WO2021169887A1 - 一种钕铁硼磁体材料、原料组合物及制备方法和应用 - Google Patents

一种钕铁硼磁体材料、原料组合物及制备方法和应用 Download PDF

Info

Publication number
WO2021169887A1
WO2021169887A1 PCT/CN2021/077172 CN2021077172W WO2021169887A1 WO 2021169887 A1 WO2021169887 A1 WO 2021169887A1 CN 2021077172 W CN2021077172 W CN 2021077172W WO 2021169887 A1 WO2021169887 A1 WO 2021169887A1
Authority
WO
WIPO (PCT)
Prior art keywords
percentage
mass
grain boundary
content
neodymium iron
Prior art date
Application number
PCT/CN2021/077172
Other languages
English (en)
French (fr)
Inventor
骆溁
廖宗博
蓝琴
黄佳莹
师大伟
林玉麟
谢菊华
龙严清
Original Assignee
厦门钨业股份有限公司
福建省长汀金龙稀土有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 厦门钨业股份有限公司, 福建省长汀金龙稀土有限公司 filed Critical 厦门钨业股份有限公司
Priority to JP2022545011A priority Critical patent/JP7342281B2/ja
Priority to EP21761557.4A priority patent/EP4113544A4/en
Priority to KR1020227024167A priority patent/KR102631761B1/ko
Priority to US17/785,041 priority patent/US20230023534A1/en
Publication of WO2021169887A1 publication Critical patent/WO2021169887A1/zh

Links

Images

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H01F41/0266—Moulding; Pressing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H01F41/0293—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets diffusion of rare earth elements, e.g. Tb, Dy or Ho, into permanent magnets
    • 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

Definitions

  • the invention specifically relates to a neodymium iron boron magnet material, a raw material composition, and a preparation method and application.
  • Nd-Fe-B permanent magnetic material is based on Nd 2 Fe l4 B compound, which has the advantages of high magnetic properties, low thermal expansion coefficient, easy processing and low price. Since its introduction, it has grown at an average annual rate of 20-30%. Become the most widely used permanent magnet material. According to the preparation method, Nd-Fe-B permanent magnets can be divided into three types: sintering, bonding and hot pressing. Among them, sintered magnets account for more than 80% of the total output and are the most widely used.
  • Chinese patent document CN110571007A discloses a rare earth permanent magnet material, which adds more than 1.5% of heavy rare earth elements and more than 0.8% of cobalt at the same time, and finally obtains Nd-Fe-B with better coercivity and magnetic properties. magnet.
  • the NdFeB magnet materials with better magnetic properties in the prior art require the addition of a large amount of heavy rare earth elements and cobalt elements, which is costly. It is a prerequisite that a small amount of heavy rare earth elements or even no cobalt elements can be added. However, technical solutions that can still reach a considerable level or even better are yet to be developed.
  • the present invention aims to overcome the need to add a large amount of cobalt element or heavy rare earth element to the neodymium iron boron magnet material of the prior art to improve the magnetic properties (coercivity, remanence and thermal stability) of the neodymium iron boron magnet material, but Due to the high cost defect, a neodymium iron boron magnet material, raw material composition, preparation method and application are provided.
  • the neodymium iron boron magnet material of the present invention can still have high coercivity, remanence and good thermal stability under the condition of adding a small amount of heavy rare earth elements and not adding cobalt elements.
  • the present invention adopts the following technical solutions to solve the above technical problems.
  • the present invention provides a raw material composition of neodymium iron boron magnet material, which includes the following components in mass content:
  • R 28-33%; said R is a rare earth element, R includes R1 and R2, said R1 is a rare earth element added during smelting, said R1 includes Nd and Dy; said R2 is a rare earth element added during grain boundary diffusion Element, the R2 includes Tb, and the content of R2 is 0.2-1%;
  • the M is one or more of Bi, Sn, Zn, Ga, In, Au, and Pb;
  • the raw material composition does not contain Co; the percentage is the mass percentage of the mass of each component to the total mass of the raw material composition.
  • the content of R is preferably 29.5% to 32.6%, such as 29.58%, 29.75%, 29.8%, 30.6%, 30.7%, 30.9%, 30.95%, 31.35% or 32.6%, more preferably 29.5-31%, the percentage is the mass percentage of the total mass of the raw material composition.
  • the content of Nd in R1 of the raw material composition may be conventional in the art, preferably 28.5% to 32.5%, such as 28.6%, 29.9%, 30.4% or 32.1%, more preferably 28.5-31%, the percentage is the mass percentage of the total mass of the raw material composition.
  • the content of Dy in said R1 is preferably less than 0.3%, but not 0, such as 0.05%, 0.08%, 0.1% or 0.3%, more preferably 0.05 to 0.2%. It is the mass percentage of the total mass of the raw material composition.
  • the R1 may also include other conventional rare earth elements in the art, for example, including one or more of Pr, Ho, Tb, Gd, and Y.
  • the addition form of Pr can be conventional in the art, for example, in the form of PrNd, or in the form of a mixture of pure Pr and pure Nd, or, in the form of "PrNd, pure Pr and pure Nd "Mixture" is added jointly.
  • Pr:Nd is preferably 25:75 or 20:80; when added in the form of a mixture of pure Pr and pure Nd, or when added as a mixture of "PrNd, pure Pr and pure Nd
  • the content of Pr is preferably 0.1-2%, for example 0.2%, and the percentage is the mass percentage of the total mass of the raw material composition.
  • the pure Pr or pure Nd in the present invention generally means that the purity is above 99.5%.
  • the content of Ho is preferably 0.1-0.2%, and the percentage is the mass percentage of the total mass of the raw material composition.
  • the content of Gd is preferably 0.1-0.2%, and the percentage is the mass percentage of the total mass of the raw material composition.
  • the content of Y is preferably 0.1-0.2%, and the percentage is the mass percentage of the total mass of the raw material composition.
  • the content of R2 is preferably 0.2-0.9%, such as 0.2%, 0.5%, 0.6%, 0.8% or 0.9%, and the percentage is the mass percentage of the total mass of the raw material composition.
  • the content of Tb in the R2 is preferably 0.2% to 1%, such as 0.2%, 0.3%, 0.6%, 0.8% or 0.9%, more preferably 0.5 to 1%, and the percentage is The mass percentage of the total mass of the raw material composition.
  • the R2 in the raw material composition, preferably further includes Pr and/or Dy.
  • the content of Pr is preferably less than 0.2%, but not 0, such as 0.1%, and the percentage is the mass percentage of the total mass of the raw material composition.
  • the content of Dy is preferably 0.3% or less, but not 0, such as 0.1%, and the percentage is the mass percentage of the total mass of the raw material composition.
  • the content of M is preferably less than 0.35%, but not 0, more preferably 0.01 to 0.35%, such as 0.01%, 0.1%, 0.15%, 0.16%, 0.2% or 0.3%,
  • the percentage is the mass percentage of the total mass of the raw material composition.
  • the type of M is preferably one or more of Zn, Ga and Bi.
  • the content of Ga is preferably below 0.35%, but not 0, such as 0.01%, 0.1%, 0.15%, 0.2%, 0.3% or 0.35%, more preferably It is 0.1-0.35%, and the percentage is the mass percentage of the total mass of the raw material composition.
  • the content of Zn is preferably less than 0.35%, but not 0, more preferably 0.05 to 0.25%, such as 0.08%, 0.1% or 0.2%, and the percentage is The mass percentage of the total mass of the raw material composition.
  • the content of Bi is preferably less than 0.35%, but not 0, more preferably 0.05 to 0.15%, such as 0.08%, and the percentage is based on the total raw material composition.
  • the mass percentage of mass is preferably less than 0.35%, but not 0, more preferably 0.05 to 0.15%, such as 0.08%, and the percentage is based on the total raw material composition. The mass percentage of mass.
  • the content of Cu is preferably 0.03 to 0.15%, for example, 0.03%, 0.05%, 0.06%, 0.07%, 0.08%, 0.1% or 0.15%; or, the content of Cu is preferably Below 0.08%, but not 0, such as 0.03%, 0.05%, 0.06%, 0.07% or 0.08%, the percentage is the mass percentage of the total mass of the raw material composition.
  • the method of adding Cu preferably includes adding during smelting and/or adding during grain boundary diffusion.
  • the content of Cu added during the grain boundary diffusion is preferably 0.03 to 0.15%, such as 0.05%, and the percentage is the mass percentage of the total mass of the raw material composition;
  • the Cu is added when the grain boundary diffuses, and the Cu is preferably added in the form of a PrCu alloy, and the mass percentage of the Cu in the PrCu is preferably 0.1-17%.
  • the content of B is preferably 0.97-1.05%, such as 0.99% or 1%, and the percentage is the mass percentage of the total mass of the raw material composition.
  • the content of Fe is preferably 65 to 69.5%, such as 65.99%, 67.21%, 67.63%, 67.71%, 68.09%, 68.19%, 68.95%, 68.96%, 69.06% or 69.91%. It is the mass percentage of the total mass of the raw material composition.
  • the raw material composition preferably further includes Al.
  • the content of Al is preferably less than 0.3%, but not 0, more preferably 0.03 to 0.2%, such as 0.03%, 0.1% or 0.2%, and the percentage is based on the total mass of the raw material composition The mass percentage.
  • the M when the M contains Ga and Ga ⁇ 0.01%, preferably, Al+Ga+Cu ⁇ 0.11% in the composition of the M element; in a preferred embodiment of the present invention, the content of Ga It is 0.01%, the sum of the content of "Al, Ga, and Cu" is 0.07%, and the percentage is the mass percentage of the total mass of the raw material composition.
  • the raw material composition of the neodymium iron boron magnet material preferably includes the following components in mass content: R: 29.5% to 32.6%; R includes R1 and R2, and R1 includes Nd and Dy, and R1 is a rare earth element added during smelting, the content of R2 is 0.2-0.9%, the R2 includes Tb, and the R2 is a rare earth element added during grain boundary diffusion; M: 0.35% or less, but not 0, The M is one or more of Zn, Ga and Bi; Cu: 0.05-0.15%; B: 0.97-1.05%; Fe: 65-69.5%, the original composition does not contain Co; the percentage is The content of each component accounts for the mass percentage of the total mass of the raw material composition.
  • the raw material composition of the neodymium iron boron magnet material preferably includes the following components in mass content: R: 29.5% to 31%; R includes R1 and R2, and R1 includes Nd and Dy, and R1 is a rare earth element added during smelting, the content of R2 is 0.2-0.8%, the R2 includes Tb, and the R2 is a rare earth element added during grain boundary diffusion; M: 0.1-0.35%, where M is One or more of Zn, Ga and Bi; Cu: 0.08% or less, but not 0; B: 0.97-1.05%; Fe: 65-69.5%, the raw material composition does not contain Co; the percentage is The content of each component accounts for the mass percentage of the total mass of the raw material composition.
  • the raw material composition of the neodymium iron boron magnet material includes the following components by mass: R1: Nd 28.6%, Dy 0.05%, Pr 0.1%, and the R1 is added during smelting R2: Tb 1%, the R2 is the rare earth element added during grain boundary diffusion; Ga 0.05%, Al 0.1%, Cu 0.05%, B 0.99% and Fe 69.06%, the raw material composition does not Containing Co, the percentage is the mass percentage of the content of each component in the total mass of the raw material composition.
  • the raw material composition of the neodymium iron boron magnet material includes the following components by mass content: R1: Nd 28.6%, Dy 0.1%, Pr 0.2%, and the R1 is added during smelting R2: Tb 0.9%, the R2 is the rare earth element added during grain boundary diffusion; Ga 0.1%, Zn 0.1%, Cu 0.05%, B 1% and Fe 68.95%, the raw material composition does not Containing Co, the percentage is the mass percentage of the content of each component in the total mass of the raw material composition.
