Wherein C, O element in rare earth oxide and rare earth carbide is introduced in a conventional manner in the field, generally introduced as impurities or introduced in an atmosphere, specifically, for example, in the process of jet milling and pressing, additives are introduced, and during sintering, the additives are removed by heating, but a small amount of C, O element residue is unavoidable; 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 scheme of the invention, Tb forms a covering layer through grain boundary diffusion, so that the coercivity is improved; dy can reduce the generation amount of alpha-Fe during smelting, and is beneficial to the improvement of the magnetic property of the product.
In the present invention, it is known to those skilled in the art that C, O elements are generally present in the form of rare earth carbides and rare earth oxides in the grain boundary phase, and thus "mass ratio of C and O in the grain boundary triangle" and "mass ratio of C and O in the two-grain boundary" correspond to the hetero-phase rare earth carbides and rare earth oxides, respectively.
Wherein the percentage in "mass ratio (%) of C and O in the two-particle grain boundary" is the ratio of the mass of C and O in the two-particle grain boundary to the total mass of all elements in the grain boundary, and the percentage in "mass ratio (%) of C and O in the triangular region of the grain boundary" is the ratio of the mass of C and O in the triangular region of the grain boundary to the total mass of all elements in the grain boundary.
In addition, according to the example 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 reason for the improvement of the grain boundary continuity from the mechanism. In the present invention, the area ratio of the grain boundary trigones is preferably 1.59% to 3.28%, for example, 1.59%, 1.88%, 2.34%, 2.36%, 2.38%, 2.45%, 2.54%, 2.62%, 2.68%, 3.28%, more preferably 1.59% to 2%.
In the present invention, the grain boundary continuity is preferably 97% or more, for example 97.01%, 97.20%, 98.50%, 98.00%, 98.10%, 98.22%, 98.41%, 98.36%, 98.80%, 99.50%, more preferably 98% or more.
In the present invention, the mass ratio of C to O in the two-particle grain boundary is preferably 0.37% to 0.4%.
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 boundary x Fe 100-x-y-z Cu y M z (ii) a Wherein R comprises one or more of Nd, Dy and Tb, M comprises one or more of Ti, Ni, V, Nb, Ta, Cr, Mo, W, Mn, Zr, Hf, Zn and Ag, x is 32-36, y is less than 0.1 but not 0, z is less than 0.15 but not 0; wherein x is preferably 32.5-35.5, y is preferably 0.02-0.1, and z is preferably 0.07-0.12.
In preferred embodiments of the present application, the structure of the novel phase is, for example, R 34.5 Fe 65.4 Cu 0.03 M 0.07 ，R 34.1 Fe 65.68 Cu 0.1 M 0.12 ，R 33.2 Fe 66.68 Cu 0.04 M 0.08 ，R 33.56 Fe 66.28 Cu 0.05 M 0.11 ，R 34.41 Fe 65.42 Cu 0.08 M 0.09 ，R 35.26 Fe 64.58 Cu 0.07 M 0.09 ，R 35.50 Fe 64.38 Cu 0.04 M 0.08 ，R 32.50 Fe 67.39 Cu 0.03 M 0.08 ，R 33.33 Fe 66.58 Cu 0.02 M 0.07 ，R 34.22 Fe 65.64 Cu 0.06 M 0.08 。
In the present invention, the chemical composition is R x Fe 100-x-y-z Cu y M z The ratio of the area of the new phase in the two-particle grain boundary to the total area of the two-particle grain boundary is preferably 0.8 to 3%, more preferably 0.81 to 2.64%.
The inventors speculate that the new phase is generated at the grain boundary of the two grains, so that the continuity of the grain boundary is further improved, and the performance of the magnet is improved.
In the invention, the amount of R in the NdFeB magnet material is preferably 29-31 wt%.
In the neodymium iron boron magnet material, the content of Nd in R can be conventional in the field, and is preferably 28-32.5 wt%, and the percentage is the mass percentage of the total mass of the neodymium iron boron magnet material.
In the present invention, in the neodymium iron boron magnet material, the content of Dy in R1 is preferably less than 0.2 wt%, for example, 0.1 to 0.2 wt%.
In the present invention, the R1 may further include other rare earth elements conventional in the art, including, for example, one or more of Pr, Ho, Tb, Gd, and Y.
Wherein, when said R1 contains Pr, the addition form of Pr is 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 combination of PrNd, pure Pr and Nd. When added as PrNd, Pr: 25 Nd: 75 or 20: 80; when the pure Pr and Nd are added in the form of a mixture or a combination of PrNd, pure Pr and Nd, the Pr content is preferably 0.1-2 wt%, such as 0.1 wt%, 0.2 wt%, wherein the percentage is the mass percentage of each component content in the total mass of the NdFeB magnet material.
When the R1 contains Ho, the content of Ho is preferably 0.1 to 0.2 wt%, and the percentage is the mass percentage of each component in the total mass of the neodymium iron boron magnet material.
When the R1 contains Gd, the content of Gd is preferably 0.1 to 0.2 wt%, and the percentage is the mass percentage of each component in the total mass of the neodymium iron boron magnet material.
When the R1 contains Y, the content of Y is preferably 0.1 to 0.2 wt%, and the percentage is the mass percentage of each component in the total mass of the neodymium iron boron magnet material.
In the invention, the content of the R2 is preferably 0.2 wt% to 0.8 wt%, and the percentage is the mass percentage of each component in the total mass of the neodymium iron boron magnet material.
In the present invention, the content of Tb in R2 is preferably 0.2 wt% to 0.8 wt%, for example, 0.6 wt%.
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.
When R2 contains Pr, the content of Pr is preferably 0.2 wt% or less, and is not 0 wt%, for example 0.2 wt%, where wt% is the mass percentage of the element in the neodymium iron boron magnet material.
Wherein, when R2 contains Dy, the content of Dy is preferably 0.3 wt% or less, and not 0 wt%, for example 0.3 wt%, wt% being the mass percentage of elements in the neodymium iron boron magnet material.
When the R2 includes Ho, the content of Ho is preferably 0.15 wt% or less and not 0 wt%, where wt% is a mass percentage of an element in the neodymium iron boron magnet material.
Wherein, when the R2 includes Gd, the content of Gd is preferably 0.15 wt% or less and not 0 wt%, wt% being the mass percentage of the element in the neodymium iron boron magnet material.
In the present invention, the content of M is preferably 0.1 wt% to 0.15 wt%, or 0.25 wt% to 0.4 wt%, for example 0.15 wt%, 0.25 wt%, 0.3 wt%, 0.35 wt%, 0.4 wt%.
In the present invention, the kind of M is preferably one or more of Ti, Zr, Nb, Ni, V, Ta, Cr, Mo, W, Mn, Hf and Ag.
Wherein, when the M includes Ti, the content of Ti is preferably 0.05 wt% to 0.3 wt%, for example, 0.05 wt%, 0.15 wt%, 0.3 wt%, and more preferably 0.1 wt% to 0.15 wt%.
Wherein, when the M contains Nb, the content of Nb is preferably 0.05 wt% to 0.15 wt%, for example 0.05 wt%, 0.15 wt%, and more preferably 0.05 wt% to 0.1 wt%.
Wherein, the M preferably also comprises one or more of Bi, Sn, Zn, Ga, In, Au and Pb.
Wherein, when the M includes Ga, the content of the Ga is preferably in the range of 0.1 to 0.3 wt%, such as 0.1 wt%, 0.15 wt%, 0.3 wt%.
When the M element includes Ga and Ga is 0.2 wt% or more and is not 0.35 wt%, it is preferable that Ti + Nb in the composition of the M element is 0.07 wt% or less and is not 0 wt%, for example, 0.05 wt%. In addition, when Ti + Nb is excessive, remanence may be reduced.