  • the raw material composition of the neodymium iron boron magnet material includes the following components by mass content: R1: Nd 28.6%, Dy 0.08%, and the R1 is a rare earth element added during smelting; R2: Tb 0.9%, the R2 is the rare earth element added during grain boundary diffusion; Ga 0.3%, Cu 0.06%, B 1.1% and Fe 68.96%, the raw material composition does not contain Co, and the percentages are for each component The content accounts for the mass percentage of the total mass of the raw material composition.
  • the raw material composition of the neodymium iron boron magnet material includes the following components by mass content: R1: Nd 29.9%, Dy 0.1%, and the R1 is a rare earth element added during smelting; R2: Tb 0.8%, Pr 0.1%, the R2 is the rare earth element added during grain boundary diffusion; Ga 0.2%, Al 0.2%, Cu 0.03% added during smelting, Cu 0.05% added during grain boundary diffusion, B 0.99% and Fe 67.63%, the raw material composition does not contain Co, and the percentage is the mass percentage of the content of each component in the total mass of the raw material composition.
  • the raw material composition of the neodymium iron boron magnet material includes the following components by mass content: R1: Nd 30.4%, Dy 0.05%, and the R1 is a rare earth element added during smelting; R2: Tb 0.8%, Dy 0.1%, the R2 is the rare earth element added during grain boundary diffusion; Ga 0.35%, Cu 0.1%, B 0.99% and Fe 67.21%, the raw material composition does not contain Co, the percentage It is the mass percentage of the content of each component in the total mass of the raw material composition.
  • the raw material composition of the neodymium iron boron magnet material preferably includes the following components by mass: R: 30-31%; R includes R1 and R2, and R1 includes Nd and Dy, and R1 is a rare earth element added during smelting, the content of R2 is 0.5 to 0.7%, the R2 includes Tb, and the R2 is a rare earth element added during grain boundary diffusion; M: 0.1 to 0.2%, where M is Zn and/or Ga; Cu: 0.05-0.09%; B: 0.97-1.05%; Fe: 67-69%, the raw material composition does not contain Co; the percentage is the content of each component in the total raw material composition The mass percentage of mass.
  • the raw material composition of the neodymium iron boron magnet material includes the following components by mass content: R1: Nd 29.9%, Dy 0.1%, Pr 0.1%, and the R1 is added during smelting R2: Tb 0.6%, the R2 is the rare earth element added during grain boundary diffusion; Ga 0.15%, Cu 0.07%, B 0.99% and Fe 68.09%, the percentages are the content of each component in the raw material combination The mass percentage of the total mass of the material.
  • the raw material composition of the neodymium iron boron magnet material includes the following components by mass content: R1: Nd 29.9%, Dy 0.1%, and the R1 is a rare earth element added during smelting; R2: Tb 0.6%, the R2 is the rare earth element added during grain boundary diffusion; Ga 0.15%, Cu 0.07%, B 0.99%, and Fe 68.19%, the raw material composition does not contain Co, and the percentage is each component The content accounts for the mass percentage of the total mass of the raw material composition.
  • the raw material composition of the neodymium iron boron magnet material includes the following components by mass content: R1: Nd 30.4%, Dy 0.05%, and the R1 is a rare earth element added during smelting; R2: Tb 0.3%, Pr 0.2%, the R2 is the rare earth element added during grain boundary diffusion; Zn 0.2%, Cu 0.12% added during smelting, Cu 0.03% added during grain boundary diffusion, B 0.99% and Fe 67.71%, the raw material composition does not contain Co, and the percentage is the mass percentage of the content of each component in the total mass of the raw material composition.
  • the raw material composition of the neodymium iron boron magnet material includes the following components by mass content: R1: Nd 32.1%, Dy 0.3%, and the R1 is a rare earth element added during smelting; R2: Tb 0.2%, the R2 is the rare earth element added during grain boundary diffusion; Zn 0.08%, Bi 0.08%, Cu 0.15%, B 1.1% and Fe 65.99%, the raw material composition does not contain Co, percentage It is the mass percentage of the content of each component in the total mass of the raw material composition.
  • the raw material composition of the neodymium iron boron magnet material includes the following components by mass: R1: Nd 28.6%, Dy 0.05%, Pr 0.1%, and the R1 is added during smelting R2: Tb 1%, the R2 is the rare earth element added during grain boundary diffusion; Ga 0.01%, Al 0.03%, Cu 0.03%, B 0.99% and Fe 69.19%, the raw material composition does not Containing Co, the percentage is the mass percentage of the content of each component in the total mass of the raw material composition.
  • the present invention also provides a method for preparing a neodymium iron boron magnet material, which adopts the raw material composition as described above.
  • the preparation method is a conventional diffusion method in the art, wherein the R1 element is in the smelting step. Add, the R2 element is added in the grain boundary diffusion step.
  • the preparation method preferably includes the following steps: the elements other than R2 in the raw material composition of the neodymium iron boron magnet material are smelted, powdered, molded, and sintered to obtain a sintered body, and then the The mixture of the sintered body and the R2 may diffuse through the grain boundary.
  • the smelting operation and conditions can be a conventional smelting process in the field.
  • the elements other than R2 in the raw material composition of the neodymium iron boron magnet material are smelted and casted by ingot casting process and quick-setting sheet process. Obtain alloy flakes.
  • an additional 0-0.3wt% of rare earth elements (generally Is Nd element), the percentage is the mass percentage of the additional rare earth element to the total mass of the raw material composition; in addition, the content of this additional rare earth element is not included in the raw material composition.
  • the smelting temperature may be 1300 to 1700°C, preferably 1450 to 1550°C.
  • the melting environment may be a vacuum of 0.05 Pa.
  • the smelting equipment is generally an intermediate frequency vacuum smelting furnace, such as an intermediate frequency vacuum induction rapid solidification belt spinning furnace.
  • the operation and conditions of the pulverizing can be conventional pulverizing processes in the field, and generally include hydrogen crushing pulverizing and/or jet milling pulverizing.
  • the hydrogen crushing and pulverizing generally includes hydrogen absorption, dehydrogenation and cooling treatment.
  • the temperature of the hydrogen absorption is generally 20 to 200°C.
  • the temperature of the dehydrogenation is generally 400-650°C, preferably 500-550°C.
  • the pressure of the hydrogen absorption is generally 50-600 kPa, preferably 300-500 kPa.
  • the air-jet milling powder is generally carried out under the conditions of 0.1-2 MPa, preferably 0.5-0.7 MPa.
  • the gas stream in the gas stream milling powder can be, for example, nitrogen gas.
  • the time for the air jet milling can be 2 to 4 hours.
  • the molding operation and conditions can be conventional molding processes in the field.
  • the magnetic field forming method for example, the magnetic field forming method.
  • the magnetic field strength of the magnetic field forming method is generally above 1.5T.
  • the sintering operation and conditions can be conventional sintering processes in the field.
  • the sintering can be carried out under the condition that the degree of vacuum is lower than 0.5Pa.
  • the sintering temperature may be 1000 to 1200°C, preferably 1030 to 1090°C.
  • the sintering time may be 0.5-10h, preferably 2-5h.
  • the R2 is generally coated in the form of fluoride or a low melting point alloy, such as fluoride of Tb.
  • Dy is coated in the form of fluoride of Dy.
  • the Pr when the R2 contains Pr, preferably, the Pr is added in the form of a PrCu alloy.
  • the quality of the Cu and the PrCu alloy is preferably 0.1-17%.
  • the timing of adding the Cu in the preparation method is the grain boundary diffusion step, or it is added at the same time as the smelting step and the grain boundary diffusion step.
  • the operation and conditions of the grain boundary diffusion treatment can be a conventional grain boundary diffusion process in the art.
  • the temperature of the grain boundary diffusion may be 800-1000°C, for example 850°C.
  • the time for the grain boundary diffusion may be 5-20h, preferably 5-15h.
  • a low-temperature tempering treatment is also performed according to the conventional practice in the art.
  • the temperature of low temperature tempering treatment is generally 460 ⁇ 560°C.
  • the low-temperature tempering time can generally be 1 to 3 hours.
  • the invention also provides a neodymium iron boron magnet material prepared by the above preparation method.
  • the present invention also provides a neodymium iron boron magnet material, which includes the following components by mass content: R: 28-33%; said R includes R1 and R2, said R1 includes Nd and Dy, and said R2 includes Tb. ; The content of R2 is 0.2% to 1%;
  • the M is one or more of Bi, Sn, Zn, Ga, In, Au, and Pb;
  • the neodymium iron boron magnet material does not contain Co; the percentage is the mass percentage of the mass of each component to the total mass of the neodymium iron boron magnet material;
  • the neodymium iron boron magnet material comprises Nd 2 Fe l4 B crystal grains and its shell layer, two grain boundaries adjacent to the Nd 2 Fe l4 B crystal grains and a grain boundary triangle region, wherein the heavy rare earth elements in R1 are distributed in Nd 2 Fe 14 B crystal grains, R2 is mainly distributed in the shell layer, the two-grain boundary and the grain boundary triangle area, and the area of the grain boundary triangle area accounts for 2 to 3.12%;
  • the boundary continuity is more than 96%; the mass ratio of C and O in the triangular region of the grain boundary is 0.4-0.5%, and the mass ratio of C and O in the two-grain boundary is 0.3-0.4%.
  • the heavy rare earth elements in R1 are mainly distributed in Nd 2 Fe l4 B crystal grains
  • Nd 2 Fe l4 B crystal grains can be understood as the main distribution of heavy rare earth elements in R1 caused by the conventional smelting and sintering process in this field (generally refers to more than 95wt% )
  • R2 is mainly distributed in the shell layer
  • R2 caused by the conventional grain boundary diffusion process in the field is mainly distributed (generally refers to more than 95wt%) in the shell layer and grain boundary of Nd 2 Fe l4 B grains. (Two-grain grain boundary and grain boundary triangle area), a small part will also diffuse into the Nd 2 Fe l4 B crystal grains, for example, at the outer edge of the Nd 2 Fe l4 B crystal grains.
  • the calculation method of the grain boundary continuity refers to the length occupied by phases other than voids in the grain boundary (phases such as B-rich phase, rare earth-rich phase, rare earth oxide, rare earth carbide, etc.) and The ratio of the total grain boundary length. Grain boundary continuity of more than 96% can be called continuous channel.
  • the grain boundary triangle area generally refers to a place where three or more grain boundary phases intersect, and there are B-rich phases, rare earth-rich phases, rare earth oxides, rare earth carbides, and cavities distributed.
  • the calculation method of the area ratio of the grain boundary triangle area refers to the ratio of the area of the grain boundary triangle area to the total area of the "grains and grain boundaries".
  • rare earth oxides and rare earth carbides are mainly produced by the C and O elements introduced during the preparation process. Due to the high content of rare earth in the grain boundaries, C and O are usually more distributed in the grain boundaries in the magnet material, and exist in the form of rare earth carbides and rare earth oxides, respectively.
  • C and O elements are introduced in conventional ways in the field, generally impurity introduction or atmosphere introduction. Specifically, for example, in the process of jet milling and pressing, additives are introduced. During sintering, these elements will be heated by heating. Additives are removed, but a small amount of C and O elements will inevitably remain; for another example, a small amount of O elements will inevitably be introduced due to the atmosphere in the preparation process.
  • the content of C and O in the final NdFeB magnet material product obtained after testing is only below 1000 ppm and 1200 ppm respectively, which belong to the category of conventional acceptable impurities in the field, so they are not included in the product element statistical table.
  • the area of the grain boundary triangle area is preferably 2.07-2.84%, such as 2.07%, 2.45%, 2.54%, 2.65%, 2.67%, 2.79% or 2.84%, more preferably 2.07-2.6 %.
  • the grain boundary continuity is preferably 97% or more, for example, 97.88%, 97.92%, 98.04%, 98.08%, 98.09%, 98.11%, 98.13%, 98.16%, 98.21% or 98.22%, and more Preferably, it is above 98%.
  • the mass ratio of C and O in the grain boundary triangle region is preferably 0.41 to 0.48%, such as 0.41%, 0.42%, 0.44%, 0.45%, 0.46%, 0.47% or 0.48%, More preferably, it is 0.41 to 0.46%, and the percentage 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.
  • the mass ratio of C and O in the two-grain boundary is preferably 0.32 to 0.39%, such as 0.32%, 0.33%, 0.34%, 0.35%, 0.36%, 0.37% or 0.39%, More preferably, it is 0.34 to 0.39%, and the percentage is the ratio of the mass of C and O in the grain boundary of the two particles to the total mass of all elements in the grain boundary.
  • C and O elements usually exist in the form of rare earth carbides and rare earth oxides in the grain boundary phase, so "the mass ratio of C and O in the grain boundary triangle area" and " The mass ratios of C and O in the grain boundaries of the two grains correspond to heterogeneous rare earth carbides and rare earth oxides, respectively.
  • the difference is smaller than the comparison ratio, and it can be obtained.
  • a new phase is also detected in the two-particle grain boundary,
  • the chemical composition of the new phase is: R x Fe 100-xyz Cu y M z , wherein R in R x Fe 100-xyz Cu y M z includes one or more of Nd, Dy and Tb,
  • the M is one or more of Bi, Sn, Zn, Ga, In, Au, and Pb;
  • x is 78-80;
  • y is 0.8-1.5;
  • z is 0.1 or less, but not zero.
  • x is preferably 78.1 to 79.5
  • y is preferably 0.99 to 1.33
  • z is preferably 0.26 to 0.38.
  • the structure of the new phase is, for example, R 78.89 Fe 19.59 Cu 1.17 M 0.35 , R 78.17 Fe 20.50 Cu 1.07 M 0.26 , R 77.87 Fe 20.50 Cu 1.33 M 0.30 , R 79.42 Fe 19.16 Cu 1.07 M 0.35 , R 78.68 Fe 19.77 Cu 1.17 M 0.38 , R 78.50 Fe 20.13 Cu 1.03 M 0.34 , R 78.87 Fe 19.79 Cu 0.99 M 0.35 , R 78.14 Fe 20.34 Cu 1.23 M 0.29 , R 78.68 Fe 19.80 Cu 1.20 M 0.32 , R 79.41 Fe 19.09 Cu 1.17 M 0.33 .
  • the chemical composition is: the area of the new phase of R x Fe 100-xyz Cu y M z in the two-grain boundary and the total area of the two-grain boundary are preferably 0.25 to 1.65%, such as 0.25%, 0.35%, 0.56%, 0.58%, 0.78%, 0.85%, 0.97%, 1.54%, 1.62% or 1.65%, more preferably 0.5 to 1.65%.
  • the inventor speculates that the new phase is formed at the grain boundary of the two particles, so the continuity of the grain boundary is further improved, thereby improving the performance of the magnet.
  • the content of R in the neodymium iron boron magnet material is preferably 29.5% to 32.6%, such as 29.58%, 29.75%, 29.8%, 30.6%, 30.7%, 30.9%, 30.95%, 31.35 % Or 32.6%, more preferably 29.5% to 31%, and the percentage is the mass percentage of the total mass of the neodymium iron boron magnet material.
  • the Nd content in the R1 of the neodymium iron boron magnet material, can be conventional in the art, preferably 28.5% to 32.5%, such as 28.6%, 29.9%, 30.4% or 32.1%, more preferably
  • the ground is 28.5-31%, and the percentage is the mass percentage of the total mass of the neodymium iron boron magnet material.
  • the content of Dy is preferably less than 0.3%, but not 0, such as 0.05%, 0.08%, 0.1% or 0.3%, more preferably 0.05-0.2%, the percentage is the mass percentage of the total mass of the neodymium iron boron magnet material.
  • the R1 may also include other conventional rare earth elements in the art, for example, including one or more of Pr, Ho, Tb, Gd, and Y.
  • the addition form of Pr can be conventional in the art, for example, in the form of PrNd, or in the form of a mixture of pure Pr and pure Nd, or, in the form of "PrNd, pure Pr and pure Nd "Mixture" is added jointly.
  • Pr:Nd is preferably 25:75 or 20:80; when added in the form of a mixture of pure Pr and pure Nd, or when added as a mixture of "PrNd, pure Pr and pure Nd
  • the content of Pr is preferably 0.1-2%, such as 0.2%, and the percentage is the mass percentage of the content of each component in the total mass of the neodymium iron boron magnet material.
  • the pure Pr or pure Nd in the present invention generally means that the purity is above 99.5%.
  • the content of Ho is preferably 0.1-0.2%, and the percentage is the mass percentage of the total mass of the neodymium iron boron magnet material.
  • the content of Gd is preferably 0.1-0.2%, and the percentage is a mass percentage of the total mass of the neodymium iron boron magnet material.
  • the content of Y is preferably 0.1-0.2%, and the percentage is the mass percentage of the total mass of the neodymium iron boron magnet material.
  • the content of R2 is preferably 0.2-0.9%, such as 0.2%, 0.5%, 0.6%, 0.8% or 0.9%, and the percentage is a mass percentage of the total mass of the neodymium iron boron magnet material.
  • the content of Tb in the R2 is preferably 0.2% to 1%, such as 0.2%, 0.3%, 0.6%, 0.8% or 0.9%, more preferably 0.5 to 1%, and the percentage is The mass percentage of the total mass of the neodymium iron boron magnet material.
  • the R2 in the neodymium iron boron magnet material, the R2 preferably further includes Pr and/or Dy.
  • the content of Pr is preferably less than 0.2%, but not 0, such as 0.1%, and the percentage is a mass percentage of the total mass of the neodymium iron boron magnet material.
  • the content of Dy is preferably less than 0.3%, but not 0, such as 0.1%, and the percentage is a mass percentage of the total mass of the neodymium iron boron magnet material.
  • the content of M is preferably less than 0.35%, but not 0, more preferably 0.01 to 0.35%, such as 0.01%, 0.1%, 0.15%, 0.16%, 0.2% or 0.3%,
  • the percentage is the mass percentage of the total mass of the neodymium iron boron magnet material.
  • the type of M is preferably one or more of Zn, Ga and Bi.
  • the content of Ga is preferably below 0.35%, but not 0, such as 0.01%, 0.1%, 0.15%, 0.2%, 0.3% or 0.35%, more preferably It is 0.1-0.35%, and the percentage is the mass percentage of the total mass of the neodymium iron boron magnet material.
  • the content of Zn is preferably less than 0.35%, but not 0, more preferably 0.05 to 0.25%, such as 0.08%, 0.1% or 0.2%, and the percentage is The mass percentage of the total mass of the neodymium iron boron magnet material.
  • the content of Bi is preferably less than 0.35%, but not 0, more preferably 0.05 to 0.15%, such as 0.08%, and the percentage is based on the neodymium iron boron magnet The mass percentage of the total mass of the material.
  • the content of Cu is preferably 0.03 to 0.15%, for example, 0.03%, 0.05%, 0.06%, 0.07%, 0.08%, 0.1% or 0.15%; or, the content of Cu is preferably Below 0.08%, but not 0, such as 0.03%, 0.05%, 0.06%, 0.07% or 0.08%, the percentage is the mass percentage of the total mass of the neodymium iron boron magnet material.
  • the method of adding Cu preferably includes adding during smelting and/or adding during grain boundary diffusion.
  • the content of Cu added during the grain boundary diffusion is preferably 0.03 to 0.15%, such as 0.05%, and the percentage is the mass percentage of the total mass of the neodymium iron boron magnet material
  • the Cu is preferably added in the form of a PrCu alloy, wherein the mass percentage of the Cu in the PrCu is preferably 0.1-17%.
  • the content of B is preferably 0.97-1.05%, such as 0.99% or 1%, and the percentage is the mass percentage of the total mass of the neodymium iron boron magnet material.
  • the content of Fe is preferably 65 to 69.5%, for example, 65.99%, 67.21%, 67.63%, 67.71%, 68.09%, 68.19%, 68.95%, 68.96%, 69.06% or 69.91%. It is the mass percentage of the total mass of the neodymium iron boron magnet material.
  • the neodymium iron boron magnet material preferably further includes Al.
  • the content of Al is preferably less than 0.3%, but not 0, more preferably less than 0.2%, but not 0, such as 0.03%, 0.1% or 0.2%, and the percentage is based on the neodymium iron The mass percentage of the total mass of the boron magnet material.
  • the M when the M contains Ga and Ga ⁇ 0.01%, preferably, in the composition of the M element, Al+Ga+Cu ⁇ 0.11%, and the percentage is the mass of the total mass of the neodymium iron boron magnet material Percentage:
  • the Ga content is 0.01%
  • the sum of the "Al, Ga, and Cu" content is 0.07%
  • the percentage is the mass percentage of the total mass of the neodymium iron boron magnet material.
  • the neodymium iron boron magnet material preferably includes the following components by mass: R: 29.5% to 32.6%; R includes R1 and R2, said R1 includes Nd and Dy, and said R1 is added during smelting
  • the content of the R2 is 0.2-0.9%, the R2 includes Tb, and the R2 is the rare earth element added during grain boundary diffusion; M: 0.35% or less but not 0, the M is Zn One or more of, Ga and Bi; Cu: 0.05 ⁇ 0.15%; B: 0.97 ⁇ 1.05%; Fe: 65 ⁇ 69.5%, the neodymium iron boron magnet material does not contain Co; the percentage is each component
  • the content accounts for the mass percentage of the total mass of the neodymium iron boron magnet material; the neodymium iron boron magnet material includes Nd 2 Fe l4 B crystal grains and its shell, and two grain boundaries adjacent to the Nd 2 Fe l4 B crystal grains And the grain boundary triangle area, where the heavy rare earth elements in R
  • the neodymium iron boron magnet material preferably includes the following components by mass content: R: 29.5-31%; R includes R1 and R2, said R1 includes Nd and Dy, and said R1 is smelted
  • the content of the added rare earth element, the R2 is 0.2-0.8%, the R2 includes Tb, the R2 is the rare earth element added during grain boundary diffusion; M: 0.01-0.35%, the M is Zn, Ga and One or more of Bi; Cu: 0.08% or less, but not 0; B: 0.97-1.05%; Fe: 65-69.5%, the neodymium iron boron magnet material does not contain Co; the percentages are for each group
  • the content of the NdFeB magnet material accounts for the mass percentage of the total mass of the NdFeB magnet material; the NdFeB magnet material includes Nd 2 Fe l4 B crystal grains and its shell, and two grains adjacent to the Nd 2 Fe l4 B crystal grains.
  • R1 is distributed in the Nd 2 Fe 14 B crystal grains, and R2 is mainly distributed in the shell layer, the two-grain boundary and the crystal boundary triangle area.