In the present invention, preferably, the neodymium iron boron magnet material further contains Al; the content thereof is preferably 0.15 wt% or less, but not 0 wt%, for example 0.15 wt%.
When the M comprises Ga and Ga is 0.01 wt% or less, Al + Ga + Cu may be 0.15 wt% or less and not 0 wt%, for example 0.12 wt%; preferably, Al + Ga + Cu is 0.11 wt% or less, and is not 0 wt%, for example 0.07 wt%.
In the present invention, the content of Cu is preferably 0.08 wt% or less but not 0 wt%, or 0.1 wt% to 0.15 wt%, for example 0.07 wt%, 0.15 wt%.
In the present invention, the content of B is preferably 0.9 wt% to 1.1 wt%, more preferably 0.97 wt% to 1.05 wt%.
In the present invention, the content of Fe is preferably 65.65 wt% to 70.88 wt%, for example 67.99 wt%, 68.19 wt%.
In the present invention, preferably, the neodymium iron boron magnet material includes:
r: 29-31 wt%; the R1 comprises Nd and Dy, wherein the Dy is used in an amount of 0.1-0.2 wt%; r2 comprises Tb, the dosage of Tb is 0.2 wt% -0.8 wt%;
B：0.9wt％～1.1wt％；
cu: 0.15 wt% or less but not 0 wt%;
ti: 0.3 wt% or less but not 0 wt%;
the balance of Fe and inevitable impurities;
wherein, the percentage is the mass percentage of each element in the neodymium iron boron magnet material.
In a preferred embodiment of the present invention, the ndfeb magnet material comprises the following components:
r: 30.6 wt%; wherein R1 is Nd and Dy, Nd is 29.90 wt%, Dy is 0.10 wt%; r2 is Tb, Tb is 0.60 wt%;
B：0.99wt％；
Cu：0.07wt％；
Ti：0.15wt％；
Fe:68.19wt％；
wherein the percentage is the mass percentage of each element in the neodymium iron boron magnet material;
the area percentage of the grain boundary triangular region is 2.34 percent; the grain boundary continuity of the neodymium iron boron magnet material is 98%; the mass ratio of C to O in the triangular region of the grain boundary is 0.45 percent, and the mass ratio of C to O in the two-particle grain boundary is 0.39 percent; detection of a New phase R in the two-particle grain boundary 34.5 Fe 65.4 Cu 0.03 M 0.07 The ratio of the area of the new phase in the two-particle grain boundaries to the total area of the two-particle grain boundaries was 2.35%.
In the present invention, preferably, the neodymium iron boron magnet material includes:
r: 29-31 wt%; the R1 comprises Nd and Dy, wherein the Dy is used in an amount of 0.1-0.2 wt%; r2 comprises Tb, the dosage of Tb is 0.2 wt% -0.8 wt%;
B：0.9wt％～1.1wt％；
cu: 0.15 wt% or less but not 0 wt%;
nb: 0.3 wt% or less but not 0 wt%;
the balance of Fe and inevitable impurities;
wherein, the percentage is the mass percentage of each element in the neodymium iron boron magnet material.
In a preferred embodiment of the present invention, the neodymium iron boron magnet material comprises the following components:
r: 30.6 wt%; wherein R1 is Nd and Dy, Nd is 29.90 wt%, Dy is 0.10 wt%, R2 is Tb, Tb is 0.60 wt%;
B：0.99wt％；
Cu：0.07wt％；
Nb：0.15wt％；
Fe:68.19wt％；
wherein the percentage is the mass percentage of each element in the neodymium iron boron magnet material;
the area percentage of the grain boundary triangular region is 2.36%; the grain boundary continuity of the neodymium iron boron magnet material is 98.41%; the mass ratio of C to O in the triangular region of the grain boundary is 0.41 percent, and the mass ratio of C to O in the two-particle grain boundary is 0.38 percent; detection of a New phase R in the two-particle grain boundary 35.26 Fe 64.58 Cu 0.07 M 0.09 The ratio of the area of the new phase in the two-particle grain boundaries to the total area of the two-particle grain boundaries was 1.12%.
In the present invention, preferably, the neodymium iron boron magnet material includes:
r: 29-31 wt%; the R1 comprises Nd and Dy, wherein the Dy accounts for 0.1-0.2 wt%; r2 comprises Tb, the dosage of Tb is 0.2 wt% -0.8 wt%;
B：0.9wt％～1.1wt％；
cu: 0.15 wt% or less but not 0 wt%;
nb: 0.3 wt% or less but not 0 wt%;
Ga：0.05wt％-0.3wt％；
the balance of Fe and inevitable impurities;
wherein, the percentage is the mass percentage of each element in the neodymium iron boron magnet material.
In a preferred embodiment of the present invention, the ndfeb magnet material comprises the following components:
r: 30.6 wt%; wherein R1 is Nd and Dy, Nd is 29.90 wt%, Dy is 0.10 wt%, R2 is Tb, Tb is 0.60 wt%;
B：0.99wt％；
Cu：0.07wt％；
Nb：0.05wt％；
Ga：0.3wt％；
Fe:67.99wt％；
wherein the percentage is the mass percentage of each element in the neodymium iron boron magnet material;
the area percentage of the grain boundary triangular region is 2.45 percent; the grain boundary continuity of the neodymium iron boron magnet material is 98.80%; the mass ratio of C to O in the triangular region of the grain boundary was 0.45%, the mass ratio of C to O in the grain boundary of the secondary particle was 0.39%, and a new phase R was detected in the grain boundary of the secondary particle 35.50 Fe 64.38 Cu 0.04 M 0.08 The ratio of the area of the new phase in the two-particle grain boundaries to the total area of the two-particle grain boundaries was 2.03%.
In another preferred embodiment of the present invention, the ndfeb magnet material comprises the following components:
r: 29 wt%; wherein R1 is Nd and Dy, Nd is 28.6 wt%, Dy is 0.10 wt%, R2 is Tb, Tb is 0.30 wt%;
B：1.01wt％；
Cu：0.07wt％；
Ti：0.15wt％；
Ga：0.15wt％；
Fe:69.62wt％；
wherein the percentage is the mass percentage of each element in the neodymium iron boron magnet material;
the area percentage of the grain boundary triangular region is 1.88%; the grain boundary continuity of the neodymium iron boron magnet material is 97.20%; the mass ratio of C to O in the triangular region of the grain boundary is 0.44%, and the mass ratio of C to O in the two-particle grain boundary is 0.38%Detection of a novel phase R in the grain boundary of two grains 34.1 Fe 65.68 Cu 0.1 M 0.12 The ratio of the area of the new phase in the two-particle grain boundaries to the total area of the two-particle grain boundaries was 1.74%.
In another preferred embodiment of the present invention, the ndfeb magnet material comprises the following components:
r: 31 wt%; wherein R1 is Nd and Dy, Nd is 30.4 wt%, Dy is 0.10 wt%, R2 is Tb, Tb is 0.50 wt%;
B：0.98wt％；
Cu：0.07wt％；
Ti：0.15wt％；
Ga：0.1wt％；
Fe:67.7wt％；
wherein the percentage is the mass percentage of each element in the neodymium iron boron magnet material;
the area percentage of the grain boundary triangular region is 2.68 percent; the continuity of the grain boundary of the neodymium iron boron magnet material is 98.36%; the mass ratio of C to O in the triangular region of the grain boundary was 0.45%, the mass ratio of C to O in the grain boundary of the secondary particle was 0.39%, and a new phase R was detected in the grain boundary of the secondary particle 33.2 Fe 66.68 Cu 0.04 M 0.08 The ratio of the area of the new phase in the two-particle grain boundaries to the total area of the two-particle grain boundaries was 1.94%.