  • the area of the crystal boundary triangle area is The proportion is 2 to 2.6%; the grain boundary continuity of the neodymium iron boron magnet material is more than 98%; the mass proportion of C and O in the triangular area of the grain boundary is 0.41 to 0.46%; the two-grain crystal
  • the mass ratio of C and O in the world is 0.32 ⁇ 0.39%;
  • the two-grain boundary contains a new phase, and the chemical composition of the new phase is: R x Fe 100-xyz Cu y M z , where, R x Fe 100-xyz Cu y M z includes one or more of Nd, Dy, and Tb, and the M is one or more of Bi, Zn, and Ga; x is 78.1-79.5 , Y is 0.99 to 1.33, z is 0.26 to 0.38; the ratio of the area of
  • the neodymium iron boron magnet material includes the following components by mass content: R1: Nd 28.6%, Dy 0.05%, Pr 0.1%, and the R1 is a rare earth element added during smelting; R2: Tb 1%, the R2 is a rare earth element added during grain boundary diffusion; Ga 0.05%, Al 0.1%, Cu 0.05%, B 0.99% and Fe 69.06%, the neodymium iron boron magnet material does not contain Co , The percentage is the mass percentage of the content of each component in the total mass of the neodymium iron boron magnet material; the neodymium iron boron magnet material includes Nd 2 Fe l4 B crystal grains and its shell layer, adjacent to the Nd 2 Fe l4 B crystal The two-grain grain boundary and the grain boundary triangle region of the grain; wherein the heavy rare earth elements in R1 are mainly distributed in the Nd 2 Fe l4 B crystal grains, and R2 is mainly
  • the neodymium iron boron magnet material includes the following components by mass content: R1: Nd 28.6%, Dy 0.1%, Pr 0.2%, and the R1 is a rare earth element added during smelting; R2: Tb 0.9%, the R2 is a rare earth element added during grain boundary diffusion; Ga 0.1%, Zn 0.1%, Cu 0.05%, B 1% and Fe 68.95%, the neodymium iron boron magnet material does not contain Co , The percentage is the mass percentage of the content of each component in the total mass of the neodymium iron boron magnet material; the neodymium iron boron magnet material includes Nd 2 Fe l4 B crystal grains and its shell layer, adjacent to the Nd 2 Fe l4 B crystal The two-grain grain boundary and the grain boundary triangle region of the grain; wherein the heavy rare earth elements in R1 are mainly distributed in the Nd 2 Fe l4 B crystal grains, and R2 is mainly distributed
  • the neodymium iron boron magnet material includes the following components by mass: R1: Nd 28.6%, Dy 0.08%, the R1 is the rare earth element added during smelting; R2: Tb 0.9 %, the R2 is the rare earth element added during grain boundary diffusion; Ga 0.3%, Cu 0.06%, B 1.1% and Fe 68.96%, the neodymium iron boron magnet material does not contain Co, and the percentage is the content of each component
  • the neodymium iron boron magnet material includes the following components by mass content: R1: Nd 29.9%, Dy 0.1%, the R1 is the rare earth element added during smelting; R2: Tb 0.8 %, Pr 0.1%, the R2 is a rare earth element added during grain boundary diffusion; Ga 0.2%, Al 0.2%, Cu 0.08%, B 0.99% and Fe 67.63%, the neodymium iron boron magnet material does not contain Co , The percentage is the mass percentage of the content of each component in the total mass of the neodymium iron boron magnet material; the neodymium iron boron magnet material includes Nd 2 Fe l4 B crystal grains and its shell layer, adjacent to the Nd 2 Fe l4 B crystal The two-grain grain boundary and the grain boundary triangle region of the grain; wherein the heavy rare earth elements in R1 are mainly distributed in the Nd 2 Fe l4 B crystal grains, and R2 is mainly distributed in
  • the neodymium iron boron magnet material includes the following components by mass content: R1: Nd 30.4%, Dy 0.05%, the R1 is the rare earth element added during smelting; R2: Tb 0.8 %, Dy 0.1%, the R2 is a rare earth element added during grain boundary diffusion; Ga 0.35%, Cu 0.1%, B 0.99% and Fe 67.21%, the neodymium iron boron magnet material does not contain Co, and the percentage is each The component content accounts for the mass percentage of the total mass of the neodymium iron boron magnet material; the neodymium iron boron magnet material comprises Nd 2 Fe l4 B crystal grains and its shell layer, and two particles adjacent to the Nd 2 Fe l4 B crystal grains The grain boundary and the grain boundary triangle region; wherein the heavy rare earth elements in R1 are mainly distributed in the Nd 2 Fe 14 B crystal grains, and R2 is mainly distributed in the shell layer, the two-grain grain
  • the neodymium iron boron magnet material includes the following components by mass content: R: 30-31%; R includes R1 and R2, said R1 includes Nd and Dy, and said R1 is a rare earth element added during smelting
  • the content of the R2 is 0.5-0.7%, the R2 includes Tb, the R2 is a rare earth element added during grain boundary diffusion; M: 0.1-0.2%, the M is Zn and/or Ga; Cu: 0.05 ⁇ 0.09%; B: 0.97 ⁇ 1.05%; Fe: 67 ⁇ 69%, the neodymium iron boron magnet material does not contain Co; the percentage is the mass percentage of the content of each component in the total mass of the neodymium iron boron magnet material
  • the neodymium iron boron magnet material includes Nd 2 Fe l4 B crystal grains and its shell layer, two grain boundaries adjacent to the Nd 2 Fe l4 B crystal grains and the grain boundary triangle region; wherein the heavy rare earth elements in R1 are mainly Distributed in
  • the neodymium iron boron magnet material includes the following components by mass content: R1: Nd 29.9%, Dy 0.1%, Pr 0.1%, and the R1 is a rare earth element added during smelting; R2: Tb 0.6%, the R2 is the rare earth element added during grain boundary diffusion; Ga 0.15%, Cu 0.07%, B 0.99% and Fe 68.09%, the neodymium iron boron magnet material does not contain Co, the percentage is each The component content accounts for the mass percentage of the total mass of the neodymium iron boron magnet material; the neodymium iron boron magnet material comprises Nd 2 Fe l4 B crystal grains and its shell layer, and two particles adjacent to the Nd 2 Fe l4 B crystal grains The grain boundary and the grain boundary triangle region; wherein the heavy rare earth elements in R1 are mainly distributed in the Nd 2 Fe 14 B crystal grains, and R2 is mainly distributed in the shell layer, the two-grain grain boundary and
  • the neodymium iron boron magnet material includes the following components by mass content: R1: Nd 29.9%, Dy 0.1%, the R1 is the rare earth element added during smelting; R2: Tb 0.6 %, the R2 is a rare earth element added during grain boundary diffusion; Ga 0.15%, Cu 0.07%, B 0.99% and Fe 68.19%, the neodymium iron boron magnet material does not contain Co, and the percentage is that the content of each component accounts for The mass percentage of the total mass of the neodymium iron boron magnet material.
  • the neodymium iron boron magnet material includes Nd 2 Fe l4 B crystal grains and its shell layer, two grain boundaries adjacent to the Nd 2 Fe l4 B crystal grains and the grain boundary triangle region; wherein the heavy rare earth elements in R1 are mainly Distributed in Nd 2 Fe 14 B crystal grains, R2 is mainly distributed in the shell layer, the two-grain boundary and the grain boundary triangle area, the area of the grain boundary triangle area accounts for 2.67%;
  • the grain boundary continuity is 98.13%; the mass ratio of C and O in the triangular region of the grain boundary is 0.47%; the mass ratio of C and O in the two-grain grain boundary is 0.37%; the two-grain grain boundary contains
  • the new phase has a chemical composition of R 78.87 Fe 19.79 Cu 0.99 M 0.35 , R is one or more of Nd, Dy and Tb, and M is Ga; the new phase is in the two-grain boundary The ratio of the area to the total area of the two grain boundaries is 0.97%.
  • the neodymium iron boron magnet material includes the following components by mass content: R1: Nd 30.4%, Dy 0.05%, the R1 is the rare earth element added during smelting; R2: Tb 0.3 %, Pr 0.2%, the R2 is a rare earth element added during grain boundary diffusion; Zn 0.2%, Cu 0.15%, B 0.99% and Fe 67.71%, the neodymium iron boron magnet material does not contain Co, and the percentage is each The component content accounts for the mass percentage of the total mass of the neodymium iron boron magnet material; the neodymium iron boron magnet material comprises Nd 2 Fe l4 B crystal grains and its shell layer, and two particles adjacent to the Nd 2 Fe l4 B crystal grains The grain boundary and the grain boundary triangle region; wherein the heavy rare earth elements in R1 are mainly distributed in the Nd 2 Fe 14 B crystal grains, and R2 is mainly distributed in the shell layer, the two-
  • the neodymium iron boron magnet material includes the following components by mass content: R1: Nd 32.1%, Dy 0.3%, the R1 is the rare earth element added during smelting; R2: Tb 0.2 %, the R2 is a rare earth element added during grain boundary diffusion; Zn 0.08%, Bi 0.08%, Cu 0.15%, B 1.1% and Fe 65.99%, the neodymium iron boron magnet material does not contain Co, and the percentage is each The component content accounts for the mass percentage of the total mass of the neodymium iron boron magnet material; the neodymium iron boron magnet material comprises Nd 2 Fe l4 B crystal grains and its shell layer, and two particles adjacent to the Nd 2 Fe l4 B crystal grains The grain boundary and the grain boundary triangle region; wherein the heavy rare earth elements in R1 are mainly distributed in the Nd 2 Fe 14 B crystal grains, and R2 is mainly distributed in the shell layer, the two-gra
  • the neodymium iron boron magnet material includes the following components by mass content: R1: Nd 28.6%, Dy 0.05%, Pr 0.1%, and the R1 is a rare earth element added during smelting; R2: Tb 1%, the R2 is a rare earth element added during grain boundary diffusion; Ga 0.01%, Al 0.03%, Cu 0.03%, B 0.99% and Fe 69.19%, the neodymium iron boron magnet material does not contain Co , The percentage is the mass percentage of the content of each component in the total mass of the neodymium iron boron magnet material; the neodymium iron boron magnet material includes Nd 2 Fe l4 B crystal grains and its shell layer, adjacent to the Nd 2 Fe l4 B crystal The two-grain grain boundary and the grain boundary triangle region of the grain; wherein the heavy rare earth elements in R1 are mainly distributed in the Nd 2 Fe l4 B crystal grains, and R2 is
  • the neodymium iron boron magnet material provided by the present invention reasonably controls the content range of the total rare earth elements TRE, Cu and M (Ga, Zn, etc.) elements, and combines the specific feeding timing of the heavy rare earth elements to make the miscellaneous phases (rare earth oxides and rare earth carbides)
  • the material is more distributed in the grain boundary of the two particles, rather than agglomerated in the triangular area of the grain boundary, so that the continuity of the grain boundary is improved, and the area of the triangular area of the grain boundary is reduced.
  • the magnet remanence Br also promotes the Tb element to be mainly uniformly distributed in the grain boundary and the main phase shell, which improves the coercive force Hcj of the magnet.
  • the invention also provides an application of the neodymium iron boron magnet material described above in the preparation of magnetic steel.
  • the magnetic steel is preferably 54SH, 54UH, 56SH magnetic steel.
  • the reagents and raw materials used in the present invention are all commercially available.
  • the positive progress effect of the present invention is that the neodymium iron boron magnet material of the present invention can be used in existing neodymium iron boron magnets without Co
  • the proportion of phases in the two-grain boundary phase is increased, and a new phase is formed in the two-grain boundary; correspondingly, the continuity of the two-grain boundary is increased, and the impurity phase in the triangular area of the grain boundary is reduced.
  • the proportion of correspondingly reduces the area of the grain boundary triangle.
  • the remanence Br, coercive force Hcj, and corresponding temperature stability of the neodymium iron boron magnet material are improved.
  • the remanence can reach 14.31 ⁇ 14.61kGs
  • the coercivity can reach 24.11 ⁇ 26.35kOe
  • the temperature coefficient of Br can reach between -0.105 ⁇ -0.109 at 20 ⁇ 120°C.
  • FIG. 1 is an EPMA microstructure diagram of the neodymium iron boron magnet material of Example 4.
  • FIG. 1 is an EPMA microstructure diagram of the neodymium iron boron magnet material of Example 4.
  • FIG. 1 the point indicated by arrow 1 is the new phase of R x Fe 100-xyz Cu y M z contained in the grain boundary of the two grains.
  • the position indicated by arrow 2 is the triangular area of the grain boundary, and the position indicated by arrow 3 is Nd. 2 Fe l4 B main phase.
  • Table 1 The formula and content of the raw material composition of the neodymium iron boron magnet material (wt%)
  • Airflow milling process Under nitrogen atmosphere, the powder after hydrogen pulverization is pulverized by airflow milling for 3 hours under the condition of 0.6 MPa in the pulverizing chamber to obtain fine powder.
  • each molded body is moved to a sintering furnace for sintering, sintered under a vacuum of less than 0.5 Pa, and sintered at 1030-1090°C for 2 to 5 hours to obtain a sintered body.
  • R2 such as Tb alloy or fluoride, Dy alloy or fluoride and PrCu alloy
  • the diffusion step is added simultaneously) coating on the surface of the sintered body and diffusing at a temperature of 850°C for 5-15 hours, then cooling to room temperature, and then performing low-temperature tempering treatment at a temperature of 460-560°C for 1 to 3 hours.
  • Magnetic performance test The sintered magnet is tested on the magnetic performance of the PFM-14 magnetic performance measuring instrument from British Hirs company.
  • the tested magnetic properties include the remanence at 20°C and 120°C, and the coercivity at 20°C and 120°C. , And the corresponding temperature coefficient of remanence.
  • the formula for calculating the temperature coefficient of remanence is: (Br high temperature- Br normal temperature )/(Br normal temperature (high temperature-normal temperature)) ⁇ 100%, and the test results are shown in Table 3 below.
  • FE-EPMA detection polishing the vertical orientation surface of the neodymium iron boron magnet material, using the field emission electron probe microanalyzer (FE-EPMA) (JEOL, 8530F) to detect. Test the area ratio of the grain boundary triangle area, the continuity of the two grain boundaries, the mass ratio of C and O, and the new phase.
  • FE-EPMA field emission electron probe microanalyzer
  • the continuity of the two-grain boundary is calculated based on EPMA's backscattering picture; the mass proportion of C and O in the two-grain boundary and the triangular area of the grain boundary and the new phase are measured by the elemental analysis of EPMA.
  • the area ratio of the grain boundary triangle area refers to the ratio of the area of the grain boundary triangle area to the total area of "grains and grain boundaries”.
  • the continuity of the two grain boundaries is: the length occupied by the phases in the grain boundaries except voids (phases such as B-rich phase, rare earth-rich phase, rare earth oxide, rare earth carbide, etc.) and the total crystal The ratio of the length of the boundary.
  • the mass ratio of C and O in the grain boundary triangle area refers to the ratio of the mass of C and O in the grain boundary triangle area to the total mass of all elements in the grain boundary.
  • the mass ratio of C and O in the two-grain boundary refers to the ratio of the mass of C and O in the two-grain boundary to the total mass of all elements in the grain boundary.
  • the area ratio (%) of the new phase in the two-grain boundary refers to the ratio of the area of the new phase in the two-grain boundary to the total area of the two-grain boundary.
  • ⁇ means that the two-grain boundary phase does not contain a new phase with a chemical composition of R x Fe 100-xyz Cu y M z.
  • the present invention can achieve a level equivalent to the current addition of a large amount of Co and heavy rare earth elements by adding a small amount of heavy rare earth elements and not adding Co elements.
  • C and O are more distributed in the grain boundaries and exist in the form of rare earth carbides and rare earth oxides, respectively.
  • FIG. 1 it is the EPMA microstructure diagram of the neodymium iron boron magnet material prepared in Example 4.
  • the point indicated by arrow 1 in the figure is the new phase of R x Fe 100-xyz Cu y M z contained in the two-grain grain boundary (light gray area), and the position indicated by arrow 2 is the triangular area of the grain boundary (silver-white area). ), the position indicated by arrow 3 is the main phase of Nd 2 Fe l4 B (dark gray area).
  • the area of the grain boundary triangle region is smaller than that of conventional magnet materials.

Abstract

一种钕铁硼磁体材料、原料组合物及制备方法和应用。该钕铁硼磁体材料的原料组合物包括如下质量含量的组分：R：28～33％；R为稀土元素，R包括R1和R2，R1为熔炼时添加的稀土元素，R1包括Nd和Dy；R2为晶界扩散时添加的稀土元素，R2包括Tb，R2的含量为0.2～1％；M：≤0.4％、但不为0，所述M为Bi、Sn、Zn、Ga、In、Au和Pb中的一种或多种；Cu：≤0.15％、但不为0；B：0.9～1.1％；Fe：60～70％，且不含Co。钕铁硼磁体材料可在添加少量的重稀土元素、且不添加钴元素的条件下，仍然具有较高的矫顽力、剩磁，且热稳定性佳。

Description

一种钕铁硼磁体材料、原料组合物及制备方法和应用 技术领域
本发明具体涉及一种钕铁硼磁体材料、原料组合物及制备方法和应用。
背景技术
Nd-Fe-B永磁材料以Nd 2Fe l4B化合物为基体，具有磁性能高、热膨胀系数小、易加工和价格低等优点，自问世以来，以平均每年20～30％的速度增长，成为应用最广泛的永磁材料。按制备方法，Nd-Fe-B永磁体可分为烧结、粘结和热压三种，其中烧结磁体占总产量的80％以上，应用最广泛。
随着制备工艺和磁体成分的不断优化，烧结Nd-Fe-B磁体的最大磁能积已接近理论值。随着近年来风力发电、混合动力汽车和变频空调等新兴行业的蓬勃发展对高性能Nd-Fe-B磁体的需求越来越大，同时，这些高温领域的应用也对烧结Nd-Fe-B磁体的性能尤其是矫顽力提出了更高的要求。
美国专利申请US5645651A通过图1表明，Nd-Fe-B磁体的居里温度会随着Co含量的提高而提升，另外表1通过样品9和样品2的对比表明，Nd-Fe-B磁体中添加20at％的Co，相比不加Co的方案，在维持剩磁基本不变的情况下，能提高矫顽力。因此Co被广泛应用于钕铁硼稀土永磁、钐钴稀土永磁、电池等高科技领域，但Co又是重要战略资源，价格较为昂贵。
中国专利文献CN110571007A公开了一种稀土永磁体材料，其同时添加了1.5％以上的重稀土元素和0.8％以上的钴元素，最终才得到了矫顽力和磁性能较佳的Nd-Fe-B磁体。
综上，现有技术中磁性能均较佳的钕铁硼磁体材料，需要添加大量的重稀土元素和钴元素，成本高昂，一种可在添加少量的重稀土元素甚至不添加钴元素的前提下，仍然能达到相当水平甚至更佳的技术方案有待开发。
发明内容
本发明旨在克服现有技术的钕铁硼磁体材料需要添加大量的钴元素或是重稀土元素，以提升钕铁硼磁体材料的磁性能(矫顽力、剩磁和热稳定性)，但成本高昂的缺陷，而提供了一种钕铁硼磁体材料、原料组合物及制备方法和应用。本发明的钕铁硼磁体材料可在添加少量的重稀土元素、且不添加钴元素的条件下，仍然具有较高的矫顽力、剩磁，且热稳定性佳。
本发明采用以下技术方案解决上述技术问题。
本发明提供了一种钕铁硼磁体材料的原料组合物，其包括如下质量含量的组分：
R：28～33％；所述R为稀土元素，R包括R1和R2，所述R1为熔炼时添加的稀土元素，所述R1包括Nd和Dy；所述R2为晶界扩散时添加的稀土元素，所述R2包括Tb，所述R2的含量为0.2～1％；
M：≤0.4％、但不为0，所述M为Bi、Sn、Zn、Ga、In、Au和Pb中的一种或多种；
Cu：≤0.15％、但不为0；
B：0.9～1.1％；
Fe：60～70％；
所述原料组合物中不含Co；百分比为各组分质量占所述原料组合物总质量的质量百分比。