In another preferred embodiment of the present invention, the ndfeb magnet material comprises the following components:
r: 30.6 wt%; wherein R1 is Nd and Dy, Nd is 29.9 wt%, Dy is 0.10 wt%, R2 is Tb, Tb is 0.60 wt%;
B：0.99wt％；
Cu：0.07wt％；
Ti：0.05wt％；
Ga：0.1wt％；
Fe:68.19wt％；
wherein the percentage is the mass percentage of each element in the neodymium iron boron magnet material;
the area percentage of the grain boundary triangular region is 2.38%; grain boundary of the neodymium iron boron magnet materialThe continuity was 98.10%; the mass ratio of C to O in the triangular region of the grain boundary was 0.44%, the mass ratio of C to O in the grain boundary of the secondary particle was 0.4%, and a new phase R was detected in the grain boundary of the secondary particle 33.56 Fe 66.28 Cu 0.05 M 0.11 The ratio of the area of the new phase in the two-particle grain boundaries to the total area of the two-particle grain boundaries was 0.81%.
In another preferred embodiment of the present invention, the ndfeb magnet material comprises the following components:
r: 30.6 wt%; wherein R1 is Nd and Dy, Nd is 29.90 wt%, Dy is 0.10 wt%, R2 is Tb, Tb is 0.60 wt%;
B：0.99wt％；
Cu：0.07wt％；
Ti：0.3wt％；
Ga：0.1wt％；
Fe:67.94wt％；
wherein the percentage is the mass percentage of each element in the neodymium iron boron magnet material;
the area percentage of the grain boundary triangular region is 2.54 percent; the grain boundary continuity of the neodymium iron boron magnet material is 98.22%; the mass ratio of C to O in the triangular region of the grain boundary was 0.43%, the mass ratio of C to O in the grain boundary of the secondary particle was 0.4%, and a new phase R was detected in the grain boundary of the secondary particle 34.41 Fe 65.42 Cu 0.08 M 0.09 The ratio of the area of the new phase in the two-particle grain boundaries to the total area of the two-particle grain boundaries was 2.64%.
In another preferred embodiment of the present invention, the ndfeb magnet material comprises the following components:
r: 28 wt%; wherein R1 is Nd and Dy, Nd is 27.3 wt%, Dy is 0.10 wt%, R2 is Tb, Tb is 0.2 wt%;
B：1.1wt％；
Cu：0.07wt％；
Ti：0.15wt％；
Nb：0.05wt％；
Ga：0.15wt％；
Fe:70.88wt％；
wherein the percentage is the mass percentage of each element in the neodymium iron boron magnet material;
the area percentage of the grain boundary triangular region is 1.59 percent; the grain boundary continuity of the neodymium iron boron magnet material is 97.01%; the ratio of C to O by mass in the trigonal region of the grain boundary triple boundaries was 0.46%, the ratio of C to O by mass in the grain boundary double boundaries was 0.38%, and a new phase R was detected in the grain boundary double boundaries 32.50 Fe 67.39 Cu 0.03 M 0.08 The ratio of the area of the new phase in the two-particle grain boundaries to the total area of the two-particle grain boundaries was 1.06%.
In another preferred embodiment of the present invention, the ndfeb magnet material comprises the following components:
r: 33 wt%; wherein R1 is Nd, Dy and Pr, Nd is 31.7 wt%, Dy is 0.20 wt%, Pr is 0.1 wt%, R2 is Tb, Tb is 1 wt%;
B：0.9wt％；
Cu：0.15wt％；
Ti：0.15wt％；
Al：0.15wt％；
Fe:65.65wt％；
wherein the percentage is the mass percentage of each element in the neodymium iron boron magnet material;
the area percentage of the grain boundary triangular region is 3.28 percent; the grain boundary continuity of the neodymium iron boron magnet material is 99.50%; the ratio of C to O by mass in the triangular region of the grain boundary was 0.46%, the ratio of C to O by mass in the grain boundary of the secondary particle was 0.37%, and a new phase R was detected in the grain boundary of the secondary particle 33.33 Fe 66.58 Cu 0.02 M 0.07 The ratio of the area of the new phase in the two-particle grain boundaries to the total area of the two-particle grain boundaries was 1.58%.
In another preferred embodiment of the present invention, the ndfeb magnet material comprises the following components:
r: 31 wt%; wherein R1 is Nd and Dy, Nd is 29.9 wt%, Dy is 0.10 wt%, R2 is Tb, Dy and Pr, wherein Tb is 0.5 wt%, Dy is 0.30 wt%, and Pr is 0.20 wt%;
B：0.97wt％；
Cu：0.07wt％；
Ti：0.15wt％；
Fe:67.81wt％；
wherein the percentage is the mass percentage of each element in the neodymium iron boron magnet material;
the area percentage of the grain boundary triangular region is 2.62 percent; the continuity of the grain boundary of the neodymium iron boron magnet material is 98.50%; the mass ratio of C to O in the triangular region of the grain boundary was 0.48%, the mass ratio of C to O in the grain boundary of the secondary particle was 0.39%, and a new phase R was detected in the grain boundary of the secondary particle 34.22 Fe 65.64 Cu 0.06 M 0.08 The ratio of the area of the new phase in the two-particle grain boundaries to the total area of the two-particle grain boundaries was 1.87%.
The neodymium iron boron magnet material provided by the invention adopts a Co-free scheme, simultaneously reasonably controls the total rare earth content TRE and the content range of Cu and M (Ti, Nb and the like), and more impurity phases are distributed in two grain boundaries instead of being agglomerated in a grain boundary triangular area, so that the continuity of the grain boundaries is improved, the area of the grain boundary triangular area is reduced, higher density is beneficial to obtaining, and the residual magnetism Br of the magnet is improved; this also promotes the Tb to be uniformly distributed in the grain boundary and the main phase shell layer, and improves the coercive force Hcj of the magnet.
The invention also provides application of the neodymium iron boron magnet material in preparation of magnetic steel.
Wherein, the magnetic steel is preferably 54SH, 54UH and 56SH 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 14.5kGs, and Hcj is more than or equal to 24.5 kOe; the Br temperature coefficient is more than or equal to-0.106%/DEG C at the temperature of 20-120 ℃;
(2) the magnet material can be used for manufacturing 54SH, 54UH and 56SH high-performance magnetic steels, 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.
In the following examples, the apparatus used for magnetic property evaluation was a PFM-14 magnetic property measuring instrument from Hirst, UK.
1. The raw material compositions of the neodymium iron boron magnet materials of examples 1 to 10 of the present invention and comparative examples 1 to 5 are shown in table 1 below.
TABLE 1 formulation and content (wt%) of raw material composition of NdFeB magnet Material
Note: "/" means that the element is not included.
The preparation method of the neodymium iron boron magnet material in examples 1 to 10 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 added as PrCu in R2 of example 10, and the content of Cu added in the grain boundary diffusion step of example 2 was 0.03 wt%) 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: 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 room temperature, 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: and (3) carrying the molded bodies to a sintering furnace for sintering, and sintering for 2-5h at the temperature of 1030-1090 ℃ under the vacuum condition of less than 0.5Pa to obtain a sintered body.
(6) And (3) a grain boundary diffusion process: after the surface of the sintered body is purified, R2 (such as Tb alloy or fluoride, Dy alloy or one or more of fluoride and PrCu alloy, wherein Cu is added in the smelting step and the grain boundary diffusion step at the same time) is coated on the surface of the sintered body, and is diffused for 5-15h at the temperature of 850 ℃, then is cooled to room temperature, and is subjected to low-temperature tempering treatment for 1-3h at the temperature of 460-560 ℃.
Effect example 1
The neodymium iron boron magnet materials in examples 1-10 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
Note: "/" means that the element is not included.
(2) 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.
(3) Testing high-temperature performance: the formula for calculating the temperature coefficient is:
the calculation results are shown in table 3.
(4) Determination of microstructure: the results of the triangular area test, the grain boundary continuity test, and the like are shown in Table 3, in which the novel phase R x Fe 100-x-y-z Cu y M z (x is 32 to 36, y is 0.1 or less but not 0, and z is 0.15 or less but not 0) according to the FE-EPMA test.
Table 3 results of performance testing
In table 3:
calculating the continuity of the grain boundary of the two particles according to the back scattering picture of the EPMA; C. the mass ratio of O in the two-particle grain boundary and the grain boundary triangle region and the new phase are measured by EPMA elemental analysis.
The area ratio of the grain boundary triangle region means: the ratio of the area of the trigones of the grain boundaries to the total area of the "grains and grain boundaries".
The continuity of the two-particle grain boundary means: the ratio of the length occupied by the phase other than the void in the grain boundary (the phase is, for example, a B-rich phase, a rare earth oxide, a rare earth carbide, or the like) to the total grain boundary length.
The mass ratio of C, O in the grain boundary triangle region means: 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, O in the two-particle grain boundary means: 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 area ratio (%) of the new phase in the two-particle grain boundary means: the ratio of the area of the new phase in the two-particle grain boundary to the total area of the two-particle grain boundary.
The result shows that the temperature coefficients of remanence are all equal to or even better than those of the comparative example, and the defect of poor high-temperature stability caused by no Co can be overcome when the Co-free magnetic alloy is not contained. In addition, according to the example 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 reason for the improvement of the grain boundary continuity from the mechanism.
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 block structure is a black cavity in the figure caused by the shedding of the neodymium-rich phase caused by grinding and polishing when preparing the sample observed by the sem. Wherein point 3 is Nd 2 Fe 14 B main phase (gray region), grain boundary phase (silver white region) at Point 2, and R included in the grain boundary of two grains at Point 1 x Fe 100-x-y-z Cu y M z Phase (off-white dough). The results show that: the area of the grain boundary trigone 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 (86)
1. The utility model provides a neodymium iron boron magnet material which characterized in that, among the neodymium iron boron magnet material, R: 28 to 33 wt%; the R comprises R1 and R2, the R1 comprises Nd and Dy, the R2 comprises Tb; the content of R2 is 0.2 wt% -1 wt%;
B：0.9～1.1wt％；
cu: 0.15 wt% or less and not 0 wt%;
m: 0.35 wt% 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：60wt％～70.88wt％；
the wt% is the mass percentage of each 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 Nd 2 Fe l4 B crystal grains and shell layer thereof, adjacent to the Nd 2 Fe l4 Two-grain boundaries and grain boundary trigones of B grains, in which the heavy rare earth element in R1 is mainly distributed in Nd 2 Fe l4 B, crystal grains, wherein R2 is mainly distributed in the shell layer, the two-particle grain boundary and the grain boundary triangular region, and the area percentage of the grain boundary triangular region is 1.5-3.5%; the grain boundary continuity of the neodymium iron boron magnet material is more than 96%; the mass ratio of C to O in the crystal boundary triangular region is 0.4-0.5%, and the mass ratio of C to O in the two-particle crystal boundary is more than 0.35%;
the grain boundary of the two particles also contains a chemical composition R x Fe 100-x-y-z Cu y M z The new phase of (a); wherein x is 32 to 36, y is 0.1 or less but not 0, and z is 0.15 or less but not 0;
the chemical composition is R x Fe 100-x-y-z Cu y M z The ratio of the area of the new phase in the two-particle grain boundary to the total area of the two-particle grain boundary is 0.8-3%.
2. The neodymium iron boron magnet material according to claim 1, wherein the area percentage of the grain boundary trigones is 1.59% -3.28%;
and/or the grain boundary continuity is 97% or more;
and/or the mass ratio of C to O in the two-particle grain boundary is 0.37-0.4%;
and/or x is 32.5-35.5, y is 0.02-0.1, and z is 0.07-0.12;
and/or the amount of R in the neodymium iron boron magnet material is 29-31 wt%;
and/or in the neodymium iron boron magnet material, the content of Nd in the R is 28-32.5 wt%, and the percentage is the mass percentage of the total mass of the neodymium iron boron magnet material;
and/or in the neodymium iron boron magnet material, the content of Dy in R1 is less than 0.2 wt%;
and/or, the R1 further comprises one or more of Pr, Ho, Tb, Gd, and Y;
and/or, when R1 contains Pr, Pr is added in the form of PrNd, or in the form of a pure mixture of Pr and Nd, or in combination of PrNd, pure mixture of Pr and Nd; when added as PrNd, Pr: nd 25:75 or 20: 80;
and/or the content of R2 is 0.2 wt% to 0.8 wt%;
and/or, in the R2, the content of Tb is 0.2 wt% -0.8 wt%;
and/or, the R2 also comprises one or more of Pr, Dy, Ho and Gd;
and/or, the content of M is 0.1 wt% -0.15 wt%, or 0.25 wt% -0.4 wt%;
and/or the M is one or more of Ti, Zr, Nb, Ni, V, Ta, Cr, Mo, W, Mn, Hf and Ag;
and/or, the M species further comprises one or more of Bi, Sn, Zn, Ga, In, Au and Pb;
and/or the neodymium iron boron magnet material also contains Al;
when the M includes Ga and Ga is 0.01 wt% or less, Al + Ga + Cu is 0.15 wt% or less and is not 0 wt%; and/or the content of Cu in the neodymium iron boron magnet material is less than 0.08 wt%, but not 0 wt%, or 0.1 wt% -0.15 wt%;
and/or the content of B in the neodymium iron boron magnet material is 0.9 wt% -1.1 wt%;
and/or the content of Fe in the neodymium iron boron magnet material is 65.65 wt% -70.88 wt%.
3. The neodymium-iron-boron magnet material according to claim 2, wherein the grain boundary trigone area proportion is 1.59% -2%.
4. The neodymium-iron-boron magnet material according to claim 2, characterized in that the grain boundary continuity is 98% or more.
5. The neodymium-iron-boron magnet material of claim 1, wherein the chemical composition is R x Fe 100-x-y-z Cu y M z The ratio of the area of the new phase in the two-particle grain boundary to the total area of the two-particle grain boundary is 0.81 to 2.64%.
6. The ndfeb magnet material as claimed in claim 2, wherein the content of Dy in R1 is 0.1-0.2 wt%.
7. The ndfeb magnet material according to claim 2, wherein the content of Pr is 0.1-2 wt% when added in the form of a mixture of pure Pr and Nd or in combination of a mixture of PrNd, pure Pr and Nd, wherein the percentages are mass percentages based on the total mass of the ndfeb magnet material.
8. The ndfeb magnet material according to claim 2, wherein when R1 contains Ho, the content of Ho is 0.1 to 0.2 wt%, and the percentage is the mass percentage of each component content in the total mass of the ndfeb magnet material.
9. The ndfeb magnet material according to claim 2, wherein when R1 contains Gd, the content of Gd is 0.1 to 0.2 wt%, and the percentage is the mass percentage of each component content in the total mass of the ndfeb magnet material.
10. The ndfeb magnet material according to claim 2, wherein when R1 contains Y, the content of Y is 0.1 to 0.2 wt%, the percentage being the mass percentage of each component content in the total mass of the ndfeb magnet material.
11. The ndfeb magnet material according to claim 2, wherein when R2 contains Pr, the content of Pr is 0.2 wt% or less and not 0 wt%.