本发明中，所述R的含量较佳地为29.5～32.6％，例如29.58％、29.75％、29.8％、30.6％、30.7％、30.9％、30.95％、31.35％或32.6％，更佳地为29.5～31％，百分比为占所述原料组合物总质量的质量百分比。
本发明中，所述原料组合物的R1中，所述Nd的含量可为本领域常规，较佳地为28.5～32.5％，例如28.6％、29.9％、30.4％或32.1％，更佳地为28.5～31％，百分比为占所述原料组合物总质量的质量百分比。
本发明中，所述R1中，所述Dy的含量较佳地在0.3％以下、但不为0，例如0.05％、0.08％、0.1％或0.3％，更佳地为0.05～0.2％，百分比为占所述原料组合物总质量的质量百分比。
本发明中，所述R1还可包括本领域其他常规的稀土元素，例如包括Pr、Ho、Tb、Gd和Y中的一种或多种。
其中，当所述R1包含Pr时，Pr的添加形式可为本领域常规，例如以PrNd的形式，或者，以纯Pr和纯Nd的混合物的形式，或者，以“PrNd、纯Pr和纯Nd的混合物”联合添加。当以PrNd的形式添加时，Pr：Nd较佳地为25:75或20：80；当以纯Pr和纯Nd的混合物的形式添加时，或者，当以“PrNd、纯Pr和纯Nd的混合物”联合添加时，所述Pr的含量较佳地为0.1～2％，例如0.2％，百分比为占所述原料组合物总质量的质量百分比。本发明中所述纯Pr或纯Nd一般指的是纯度在99.5％以上。
其中，当所述的R1包含Ho时，所述Ho的含量较佳地为0.1～0.2％，百分比为占所述原料组合物总质量的质量百分比。
其中，当所述的R1包含Gd时，所述Gd的含量较佳地为0.1～0.2％，百分比为占所述原料组合物总质量的质量百分比。
其中，当所述的R1包含Y时，所述Y的含量较佳地为0.1～0.2％，百分比为占所述原料组合物总质量的质量百分比。
本发明中，所述R2的含量较佳地为0.2～0.9％，例如0.2％、0.5％、0.6％、0.8％或0.9％，百分比为占所述原料组合物总质量的质量百分比。
本发明中，所述R2中，Tb的含量较佳地为0.2％～1％，例如0.2％、0.3％、0.6％、0.8％或0.9％，更佳地为0.5～1％，百分比为占所述原料组合物总质量的质量百分比。
本发明中，所述原料组合物中，所述R2较佳地还包括Pr和/或Dy。
其中，当所述的R2包含Pr时，所述Pr的含量较佳地为0.2％以下、但不为0，例如0.1％，百分比为占所述原料组合物总质量的质量百分比。
其中，当所述R2包含Dy时，所述Dy的含量较佳地为0.3％以下、但不为0，例如0.1％，百分比为占所述原料组合物总质量的质量百分比。
本发明中，所述M的含量较佳地在0.35％以下、但不为0，更佳地为0.01～0.35％，例如0.01％、0.1％、0.15％、0.16％、0.2％或0.3％，百分比为 占所述原料组合物总质量的质量百分比。
本发明中，所述M的种类较佳地为Zn、Ga和Bi中的一种或多种。
其中，当所述M包含Ga时，所述Ga的含量较佳地在0.35％以下、但不为0，例如0.01％、0.1％、0.15％、0.2％、0.3％或0.35％，更佳地为0.1～0.35％，百分比为占所述原料组合物总质量的质量百分比。
其中，当所述M包含Zn时，所述Zn的含量较佳地在0.35％以下、但不为0，更佳地为0.05～0.25％，例如0.08％、0.1％或0.2％，百分比为占所述原料组合物总质量的质量百分比。
其中，当所述M包含Bi时，所述Bi的含量较佳地在0.35％以下、但不为0，更佳地为0.05～0.15％，例如0.08％，百分比为占所述原料组合物总质量的质量百分比。
本发明中，所述Cu的含量较佳地为0.03～0.15％，例如0.03％、0.05％、0.06％、0.07％、0.08％、0.1％或0.15％；或者，所述Cu的含量较佳地在0.08％以下、但不为0，例如0.03％、0.05％、0.06％、0.07％或0.08％，百分比为占所述原料组合物总质量的质量百分比。
本发明中，所述Cu的添加方式较佳地包括在熔炼时添加和/或在晶界扩散时添加。
当所述Cu在晶界扩散时添加，所述晶界扩散时添加的Cu的含量较佳地为0.03～0.15％，例如0.05％，百分比为占所述原料组合物总质量的质量百分比；当所述Cu在晶界扩散时添加，所述Cu较佳地以PrCu合金的形式添加，其中所述Cu占所述PrCu的质量百分比较佳地为0.1～17％。
本发明中，所述B的含量较佳地为0.97～1.05％，例如0.99％或1％，百分比为占所述原料组合物总质量的质量百分比。
本发明中，所述Fe的含量较佳地为65～69.5％，例如65.99％、67.21％、67.63％、67.71％、68.09％、68.19％、68.95％、68.96％、69.06％或69.91％，百分比为占所述原料组合物总质量的质量百分比。
本发明中，所述原料组合物中，较佳地还包括Al。
其中，所述Al的含量较佳地在0.3％以下、但不为0，更佳地为0.03～0.2％，例如0.03％、0.1％或0.2％，百分比为占所述原料组合物总质量的质量百分比。
本发明中，当所述M包含Ga，且Ga≤0.01％时，较佳地，M元素的组成中Al+Ga+Cu≤0.11％；在本发明一较佳实施例中所述Ga的含量为0.01％，“Al、Ga和Cu”含量的和为0.07％，百分比为占所述原料组合物总质量的质量百分比。
本发明中，所述钕铁硼磁体材料的原料组合物，较佳地包括如下质量含量的组分：R：29.5～32.6％；R包括R1和R2，所述R1包括Nd和Dy，所述R1为熔炼时添加的稀土元素，所述R2的含量为0.2～0.9％，所述R2包括Tb，所述R2为晶界扩散时添加的稀土元素；M：0.35％以下、但不为0，所述M为Zn、Ga和Bi中的一种或多种；Cu：0.05～0.15％；B：0.97～1.05％；Fe：65～69.5％，所述原组合物中不含Co；百分比为各组分含量占所述原料组合物总质量的质量百分比。
本发明中，所述钕铁硼磁体材料的原料组合物，较佳地包括如下质量含量的组分：R：29.5～31％；R包括R1和R2，所述R1包括Nd和Dy，所述R1为熔炼时添加的稀土元素，所述R2的含量为0.2～0.8％，所述R2包括Tb，所述R2为晶界扩散时添加的稀土元素；M：0.1～0.35％，所述M为Zn、Ga和Bi中的一种或多种；Cu：0.08％以下、但不为0；B：0.97～1.05％；Fe：65～69.5％，所述原料组合物中不含Co；百分比为各组分含量占所述原料组合物总质量的质量百分比。
在本发明一较佳实施方式中，所述钕铁硼磁体材料的原料组合物包括如下质量含量的组分：R1：Nd 28.6％、Dy 0.05％、Pr 0.1％，所述R1为熔炼时添加的稀土元素；R2：Tb 1％，所述R2为晶界扩散时添加的稀土元素；Ga 0.05％、Al 0.1％、Cu 0.05％、B 0.99％和Fe 69.06％，所述原料组合物中不含Co，百分比为各组分含量占所述原料组合物总质量的质量百分比。
在本发明一较佳实施方式中，所述钕铁硼磁体材料的原料组合物包括如下质量含量的组分：R1：Nd 28.6％、Dy 0.1％、Pr 0.2％，所述R1为熔炼时 添加的稀土元素；R2：Tb 0.9％，所述R2为晶界扩散时添加的稀土元素；Ga 0.1％、Zn 0.1％、Cu 0.05％、B 1％和Fe 68.95％，所述原料组合物中不含Co，百分比为各组分含量占所述原料组合物总质量的质量百分比。
在本发明一较佳实施方式中，所述钕铁硼磁体材料的原料组合物包括如下质量含量的组分：R1：Nd 28.6％、Dy 0.08％，所述R1为熔炼时添加的稀土元素；R2：Tb 0.9％，所述R2为晶界扩散时添加的稀土元素；Ga 0.3％、Cu 0.06％、B 1.1％和Fe 68.96％，所述原料组合物中不含Co，百分比为各组分含量占所述原料组合物总质量的质量百分比。
在本发明一较佳实施方式中，所述钕铁硼磁体材料的原料组合物包括如下质量含量的组分：R1：Nd 29.9％、Dy 0.1％，所述R1为熔炼时添加的稀土元素；R2：Tb 0.8％、Pr 0.1％，所述R2为晶界扩散时添加的稀土元素；Ga 0.2％、Al 0.2％、Cu 0.03％在熔炼时添加、Cu 0.05％在晶界扩散时添加、B 0.99％和Fe 67.63％，所述原料组合物中不含Co，百分比为各组分含量占所述原料组合物总质量的质量百分比。
在本发明一较佳实施方式中，所述钕铁硼磁体材料的原料组合物包括如下质量含量的组分：R1：Nd 30.4％、Dy 0.05％，所述R1为熔炼时添加的稀土元素；R2：Tb 0.8％、Dy 0.1％，所述R2为晶界扩散时添加的稀土元素；Ga 0.35％、Cu 0.1％、B 0.99％和Fe 67.21％，所述原料组合物中不含Co，百分比为各组分含量占所述原料组合物总质量的质量百分比。
本发明中，所述钕铁硼磁体材料的原料组合物，较佳地包括如下质量含量的组分：R：30～31％；R包括R1和R2，所述R1包括Nd和Dy，所述R1为熔炼时添加的稀土元素，所述R2的含量为0.5～0.7％，所述R2包括Tb，所述R2为晶界扩散时添加的稀土元素；M：0.1～0.2％，所述M为Zn和/或Ga；Cu：0.05～0.09％；B：0.97～1.05％；Fe：67～69％，所述原料组合物中不含Co；百分比为各组分含量占所述原料组合物总质量的质量百分比。
在本发明一较佳实施方式中，所述钕铁硼磁体材料的原料组合物包括如下质量含量的组分：R1：Nd 29.9％、Dy 0.1％、Pr 0.1％，所述R1为熔炼时 添加的稀土元素；R2：Tb 0.6％，所述R2为晶界扩散时添加的稀土元素；Ga 0.15％、Cu 0.07％、B 0.99％和Fe 68.09％，百分比为各组分含量占所述原料组合物总质量的质量百分比。
在本发明一较佳实施方式中，所述钕铁硼磁体材料的原料组合物包括如下质量含量的组分：R1：Nd 29.9％、Dy 0.1％，所述R1为熔炼时添加的稀土元素；R2：Tb 0.6％，所述R2为晶界扩散时添加的稀土元素；Ga 0.15％、Cu 0.07％、B 0.99％和Fe 68.19％，所述原料组合物中不含Co，百分比为各组分含量占所述原料组合物总质量的质量百分比。
在本发明一较佳实施方式中，所述钕铁硼磁体材料的原料组合物包括如下质量含量的组分：R1：Nd 30.4％、Dy 0.05％，所述R1为熔炼时添加的稀土元素；R2：Tb 0.3％、Pr 0.2％，所述R2为晶界扩散时添加的稀土元素；Zn 0.2％、Cu 0.12％在熔炼时添加、Cu 0.03％在晶界扩散时添加、B 0.99％和Fe 67.71％，所述原料组合物中不含Co，百分比为各组分含量占所述原料组合物总质量的质量百分比。
在本发明一较佳实施方式中，所述钕铁硼磁体材料的原料组合物包括如下质量含量的组分：R1：Nd 32.1％、Dy 0.3％，所述R1为熔炼时添加的稀土元素；R2：Tb 0.2％，所述R2为晶界扩散时添加的稀土元素；Zn 0.08％、Bi 0.08％、Cu 0.15％、B 1.1％和Fe 65.99％，所述原料组合物中不含Co，百分比为各组分含量占所述原料组合物总质量的质量百分比。
在本发明一较佳实施方式中，所述钕铁硼磁体材料的原料组合物包括如下质量含量的组分：R1：Nd 28.6％、Dy 0.05％、Pr 0.1％，所述R1为熔炼时添加的稀土元素；R2：Tb 1％，所述R2为晶界扩散时添加的稀土元素；Ga 0.01％、Al 0.03％、Cu 0.03％、B 0.99％和Fe 69.19％，所述原料组合物中不含Co，百分比为各组分含量占所述原料组合物总质量的质量百分比。
本发明还提供了一种钕铁硼磁体材料的制备方法，其采用如上所述的原料组合物进行，所述制备方法为本领域常规的扩散制法，其中，所述R1元素在熔炼步骤中添加，所述R2元素在晶界扩散步骤中添加。
本发明中，所述制备方法较佳地包括如下步骤：将上述钕铁硼磁体材料的原料组合物中除R2以外的元素经熔炼、制粉、成型、烧结得烧结体，接着将所述的烧结体与所述R2的混合物经晶界扩散即可。
其中，所述熔炼的操作和条件可为本领域常规的熔炼工艺，一般将所述钕铁硼磁体材料的原料组合物中除R2以外的元素采用铸锭工艺和速凝片工艺进行熔炼浇铸，得到合金片。