12. The neodymium-iron-boron magnet material according to claim 2, wherein when R2 contains Dy, the content of Dy is 0.3 wt% or less and is not 0 wt%.
13. The ndfeb magnet material of claim 2, wherein when the R2 includes Ho, the Ho content is 0.15 wt% or less and not 0 wt%, wt% being the mass percentage of elements in the ndfeb magnet material.
14. The ndfeb magnet material of claim 2, wherein when R2 includes Gd, the Gd content is 0.15 wt% or less and not 0 wt%, wt% being the mass percentage of elements in the ndfeb magnet material.
15. The neodymium-iron-boron magnet material according to claim 1, wherein when the M contains Ti, the content of Ti is 0.05 wt% to 0.3 wt%.
16. The neodymium-iron-boron magnet material according to claim 15, wherein the content of Ti is 0.1 wt% to 0.15 wt%.
17. The neodymium-iron-boron magnet material according to claim 1, wherein when the M contains Nb, the content of Nb is 0.05 wt% to 0.15 wt%.
18. The neodymium-iron-boron magnet material according to claim 1, wherein the content of Nb is 0.05 wt% to 0.1 wt%.
19. The neodymium-iron-boron magnet material according to claim 1, wherein when the M includes Ga, the content of the Ga is in a range of 0.1 to 0.3 wt%.
20. The neodymium-iron-boron magnet material according to claim 1, wherein when the M element includes Ga, and Ga is 0.2 wt% or more and is not 0.35 wt%, Ti + Nb in the composition of the M element is 0.07 wt% or less and is not 0 wt%.
21. The neodymium-iron-boron magnet material according to claim 2, characterized in that the Al content is 0.15 wt% or less but not 0 wt%.
22. The neodymium-iron-boron magnet material according to claim 2, wherein when M includes Ga, and Ga is 0.01 wt% or less, Al + Ga + Cu is 0.11 wt% or less, and is not 0 wt%.
23. The ndfeb magnet material according to claim 2, wherein the content of B in the ndfeb magnet material is 0.97 wt% to 1.05 wt%.
24. The ndfeb magnet material as set forth in claim 1, wherein the ndfeb magnet material comprises:
r: 29-31 wt%; the R1 comprises Nd and Dy, wherein the Dy is used in an amount of 0.1-0.2 wt%; r2 comprises Tb, the dosage of Tb is 0.2 wt% -0.8 wt%;
B：0.9wt％～1.1wt％；
cu: 0.15 wt% or less but not 0 wt%;
ti: 0.3 wt% or less but not 0 wt%;
the balance of Fe and inevitable impurities;
wherein, the percentage is the mass percentage of each element in the neodymium iron boron magnet material.
25. The ndfeb magnet material as claimed in claim 1, wherein the ndfeb magnet material comprises the following components:
r: 30.6 wt%; wherein R1 is Nd and Dy, Nd is 29.90 wt%, Dy is 0.10 wt%; r2 is Tb, Tb is 0.60 wt%;
B：0.99wt％；
Cu：0.07wt％；
Ti：0.15wt％；
Fe:68.19wt％；
wherein the percentage is the mass percentage of each element in the neodymium iron boron magnet material;
the area percentage of the grain boundary triangular region is 2.34 percent; the grain boundary continuity of the neodymium iron boron magnet material is 98%; the mass ratio of C to O in the triangular region of the grain boundary is 0.45 percent, and the mass ratio of C to O in the two-particle grain boundary is 0.39 percent; new phase R detected in two-particle grain boundary 34.5 Fe 65.4 Cu 0.03 M 0.07 The ratio of the area of the new phase in the two-particle grain boundaries to the total area of the two-particle grain boundaries is 2.35%;
or, the neodymium iron boron magnet material comprises:
r: 29-31 wt%; the R1 comprises Nd and Dy, wherein the Dy accounts for 0.1-0.2 wt%; r2 comprises Tb, the dosage of Tb is 0.2 wt% -0.8 wt%;
B：0.9wt％～1.1wt％；
cu: 0.15 wt% or less but not 0 wt%;
nb: 0.3 wt% or less but not 0 wt%;
the balance of Fe and inevitable impurities;
wherein, the percentage is the mass percentage of each element in the neodymium iron boron magnet material.
26. The ndfeb magnet material as claimed in claim 1, wherein the ndfeb magnet material comprises the following components:
r: 30.6 wt%; wherein R1 is Nd and Dy, Nd is 29.90 wt%, Dy is 0.10 wt%, R2 is Tb, Tb is 0.60 wt%;
B：0.99wt％；
Cu：0.07wt％；
Nb：0.15wt％；
Fe:68.19wt％；
wherein the percentage is the mass percentage of each element in the neodymium iron boron magnet material;
the grain boundaryThe area percentage of the triangular area is 2.36 percent; the grain boundary continuity of the neodymium iron boron magnet material is 98.41%; the mass ratio of C to O in the triangular region of the grain boundary is 0.41 percent, and the mass ratio of C to O in the two-particle grain boundary is 0.38 percent; new phase R detected in two-particle grain boundary 35.26 Fe 64.58 Cu 0.07 M 0.09 The ratio of the area of the new phase in the two-particle grain boundaries to the total area of the two-particle grain boundaries is 1.12%;
or, the neodymium iron boron magnet material comprises:
r: 29-31 wt%; the R1 comprises Nd and Dy, wherein the Dy accounts for 0.1-0.2 wt%; r2 comprises Tb, the dosage of Tb is 0.2 wt% -0.8 wt%;
B：0.9wt％～1.1wt％；
cu: 0.15 wt% or less but not 0 wt%;
nb: 0.3 wt% or less but not 0 wt%;
Ga：0.05wt％-0.3wt％；
the balance of Fe and inevitable impurities;
wherein, the percentage is the mass percentage of each element in the neodymium iron boron magnet material.
27. The ndfeb magnet material as claimed in claim 1, wherein the ndfeb magnet material comprises the following components:
r: 30.6 wt%; wherein R1 is Nd and Dy, Nd is 29.90 wt%, Dy is 0.10 wt%, R2 is Tb, Tb is 0.60 wt%;
B：0.99wt％；
Cu：0.07wt％；
Nb：0.05wt％；
Ga：0.3wt％；
Fe:67.99wt％；
wherein the percentage is the mass percentage of each element in the neodymium iron boron magnet material;
the area percentage of the grain boundary triangular region is 2.45 percent; the grain boundary continuity of the neodymium iron boron magnet material is 98.80%; the mass ratio of C to O in the triangular region of the grain boundary was 0.45%, the mass ratio of C to O in the two-grain boundary was 0.39%, and the mass ratio of C to O in the two-grain boundary was two grainsDetection of a novel phase R in grain boundaries 35.50 Fe 64.38 Cu 0.04 M 0.08 The ratio of the area of the new phase in the two-particle grain boundary to the total area of the two-particle grain boundary is 2.03%;
or, the neodymium iron boron magnet material comprises the following components:
r: 29 wt%; wherein R1 is Nd and Dy, Nd is 28.6 wt%, Dy is 0.10 wt%, R2 is Tb, Tb is 0.30 wt%;
B：1.01wt％；
Cu：0.07wt％；
Ti：0.15wt％；
Ga：0.15wt％；
Fe:69.62wt％；
wherein the percentage is the mass percentage of each element in the neodymium iron boron magnet material;
the area percentage of the grain boundary triangular region is 1.88%; the grain boundary continuity of the neodymium iron boron magnet material is 97.20%; the ratio of C to O by mass in the triangular region of the grain boundary was 0.44%, the ratio of C to O by mass in the grain boundary of the secondary particle was 0.38%, and a new phase R was detected in the grain boundary of the secondary particle 34.1 Fe 65.68 Cu 0.1 M 0.12 The ratio of the area of the new phase in the two-particle grain boundaries to the total area of the two-particle grain boundaries is 1.74%;
or, the neodymium iron boron magnet material comprises the following components:
r: 31 wt%; wherein R1 is Nd and Dy, Nd is 30.4 wt%, Dy is 0.10 wt%, R2 is Tb, Tb is 0.50 wt%;
B：0.98wt％；
Cu：0.07wt％；
Ti：0.15wt％；
Ga：0.1wt％；
Fe:67.7wt％；
wherein the percentage is the mass percentage of each element in the neodymium iron boron magnet material;
the area percentage of the grain boundary triangular region is 2.68 percent; the grain boundary continuity of the neodymium iron boron magnet material is 98.36%; the mass ratio of C to O in the triangular region of the grain boundary was 0.45%, and the mass ratio of C to O in the two-grain boundary was0.39%, and a new phase R was detected in the grain boundary of the two grains 33.2 Fe 66.68 Cu 0.04 M 0.08 The ratio of the area of the new phase in the two-particle grain boundaries to the total area of the two-particle grain boundaries is 1.94%;
or, the neodymium iron boron magnet material comprises the following components:
r: 30.6 wt%; wherein R1 is Nd and Dy, Nd is 29.9 wt%, Dy is 0.10 wt%, R2 is Tb, Tb is 0.60 wt%;
B：0.99wt％；
Cu：0.07wt％；
Ti：0.05wt％；
Ga：0.1wt％；
Fe:68.19wt％；
wherein the percentage is the mass percentage of each element in the neodymium iron boron magnet material;
the area percentage of the grain boundary triangular region is 2.38%; the grain boundary continuity of the neodymium iron boron magnet material is 98.10%; the mass ratio of C to O in the triangular region of the grain boundary was 0.44%, the mass ratio of C to O in the grain boundary of the secondary particle was 0.4%, and a new phase R was detected in the grain boundary of the secondary particle 33.56 Fe 66.28 Cu 0.05 M 0.11 The ratio of the area of the new phase in the two-particle grain boundaries to the total area of the two-particle grain boundaries is 0.81%;
or, the neodymium iron boron magnet material comprises the following components:
r: 30.6 wt%; wherein R1 is Nd and Dy, Nd is 29.90 wt%, Dy is 0.10 wt%, R2 is Tb, Tb is 0.60 wt%;
B：0.99wt％；
Cu：0.07wt％；
Ti：0.3wt％；
Ga：0.1wt％；
Fe:67.94wt％；
wherein the percentage is the mass percentage of each element in the neodymium iron boron magnet material;
the area percentage of the grain boundary triangular region is 2.54 percent; the grain boundary continuity of the neodymium iron boron magnet material is 98.22%; the mass ratio of C to O in the triangular region of the grain boundary was 0.43%, and the mass ratio of C to O in the two-grain boundary was 0.43%The mass ratio of O is 0.4%, and a new phase R is detected in the two-particle grain boundary 34.41 Fe 65.42 Cu 0.08 M 0.09 The ratio of the area of the new phase in the two-particle grain boundaries to the total area of the two-particle grain boundaries is 2.64%;
or, the neodymium iron boron magnet material comprises the following components:
r: 28 wt%; wherein R1 is Nd and Dy, Nd is 27.3 wt%, Dy is 0.10 wt%, R2 is Tb, Tb is 0.2 wt%;
B：1.1wt％；
Cu：0.07wt％；
Ti：0.15wt％；
Nb：0.05wt％；
Ga：0.15wt％；
Fe:70.88wt％；
wherein, the percentage is the mass percentage of each element in the neodymium iron boron magnet material;
the area percentage of the grain boundary triangular region is 1.59 percent; the continuity of the grain boundary of the neodymium iron boron magnet material is 97.01%; the ratio of C to O by mass in the trigonal region of the grain boundary triple boundaries was 0.46%, the ratio of C to O by mass in the grain boundary double boundaries was 0.38%, and a new phase R was detected in the grain boundary double boundaries 32.50 Fe 67.39 Cu 0.03 M 0.08 The ratio of the area of the new phase in the two-particle grain boundaries to the total area of the two-particle grain boundaries is 1.06%;
or, the neodymium iron boron magnet material comprises the following components:
r: 33 wt%; wherein R1 is Nd, Dy and Pr, Nd is 31.7 wt%, Dy is 0.20 wt%, Pr is 0.1 wt%, R2 is Tb, Tb is 1 wt%;
B：0.9wt％；
Cu：0.15wt％；
Ti：0.15wt％；
Al：0.15wt％；
Fe:65.65wt％；
wherein the percentage is the mass percentage of each element in the neodymium iron boron magnet material;
the area percentage of the grain boundary triangular region is 3.28 percent; the grain boundary of the neodymium iron boron magnet material is connectedThe continuity is 99.50%; the ratio of C to O by mass in the triangular region of the grain boundary was 0.46%, the ratio of C to O by mass in the grain boundary of the secondary particle was 0.37%, and a new phase R was detected in the grain boundary of the secondary particle 33.33 Fe 66.58 Cu 0.02 M 0.07 The ratio of the area of the new phase in the two-particle grain boundaries to the total area of the two-particle grain boundaries is 1.58%;
or, the neodymium iron boron magnet material comprises the following components:
r: 31 wt%; wherein R1 is Nd and Dy, Nd is 29.9 wt%, Dy is 0.10 wt%, R2 is Tb, Dy and Pr, wherein Tb is 0.5 wt%, Dy is 0.30 wt%, and Pr is 0.20 wt%;
B：0.97wt％；
Cu：0.07wt％；
Ti：0.15wt％；
Fe:67.81wt％；
wherein the percentage is the mass percentage of each element in the neodymium iron boron magnet material;
the area percentage of the grain boundary triangular region is 2.62 percent; the grain boundary continuity of the neodymium iron boron magnet material is 98.50%; the mass ratio of C to O in the triangular region of the grain boundary was 0.48%, the mass ratio of C to O in the grain boundary of the secondary particle was 0.39%, and a new phase R was detected in the grain boundary of the secondary particle 34.22 Fe 65.64 Cu 0.06 M 0.08 The ratio of the area of the new phase in the two-particle grain boundaries to the total area of the two-particle grain boundaries was 1.87%.
28. A raw material composition of a neodymium iron boron magnet material according to any one of claims 1 to 27, characterized by comprising the following components by mass: r: 28 to 33 wt%;
r is rare earth elements including R1 and R2, R1 is rare earth element added during smelting, and R1 includes Nd and Dy; the R2 is a rare earth element added during grain boundary diffusion, the R2 comprises Tb, and the content of R2 is 0.2-1 wt%;
m: less than or equal to 0.4 wt% and not less than 0 wt%, the species of M including one or more of Ti, Ni, V, Nb, Ta, Cr, Mo, W, Mn, Zr, Hf and Ag;
cu: less than or equal to 0.15wt percent and less than 0wt percent;
B：0.9～1.1wt％；
Fe：60wt％～70.88wt％；
the wt% is the mass percentage of each element content in the total mass of the raw material composition;
the raw material composition does not contain Co.