本领域技术人员知晓，因熔炼和烧结工艺中通常会损耗稀土元素，为保证终产品的质量，一般熔炼过程中会在原料组合物配方的基础中额外添加0～0.3wt％的稀土元素(一般为Nd元素)，百分比为额外添加的稀土元素的质量占所述原料组合物的总质量的质量百分比；另外这部分额外添加的稀土元素的含量不计入原料组合物的范畴。
所述熔炼的温度可为1300～1700℃，较佳地为1450～1550℃。
所述熔炼的环境可为0.05Pa的真空。
所述熔炼的设备一般为中频真空熔炼炉，例如中频真空感应速凝甩带炉。
其中，所述制粉的操作和条件可为本领域常规制粉工艺，一般包括氢破制粉和/或气流磨制粉。
所述氢破制粉一般包括吸氢、脱氢和冷却处理。所述吸氢的温度一般为20～200℃。所述脱氢的温度一般为400～650℃，较佳地为500～550℃。所述吸氢的压力一般为50～600kPa，较佳地为300～500kPa。
所述气流磨制粉一般在0.1～2MPa，优选0.5～0.7MPa的条件下进行气流磨制粉。所述气流磨制粉中的气流例如可为氮气。所述气流磨制粉的时间可为2～4h。
其中，所述成型的操作和条件可为本领域常规的成型工艺。例如磁场成型法。所述的磁场成型法的磁场强度一般在1.5T以上。
其中，所述烧结的操作和条件可为本领域常规的烧结工艺。
所述烧结可在真空度低于0.5Pa的条件下进行。
所述烧结的温度可为1000～1200℃，较佳地为1030～1090℃。
所述烧结的时间可为0.5～10h，较佳地为2～5h。
本发明中，本领域技术人员知晓，在所述的晶界扩散之前一般还包括所述R2的涂覆操作。
其中，所述R2一般是以氟化物或低熔点合金的形式涂覆，例如Tb的氟化物。当还包含Dy时，较佳地，Dy以Dy的氟化物形式涂覆。
其中，当所述R2包含Pr时，较佳地，所述Pr以PrCu合金的形式添加。所述PrCu合金中，所述Cu与所述PrCu合金的质量比较佳地为0.1～17％。
较佳地，所述Cu在所述制备方法中的添加时机为晶界扩散步骤，或者在熔炼步骤和晶界扩散步骤同时添加。本发明中，所述晶界扩散处理的操作和条件可为本领域常规的晶界扩散工艺。
所述晶界扩散的温度可为800～1000℃，例如850℃。
所述晶界扩散的时间可为5～20h，较佳地为5～15h。
所述晶界扩散之后，按照本领域常规还进行低温回火处理。低温回火处理的温度一般为460～560℃。所述低温回火的时间一般可为1～3h。
本发明还提供了一种由上述制备方法制得的钕铁硼磁体材料。
本发明还提供了一种钕铁硼磁体材料，其包括如下质量含量的组分：R：28～33％；所述R包括R1和R2，所述R1包括Nd和Dy，所述R2包括Tb；R2的含量为0.2％～1％；
M：≤0.4％、但不为0，所述M为Bi、Sn、Zn、Ga、In、Au和Pb中的一种或多种；
Cu：≤0.15％、但不为0；
B：0.9～1.1％；
Fe：60～70％；
所述钕铁硼磁体材料中不含Co；百分比为各组分质量占所述钕铁硼磁体材料总质量的质量百分比；
所述钕铁硼磁体材料包含Nd 2Fe l4B晶粒和其壳层、邻接所述Nd 2Fe l4B 晶粒的二颗粒晶界和晶界三角区，其中R1中的重稀土元素分布在Nd 2Fe l4B晶粒，R2主要分布在所述壳层、二颗粒晶界和晶界三角区，所述晶界三角区面积占比为2～3.12％；所述二颗粒晶界的晶界连续性为96％以上；所述晶界三角区中C和O的质量占比为0.4～0.5％，所述二颗粒晶界中C和O的质量占比为0.3～0.4％。
本发明中，“R1中的重稀土元素主要分布在Nd 2Fe l4B晶粒”可理解为，本领域常规的熔炼烧结工艺引起的R1中的重稀土元素主要分布(一般是指95wt％以上)在Nd 2Fe l4B晶粒，少量分布在晶界。“R2主要分布在所述壳层”可理解为，本领域常规的晶界扩散工艺引起的R2主要分布在(一般是指95wt％以上)在Nd 2Fe l4B晶粒的壳层和晶界(二颗粒晶界和晶界三角区)，少部分也会扩散进入Nd 2Fe l4B晶粒中，例如在Nd 2Fe l4B晶粒的外缘。
本发明中，所述晶界连续性的计算方式是指晶界中除空洞外的物相占据的长度(物相例如为富B相、富稀土相、稀土氧化物、稀土碳化物等)与总晶界长度的比值。晶界连续性超过96％即可称为连续通道。
本发明中，所述晶界三角区一般是指三条或以上的晶界相交叉的地方，分布有富B相、富稀土相、稀土氧化物、稀土碳化物和空洞。所述晶界三角区的面积占比的计算方式是指晶界三角区的面积与“晶粒和晶界”总面积之比。
其中，稀土氧化物、稀土碳化物主要是通过在制备过程中引入的C、O元素产生的。由于晶界的稀土含量高，C、O在磁体材料中通常更多地分布在晶界中，并分别以稀土碳化物和稀土氧化物的形式存在。需要说明的是：C、O元素为本领域常规方式引入，一般为杂质引入或者气氛引入，具体例如，在气流磨、压制过程中，有添加剂的引入，在烧结的时候，会通过加热对这些添加剂进行脱去处理，但是不可避免会有少量C、O元素残留；再例如，在制备工艺中不可避免地会因气氛引入少量O元素。在本发明中，经检测最终得到的钕铁硼磁体材料产品中，C、O含量分别只有1000、1200ppm以下，属于本领域常规的可接受的杂质范畴，故未纳入产品元素统计表。
本发明中，所述晶界三角区面积占比较佳地为2.07～2.84％，例如2.07％、2.45％、2.54％、2.65％、2.67％、2.79％或2.84％，更佳地在2.07～2.6％。
本发明中，所述晶界连续性较佳地为97％以上，例如97.88％、97.92％、98.04％、98.08％、98.09％、98.11％、98.13％、98.16％、98.21％或98.22％，更佳地为在98％以上。
本发明中，所述晶界三角区中C和O的质量占比为较佳地为0.41～0.48％，例如0.41％、0.42％、0.44％、0.45％、0.46％、0.47％或0.48％，更佳地为0.41～0.46％，百分比为晶界三角区中C和O的质量与晶界中所有元素的总质量的比。
本发明中，所述二颗粒晶界中C和O的质量占比为较佳地为0.32～0.39％，例如0.32％、0.33％、0.34％、0.35％、0.36％、0.37％或0.39％，更佳地为0.34～0.39％，百分比为二颗粒晶界中C和O的质量与晶界中所有元素的总质量的比。
本发明中，本领域技术人员知晓，C、O元素在晶界相中通常是以稀土碳化物和稀土氧化物的形式存在，因此“晶界三角区中C和O的质量占比”以及“二颗粒晶界中C和O的质量占比”分别对应杂相稀土碳化物和稀土氧化物。另外，根据实施例中“晶界三角区中C和O的质量占比”减去“二颗粒晶界中C和O的质量占比(％)”的差值相比对比例缩小，可得到杂相从晶界三角区迁移到二颗粒晶界的结论，这从机理上解释了晶界连续性的提升原因。
本发明中，所述钕铁硼磁体材料的二颗粒晶界中，除稀土氧化物和稀土碳化物这两种杂相外，较佳地，还在二颗粒晶界中检测到新物相，所述新物相的化学组成为：R xFe 100-x-y-zCu yM z，其中，R xFe 100-x-y-zCu yM z中的R包括Nd、Dy和Tb中的一种或多种，所述M为Bi、Sn、Zn、Ga、In、Au和Pb中的一种或多种；x为78～80；y为0.8～1.5；z为0.1以下，但不为0。
R xFe 100-x-y-zCu yM z中，x较佳地为78.1～79.5，y较佳地为0.99～1.33，z较佳地为0.26～0.38。
在本发明的较佳实施方式中，所述新物相的结构例如，R 78.89Fe 19.59Cu 1.17M 0.35、R 78.17Fe 20.50Cu 1.07M 0.26、R 77.87Fe 20.50Cu 1.33M 0.30、R 79.42Fe 19.16Cu 1.07M 0.35、R 78.68Fe 19.77Cu 1.17M 0.38、R 78.50Fe 20.13Cu 1.03M 0.34、R 78.87Fe 19.79Cu 0.99M 0.35、R 78.14Fe 20.34Cu 1.23M 0.29、R 78.68Fe 19.80Cu 1.20M 0.32、R 79.41Fe 19.09Cu 1.17M 0.33。
本发明中，化学组成为：R xFe 100-x-y-zCu yM z的所述新物相在所述二颗粒晶界中的面积与所述二颗粒晶界总面积的比较佳地为0.25～1.65％，例如0.25％、0.35％、0.56％、0.58％、0.78％、0.85％、0.97％、1.54％、1.62％或1.65％，更佳地为0.5～1.65％。
发明人推测，该新物相在二颗粒晶界生成，所以进一步提高了晶界连续性，从而提升了磁体性能。
本发明中，所述钕铁硼磁体材料中，所述R的含量较佳地为29.5～32.6％，例如29.58％、29.75％、29.8％、30.6％、30.7％、30.9％、30.95％、31.35％或32.6％，更佳地为29.5～31％，百分比为占所述钕铁硼磁体材料总质量的质量百分比。
本发明中，所述钕铁硼磁体材料的R1中，所述Nd的含量可为本领域常规，较佳地为28.5～32.5％，例如28.6％、29.9％、30.4％或32.1％，更佳地为28.5～31％，百分比为占所述钕铁硼磁体材料总质量的质量百分比。
本发明中，所述钕铁硼磁体材料的R1中，所述Dy的含量较佳地在0.3％以下、但不为0，例如0.05％、0.08％、0.1％或0.3％，更佳地为0.05～0.2％，百分比为占所述钕铁硼磁体材料总质量的质量百分比。
本发明中，所述R1还可包括本领域其他常规的稀土元素，例如包括Pr、Ho、Tb、Gd和Y中的一种或多种。
其中，当所述R1包含Pr时，Pr的添加形式可为本领域常规，例如以PrNd的形式，或者，以纯Pr和纯Nd的混合物的形式，或者，以“PrNd、纯Pr和纯Nd的混合物”联合添加。当以PrNd的形式添加时，Pr：Nd较佳地为25:75或20：80；当以纯Pr和纯Nd的混合物的形式添加时，或者，当 以“PrNd、纯Pr和纯Nd的混合物”联合添加时，所述Pr的含量较佳地为0.1～2％，例如0.2％，百分比为各组分含量占所述钕铁硼磁体材料总质量的质量百分比。本发明中所述纯Pr或纯Nd一般指的是纯度在99.5％以上。
其中，当所述的R1包含Ho时，所述Ho的含量较佳地为0.1～0.2％，百分比为占所述钕铁硼磁体材料总质量的质量百分比。
其中，当所述的R1包含Gd时，所述Gd的含量较佳地为0.1～0.2％，百分比为占所述钕铁硼磁体材料总质量的质量百分比。
其中，当所述的R1包含Y时，所述Y的含量较佳地为0.1～0.2％，百分比为占所述钕铁硼磁体材料总质量的质量百分比。
本发明中，所述R2的含量较佳地为0.2～0.9％，例如0.2％、0.5％、0.6％、0.8％或0.9％，百分比为占所述钕铁硼磁体材料总质量的质量百分比。
本发明中，所述R2中，Tb的含量较佳地为0.2％～1％，例如0.2％、0.3％、0.6％、0.8％或0.9％，更佳地为0.5～1％，百分比为占所述钕铁硼磁体材料总质量的质量百分比。
本发明中，所述钕铁硼磁体材料中，所述R2较佳地还包括Pr和/或Dy。
其中，当所述的R2包含Pr时，所述Pr的含量较佳地为0.2％以下、但不为0，例如0.1％，百分比为占所述钕铁硼磁体材料总质量的质量百分比。
其中，当所述R2包含Dy时，所述Dy的含量较佳地为0.3％以下、但不为0，例如0.1％，百分比为占所述钕铁硼磁体材料总质量的质量百分比。
本发明中，所述M的含量较佳地在0.35％以下、但不为0，更佳地为0.01～0.35％，例如0.01％、0.1％、0.15％、0.16％、0.2％或0.3％，百分比为占所述钕铁硼磁体材料总质量的质量百分比。
本发明中，所述M的种类较佳地为Zn、Ga和Bi中的一种或多种。
其中，当所述M包含Ga时，所述Ga的含量较佳地在0.35％以下、但不为0，例如0.01％、0.1％、0.15％、0.2％、0.3％或0.35％，更佳地为0.1～0.35％，百分比为占所述钕铁硼磁体材料总质量的质量百分比。
其中，当所述M包含Zn时，所述Zn的含量较佳地在0.35％以下、但 不为0，更佳地为0.05～0.25％，例如0.08％、0.1％或0.2％，百分比为占所述钕铁硼磁体材料总质量的质量百分比。
其中，当所述M包含Bi时，所述Bi的含量较佳地在0.35％以下、但不为0，更佳地为0.05～0.15％，例如0.08％，百分比为占所述钕铁硼磁体材料总质量的质量百分比。