29. The raw material composition of a neodymium-iron-boron magnet material as claimed in claim 28, wherein the amount of R is 29-31 wt%;
and/or the content of Nd in the R1 is 28-32.5 wt%, and the percentage is the mass percentage of the total mass of the raw material composition;
and/or the content of Dy in the R1 is less than 0.2 wt%;
and/or, the R1 further comprises one or more of Pr, Ho, Tb, Gd, and Y;
and/or, when said 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 combination of PrNd, pure Pr and Nd; when added as PrNd, Pr: nd 25:75 or 20: 80;
and/or the content of R2 is 0.2 wt% to 0.8 wt%;
and/or, in the R2, the content of Tb is 0.2 wt% -0.8 wt%;
and/or, the R2 also comprises one or more of Pr, Dy, Ho and Gd;
and/or, the content of M is 0.1 wt% -0.15 wt%, or 0.25 wt% -0.4 wt%;
and/or the M is one or more of Ti, Zr, Nb, Ni, V, Ta, Cr, Mo, W, Mn, Hf and Ag;
and/or, the M species further comprises one or more of Bi, Sn, Zn, Ga, In, Au and Pb;
and/or, the raw material composition also contains Al;
when the M includes Ga and Ga is 0.01 wt% or less, Al + Ga + Cu is 0.15 wt% or less and is not 0 wt%;
and/or the Cu content in the raw material composition is less than 0.08 wt% but not 0 wt%, or 0.1 wt% to 0.15 wt%;
and/or the content of B in the raw material composition is 0.9-1.1 wt%;
and/or the content of the Fe in the raw material composition is 65.65 wt% -70.88 wt%.
30. The raw material composition according to claim 29, wherein Dy content of R1 is 0.1 to 0.2 wt%.
31. The raw material composition according to claim 29, wherein when added in the form of a mixture of pure Pr and Nd or in combination of a mixture of PrNd, pure Pr and Nd, the content of Pr is 0.1 to 2 wt%, wherein the percentage is a mass percentage based on the total mass of the raw material composition.
32. The raw material composition of claim 29, wherein when R1 comprises Ho, the Ho content is 0.1 to 0.2 wt%, and the percentage is the mass percentage of each component content in the total mass of the raw material composition.
33. The raw material composition of claim 29, wherein when R1 contains Gd, the Gd content is 0.1-0.2 wt%, and the percentage is the mass percentage of each component in the total mass of the raw material composition.
34. The raw material composition of claim 29, wherein when R1 contains Y, the content of Y is 0.1 to 0.2 wt%, and the percentage is the mass percentage of each component in the total mass of the raw material composition.
35. The feed composition of claim 29, wherein when R2 comprises Pr, the content of Pr is 0.2 wt% or less and is not 0 wt%.
36. The raw material composition as claimed in claim 29, wherein when R2 contains Dy, the content of Dy is 0.3 wt% or less and is not 0 wt%.
37. The feed composition of claim 29, wherein when said R2 comprises Ho, said Ho is present in an amount less than 0.15 wt% and not 0 wt%.
38. The starting composition according to claim 29, wherein when R2 comprises Gd, the Gd content is 0.15 wt% or less and is not 0 wt%.
39. The feedstock composition of claim 28, wherein when said M comprises Ti, said Ti is present in an amount of 0.05 wt% to 0.3 wt%.
40. The feedstock composition of claim 39, wherein the Ti is present in an amount of 0.1 wt% to 0.15 wt%.
41. The feedstock composition of claim 28, wherein when said M comprises Nb, said Nb is present in an amount of 0.05 wt% to 0.15 wt%.
42. The feedstock composition of claim 28, wherein the Nb content is in the range of 0.05 wt% to 0.1 wt%.
43. The feedstock composition of claim 28, wherein when said M comprises Ga, said Ga is present in an amount ranging from 0.1 to 0.3 wt%.
44. The raw material composition according to claim 28, wherein when the M element includes Ga, and Ga is 0.2 wt% or more and is not 0.35 wt%, Ti + Nb in the composition of the M element is 0.07 wt% or less and is not 0 wt%.
45. A feedstock composition according to claim 29, wherein the Al content in said feedstock composition is less than 0.15 wt% but not 0 wt%.
46. The raw material composition according to claim 29, wherein when M includes Ga and Ga is 0.01 wt% or less, Al + Ga + Cu is 0.11 wt% or less and is not 0 wt%.
47. The feed composition of claim 29, wherein B is present in an amount of 0.97 wt% to 1.05 wt% of the feed composition.
48. The feed composition of claim 28, wherein said feed composition comprises:
r: 29-31 wt%; the R1 comprises Nd and Dy, wherein the Dy is used in an amount of 0.1-0.2 wt%; r2 comprises Tb, the dosage of Tb is 0.2 wt% -0.8 wt%;
B：0.9wt％～1.1wt％；
cu: 0.15 wt% or less but not 0 wt%;
ti: 0.3 wt% or less but not 0 wt%;
the balance of Fe and inevitable impurities;
wherein the percentage is the mass percentage of each element in the raw material composition.
49. A feedstock composition as set forth in claim 28, wherein said feedstock composition comprises the following components:
r: 30.6 wt%; wherein R1 is Nd and Dy, Nd is 29.90 wt%, Dy is 0.10 wt%; r2 is Tb, Tb is 0.60 wt%;
B：0.99wt％；
Cu：0.07wt％；
Ti：0.15wt％；
Fe:68.19wt％；
wherein the percentage is the mass percentage of each element in the raw material composition;
or, the raw material composition comprises:
r: 29-31 wt%; the R1 comprises Nd and Dy, wherein the Dy is used in an amount of 0.1-0.2 wt%; r2 comprises Tb, the dosage of Tb is 0.2 wt% -0.8 wt%;
B：0.9wt％～1.1wt％；
cu: 0.15 wt% or less but not 0 wt%;
nb: 0.3 wt% or less but not 0 wt%;
the balance of Fe and inevitable impurities;
wherein the percentage is the mass percentage of each element in the raw material composition.
50. A feedstock composition as set forth in claim 28, wherein said feedstock composition comprises the following components:
r: 30.6 wt%; wherein R1 is Nd and Dy, Nd is 29.90 wt%, Dy is 0.10 wt%, R2 is Tb, Tb is 0.60 wt%;
B：0.99wt％；
Cu：0.07wt％；
Nb：0.15wt％；
Fe:68.19wt％；
wherein the percentage is the mass percentage of each element in the raw material composition;
or, the raw material composition comprises:
r: 29-31 wt%; the R1 comprises Nd and Dy, wherein the Dy is used in an amount of 0.1-0.2 wt%; r2 comprises Tb, the dosage of Tb is 0.2 wt% -0.8 wt%;
B：0.9wt％～1.1wt％；
cu: 0.15 wt% or less but not 0 wt%;
nb: 0.3 wt% or less but not 0 wt%;
Ga：0.05wt％-0.3wt％；
the balance of Fe and inevitable impurities;
wherein, the percentage is the mass percentage of each element in the raw material composition.
51. A feedstock composition according to claim 48, comprising the following components:
r: 30.6 wt%; wherein R1 is Nd and Dy, Nd is 29.90 wt%, Dy is 0.10 wt%, R2 is Tb, Tb is 0.60 wt%;
B：0.99wt％；
Cu：0.07wt％；
Nb：0.05wt％；
Ga：0.3wt％；
Fe:67.99wt％；
wherein the percentage is the mass percentage of each element in the raw material composition;
or, the raw material composition comprises the following components:
r: 29 wt%; wherein R1 is Nd and Dy, Nd is 28.6 wt%, Dy is 0.10 wt%, R2 is Tb, Tb is 0.30 wt%;
B：1.01wt％；
Cu：0.07wt％；
Ti：0.15wt％；
Ga：0.15wt％；
Fe:69.62wt％；
wherein the percentage is the mass percentage of each element in the raw material composition;
or, the raw material composition comprises the following components:
r: 31 wt%; wherein R1 is Nd and Dy, Nd is 30.4 wt%, Dy is 0.10 wt%, R2 is Tb, Tb is 0.50 wt%;
B：0.98wt％；
Cu：0.07wt％；
Ti：0.15wt％；
Ga：0.1wt％；
Fe:67.7wt％；
wherein the percentage is the mass percentage of each element in the raw material composition;
or, the raw material composition comprises the following components:
r: 30.6 wt%; wherein R1 is Nd and Dy, Nd is 29.9 wt%, Dy is 0.10 wt%, R2 is Tb, Tb is 0.60 wt%;
B：0.99wt％；
Cu：0.07wt％；
Ti：0.05wt％；
Ga：0.1wt％；
Fe:68.19wt％；
wherein the percentage is the mass percentage of each element in the raw material composition;
or, the raw material composition comprises the following components:
r: 30.6 wt%; wherein R1 is Nd and Dy, Nd is 29.90 wt%, Dy is 0.10 wt%, R2 is Tb, Tb is 0.60 wt%;
B：0.99wt％；
Cu：0.07wt％；
Ti：0.3wt％；
Ga：0.1wt％；
Fe:67.94wt％；
wherein the percentage is the mass percentage of each element in the raw material composition;
or, the raw material composition comprises the following components:
r: 28 wt%; wherein R1 is Nd and Dy, Nd is 27.3 wt%, Dy is 0.10 wt%, R2 is Tb, Tb is 0.2 wt%;
B：1.1wt％；
Cu：0.07wt％；
Ti：0.15wt％；
Nb：0.05wt％；
Ga：0.15wt％；
Fe:70.88wt％；
wherein, the percentage is the mass percentage of each element in the raw material composition;
or, the raw material composition comprises the following components:
r: 33 wt%; wherein R1 is Nd, Dy and Pr, Nd is 31.7 wt%, Dy is 0.20 wt%, Pr is 0.1 wt%, R2 is Tb, Tb is 1 wt%;
B：0.9wt％；
Cu：0.15wt％；
Ti：0.15wt％；
Al：0.15wt％；
Fe:65.65wt％；
wherein the percentage is the mass percentage of each element in the raw material composition;
or, the raw material composition comprises the following components:
r: 31 wt%; wherein R1 is Nd and Dy, Nd is 29.9 wt%, Dy is 0.10 wt%, R2 is Tb, Dy and Pr, wherein Tb is 0.5 wt%, Dy is 0.30 wt%, and Pr is 0.20 wt%;
B：0.97wt％；
Cu：0.07wt％；
Ti：0.15wt％；
Fe:67.81wt％；
wherein the percentage is the mass percentage of each element in the raw material composition.
52. A method for preparing a neodymium iron boron magnet material according to any one of claims 1 to 27, which is performed by using the raw material composition according to any one of claims 28 to 51, and the preparation method is a diffusion method, wherein the R1 element is added in a smelting step, and the R2 element is added in a grain boundary diffusion step.
53. The method of preparing a neodymium-iron-boron magnet material of claim 52, wherein the method comprises the steps of: 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 the R2 is subjected to grain boundary diffusion to obtain the neodymium iron boron magnet material;
and the smelting operation is to carry out smelting casting on elements except R2 in the neodymium iron boron magnet material by adopting an ingot casting process and a rapid hardening sheet process to obtain an alloy sheet.
54. The preparation method of claim 53, wherein the smelting temperature is 1300-1700 ℃.
55. The method of claim 54, wherein the melting temperature is 1450-1550 ℃.
56. The method of claim 53, wherein milling comprises hydrogen milling and/or jet milling.
57. The method of claim 56, wherein said hydrogen-reduced powder comprises hydrogen absorption, dehydrogenation and cooling processes.
58. A production method according to claim 57, wherein the temperature of hydrogen absorption is 20 to 200 ℃.
59. The method of claim 57, wherein the dehydrogenation temperature is from 400 ℃ to 650 ℃.
60. The method of claim 59, wherein the dehydrogenation temperature is from 500 ℃ to 550 ℃.
61. The production method according to claim 57, wherein the pressure of hydrogen absorption is 50 to 600 kPa.
62. The method of claim 56, wherein the jet milling is performed at 0.1 to 2 MPa.
63. The method of claim 62, wherein the jet milling is performed at 0.5 MPa to 0.7 MPa.
64. The method of claim 56, wherein the gas stream in the gas stream milled powder is nitrogen.
65. The method of claim 56, wherein the jet milled powder is in a time of 2 to 4 hours.
66. The method of claim 53, wherein the molding is a magnetic field molding method, and the magnetic field strength of the magnetic field molding method is 1.5T or more.
67. The method of claim 53, wherein said sintering is performed in a vacuum of less than 5 x 10 -1 Pa, and the like.
68. The method of claim 53, wherein the sintering temperature is 1000-1200 ℃.
69. The method of claim 68, wherein the sintering temperature is 1030-1090 ℃.
70. The method of claim 53, wherein the sintering time is 0.5 to 10 hours.
71. The method of claim 70, wherein the sintering time is between 2 and 5 hours.
72. The method of claim 53, further comprising a coating operation of R2 prior to the grain boundary diffusion.
73. The method of claim 72, wherein said R2 is coated as fluoride or a low melting point alloy.
74. The method of claim 73, wherein R2 is applied as a fluoride of Tb.
75. The method of claim 73, wherein when R2 further comprises Dy, the Dy is coated as a fluoride of Dy.
76. The method of claim 73, wherein when R2 further comprises Pr, the Pr is added in the form of a PrCu alloy.
77. The method of claim 53, wherein when R2 contains Pr and Pr participates in grain boundary diffusion in the form of a PrCu alloy, the Cu is added at the grain boundary diffusion step or at the same time in the melting step and the grain boundary diffusion step.
78. The method of claim 77, wherein the Cu is added when the Cu diffuses at the grain boundaries, the Cu content being 0.03 wt% to 0.15 wt%, wt% being the mass percent of the element in the raw material composition; wherein the percentage of Cu in PrCu is 0.1-17 wt%.
79. The method of claim 53, wherein the temperature of the grain boundary diffusion is 800-1000 ℃.
80. The preparation method of claim 53, wherein the time for the grain boundary diffusion is 5 to 20 hours.
81. The method of claim 78, wherein the grain boundary diffusion time is 5-15 hours.
82. The method of claim 53, wherein the grain boundary diffusion is followed by a low temperature tempering treatment.
83. The method as claimed in claim 82, wherein the low temperature tempering treatment is performed at 460 ℃ and 560 ℃ for 1-3 h.
84. A neodymium iron boron magnet material prepared by the preparation method of any one of claims 53-83.
85. Use of a neodymium iron boron magnet material according to any one of claims 1 to 27 in the preparation of magnetic steel.
86. Use of a neodymium iron boron magnet material according to claim 85 in the preparation of magnetic steel, said magnetic steel being 54SH, 54UH, 56SH high performance magnetic steel.
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Effective date of registration: 20220629 Address after: 366300 new industrial zone, Changting Economic Development Zone, Longyan City, Fujian Province Applicant after: FUJIAN CHANGTING GOLDEN DRAGON RARE-EARTH Co.,Ltd. Address before: 361000 Ke Gang, Haicang District, Fujian, Xiamen Applicant before: XIAMEN TUNGSTEN Co.,Ltd. Applicant before: FUJIAN CHANGTING GOLDEN DRAGON RARE-EARTH Co.,Ltd. |
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Address after: 366300 new industrial zone, Changting Economic Development Zone, Longyan City, Fujian Province Patentee after: Fujian Jinlong Rare Earth Co.,Ltd. Address before: 366300 new industrial zone, Changting Economic Development Zone, Longyan City, Fujian Province Patentee before: FUJIAN CHANGTING GOLDEN DRAGON RARE-EARTH Co.,Ltd. |