本发明中，所述Cu的含量较佳地为0.03～0.15％，例如0.03％、0.05％、0.06％、0.07％、0.08％、0.1％或0.15％；或者，所述Cu的含量较佳地在0.08％以下、但不为0，例如0.03％、0.05％、0.06％、0.07％或0.08％，，百分比为占所述钕铁硼磁体材料总质量的质量百分比。
本发明中，所述Cu的添加方式较佳地包括在熔炼时添加和/或在晶界扩散时添加。当所述Cu在晶界扩散时添加，所述晶界扩散时添加的Cu的含量较佳地为0.03～0.15％，例如0.05％，百分比为占所述钕铁硼磁体材料总质量的质量百分比；当所述Cu在晶界扩散时添加，所述Cu较佳地以PrCu合金的形式添加，其中所述Cu占所述PrCu的质量百分比较佳地为0.1～17％。
本发明中，所述B的含量较佳地为0.97～1.05％，例如0.99％或1％，百分比为占所述钕铁硼磁体材料总质量的质量百分比。
本发明中，所述Fe的含量较佳地为65～69.5％，例如65.99％、67.21％、67.63％、67.71％、68.09％、68.19％、68.95％、68.96％、69.06％或69.91％，百分比为占所述钕铁硼磁体材料总质量的质量百分比。
本发明中，所述钕铁硼磁体材料中，较佳地还包括Al。
其中，所述Al的含量较佳地在0.3％以下、但不为0，更佳地在0.2％以下、但不为0，例如0.03％、0.1％或0.2％，百分比为占所述钕铁硼磁体材料总质量的质量百分比。
本发明中，当所述M包含Ga，且Ga≤0.01％时，较佳地，M元素的组成中Al+Ga+Cu≤0.11％，百分比为占所述钕铁硼磁体材料总质量的质量百分比；在本发明一较佳实施例中所述Ga的含量为0.01％，“Al、Ga和Cu”含量的和为0.07％，百分比为占所述钕铁硼磁体材料总质量的质量百分比。
本发明中，所述钕铁硼磁体材料较佳地包括如下质量含量的组分：R：29.5～32.6％；R包括R1和R2，所述R1包括Nd和Dy，所述R1为熔炼时时添加的稀土元素，所述R2的含量为0.2～0.9％，所述R2包括Tb，所述R2为晶界扩散时添加的稀土元素；M：0.35％以下、但不为0，所述M为Zn、Ga和Bi中的一种或多种；Cu：0.05～0.15％；B：0.97～1.05％；Fe：65～69.5％，所述钕铁硼磁体材料中不含Co；百分比为各组分含量占所述钕铁硼磁体材料总质量的质量百分比；所述钕铁硼磁体材料包含Nd 2Fe l4B晶粒和其壳层、邻接所述Nd 2Fe l4B晶粒的二颗粒晶界和晶界三角区，其中R1中的重稀土元素分布在Nd 2Fe l4B晶粒，R2主要分布在所述壳层、二颗粒晶界和晶界三角区，所述晶界三角区面积占比为2～2.84％；所述钕铁硼磁体材料的晶界连续性为97％以上；所述晶界三角区中C和O的质量占比为0.41～0.48％；所述二颗粒晶界中C和O的质量占比为0.32～0.39％；所述二颗粒晶界中含有新物相，所述新物相的化学组成为：R xFe 100-x-y-zCu yM z，其中，R xFe 100-x-y-zCu yM z中的R包括Nd、Dy和Tb中的一种或多种，所述M为Bi、Sn、Zn、Ga、In、Au和Pb中的一种或多种；x为78.1～79.5，y为0.99～1.33，z为0.26～0.38；所述新物相在所述二颗粒晶界中的面积与所述二颗粒晶界总面积的比为0.25～1.65％。
本发明中，所述钕铁硼磁体材料，较佳地包括如下质量含量的组分：R：29.5～31％；R包括R1和R2，所述R1包括Nd和Dy，所述R1为熔炼时添加的稀土元素，所述R2的含量为0.2～0.8％，所述R2包括Tb，所述R2为晶界扩散时添加的稀土元素；M：0.01～0.35％，所述M为Zn、Ga和Bi中的一种或多种；Cu：0.08％以下、但不为0；B：0.97～1.05％；Fe：65～69.5％，所述钕铁硼磁体材料中不含Co；百分比为各组分含量占所述钕铁硼磁体材料总质量的质量百分比；所述钕铁硼磁体材料包含Nd 2Fe l4B晶粒和其壳层、邻接所述Nd 2Fe l4B晶粒的二颗粒晶界和晶界三角区，其中R1中的重稀土元素分布在Nd 2Fe l4B晶粒，R2主要分布在所述壳层、二颗粒晶界和晶界三角区，所述晶界三角区面积占比为2～2.6％；所述钕铁硼磁体材料的晶界连续 性为98％以上；所述晶界三角区中C和O的质量占比为0.41～0.46％；所述二颗粒晶界中C和O的质量占比为0.32～0.39％；所述二颗粒晶界中含有新物相，所述新物相的化学组成为：R xFe 100-x-y-zCu yM z，其中，R xFe 100-x-y-zCu yM z中的R包括Nd、Dy和Tb中的一种或多种，所述M为Bi、Zn、和Ga中的一种或多种；x为78.1～79.5，y为0.99～1.33，z为0.26～0.38；所述新物相在所述二颗粒晶界中的面积与所述二颗粒晶界总面积的比为0.5～1.65％。
在本发明一较佳实施方式中，所述钕铁硼磁体材料包括如下质量含量的组分：R1：Nd 28.6％、Dy 0.05％、Pr 0.1％，所述R1为熔炼时添加的稀土元素；R2：Tb 1％，所述R2为晶界扩散时添加的稀土元素；Ga 0.05％、Al 0.1％、Cu 0.05％、B 0.99％和Fe 69.06％，所述钕铁硼磁体材料中不含Co，百分比为各组分含量占所述钕铁硼磁体材料总质量的质量百分比；所述钕铁硼磁体材料包含Nd 2Fe l4B晶粒和其壳层、邻接所述Nd 2Fe l4B晶粒的二颗粒晶界和晶界三角区；其中R1中的重稀土元素主要分布在Nd 2Fe l4B晶粒，R2主要分布在所述壳层、二颗粒晶界和晶界三角区，所述晶界三角区的面积占比为2.84％；所述二颗粒晶界的晶界连续性为98.11％；所述晶界三角区中C和O的质量占比为0.44％；所述二颗粒晶界中C和O的质量占比为0.39％；二颗粒晶界中含有新物相，其化学组成为R 78.89Fe 19.59Cu 1.17M 0.35，R为Nd、Dy、Pr和Tb中的一种或多种，M为Ga；所述新物相在所述二颗粒晶界中的面积与所述二颗粒晶界总面积的比为0.85％。
在本发明一较佳实施方式中，所述钕铁硼磁体材料包括如下质量含量的组分：R1：Nd 28.6％、Dy 0.1％、Pr 0.2％，所述R1为熔炼时添加的稀土元素；R2：Tb 0.9％，所述R2为晶界扩散时添加的稀土元素；Ga 0.1％、Zn 0.1％、Cu 0.05％、B 1％和Fe 68.95％，所述钕铁硼磁体材料中不含Co，百分比为各组分含量占所述钕铁硼磁体材料总质量的质量百分比；所述钕铁硼磁体材料包含Nd 2Fe l4B晶粒和其壳层、邻接所述Nd 2Fe l4B晶粒的二颗粒晶界和晶界三角区；其中R1中的重稀土元素主要分布在Nd 2Fe l4B晶粒，R2主要分布在所述壳层、二颗粒晶界和晶界三角区，所述晶界三角区的面积占比为2.65％； 所述二颗粒晶界的晶界连续性为98.09；所述晶界三角区中C和O的质量占比为0.41％；所述二颗粒晶界中C和O的质量占比为0.32％；二颗粒晶界中含有新物相，其化学组成为R 78.17Fe 20.50Cu 1.07M 0.26，R为Nd、Dy、Pr和Tb中的一种或多种，M为Zn和Ga；所述新物相在所述二颗粒晶界中的面积与所述二颗粒晶界总面积的比为0.56％。
在本发明一较佳实施方式中，所述钕铁硼磁体材料包括如下质量含量的组分：R1：Nd 28.6％、Dy 0.08％，所述R1为熔炼时添加的稀土元素；R2：Tb 0.9％，所述R2为晶界扩散时添加的稀土元素；Ga 0.3％、Cu 0.06％、B 1.1％和Fe 68.96％，所述钕铁硼磁体材料中不含Co，百分比为各组分含量占所述钕铁硼磁体材料总质量的质量百分比；所述钕铁硼磁体材料包含Nd 2Fe l4B晶粒和其壳层、邻接所述Nd 2Fe l4B晶粒的二颗粒晶界和晶界三角区；其中R1中的重稀土元素主要分布在Nd 2Fe l4B晶粒，R2主要分布在所述壳层、二颗粒晶界和晶界三角区，所述晶界三角区的面积占比为2.67％；所述二颗粒晶界的晶界连续性为97.92％；所述晶界三角区中C和O的质量占比为0.42％；所述二颗粒晶界中C和O的质量占比为0.34％；二颗粒晶界中含有新物相，其化学组成为R 77.87Fe 20.50Cu 1.33M 0.30，R为Nd、Dy和Tb中的一种或多种，M为Ga；所述新物相在所述二颗粒晶界中的面积与所述二颗粒晶界总面积的比为0.58％。
在本发明一较佳实施方式中，所述钕铁硼磁体材料包括如下质量含量的组分：R1：Nd 29.9％、Dy 0.1％，所述R1为熔炼时添加的稀土元素；R2：Tb 0.8％、Pr 0.1％，所述R2为晶界扩散时添加的稀土元素；Ga 0.2％、Al 0.2％、Cu 0.08％、B 0.99％和Fe 67.63％，所述钕铁硼磁体材料中不含Co，百分比为各组分含量占所述钕铁硼磁体材料总质量的质量百分比；所述钕铁硼磁体材料包含Nd 2Fe l4B晶粒和其壳层、邻接所述Nd 2Fe l4B晶粒的二颗粒晶界和晶界三角区；其中R1中的重稀土元素主要分布在Nd 2Fe l4B晶粒，R2主要分布在所述壳层、二颗粒晶界和晶界三角区，所述晶界三角区的面积占比为2.54％；所述二颗粒晶界的晶界连续性为98.22％；所述晶界三角区中C和O 的质量占比为0.48％；所述二颗粒晶界中C和O的质量占比为0.33％；二颗粒晶界中含有新物相，其化学组成为R 79.42Fe 19.16Cu 1.07M 0.35，R为Nd、Dy和Tb中的一种或多种，M为Al和Ga；所述新物相在所述二颗粒晶界中的面积与所述二颗粒晶界总面积的比为1.65％。
在本发明一较佳实施方式中，所述钕铁硼磁体材料包括如下质量含量的组分：R1：Nd 30.4％、Dy 0.05％，所述R1为熔炼时添加的稀土元素；R2：Tb 0.8％、Dy 0.1％，所述R2为晶界扩散时添加的稀土元素；Ga 0.35％、Cu 0.1％、B 0.99％和Fe 67.21％，所述钕铁硼磁体材料中不含Co，百分比为各组分含量占所述钕铁硼磁体材料总质量的质量百分比；所述钕铁硼磁体材料包含Nd 2Fe l4B晶粒和其壳层、邻接所述Nd 2Fe l4B晶粒的二颗粒晶界和晶界三角区；其中R1中的重稀土元素主要分布在Nd 2Fe l4B晶粒，R2主要分布在所述壳层、二颗粒晶界和晶界三角区，所述晶界三角区的面积占比为2.07％；所述二颗粒晶界的晶界连续性为98.04％；所述晶界三角区中C和O的质量占比为0.46％；所述二颗粒晶界中C和O的质量占比为0.35％；二颗粒晶界中含有新物相，其化学组成为R 78.68Fe 19.77Cu 1.17M 0.38，R为Nd、Dy和Tb中的一种或多种，M为Ga；所述新物相在所述二颗粒晶界中的面积与所述二颗粒晶界总面积的比为1.54％。
本发明中，所述钕铁硼磁体材料包括如下质量含量的组分：R：30～31％；R包括R1和R2，所述R1包括Nd和Dy，所述R1为熔炼时添加的稀土元素，所述R2的含量为0.5～0.7％，所述R2包括Tb，所述R2为晶界扩散时添加的稀土元素；M：0.1～0.2％，所述M为Zn和/或Ga；Cu：0.05～0.09％；B：0.97～1.05％；Fe：67～69％，所述钕铁硼磁体材料中不含Co；百分比为各组分含量占所述钕铁硼磁体材料总质量的质量百分比；所述钕铁硼磁体材料包含Nd 2Fe l4B晶粒和其壳层、邻接所述Nd 2Fe l4B晶粒的二颗粒晶界和晶界三角区；其中R1中的重稀土元素主要分布在Nd 2Fe l4B晶粒，R2主要分布在所述壳层、二颗粒晶界和晶界三角区，所述晶界三角区的面积占比为2.07～2.6％；所述二颗粒晶界的晶界连续性为98％～98.3％；所述晶界三角区 中C和O的质量占比为0.41～0.46％；所述二颗粒晶界中C和O的质量占比为0.34～0.39％；所述二颗粒晶界中含有新物相，所述新物相的化学组成为：R xFe 100-x-y-zCu yM z，其中，R xFe 100-x-y-zCu yM z中的R包括Nd、Dy和Tb中的一种或多种，所述M为Bi、Sn、Zn、Ga、In、Au和Pb中的一种或多种；x为78.1～79.5，y为0.99～1.33，z为0.26～0.38；所述新物相在所述二颗粒晶界中的面积与所述二颗粒晶界总面积的比为0.5～1.65％。
在本发明一较佳实施方式中，所述钕铁硼磁体材料包括如下质量含量的组分：R1：Nd 29.9％、Dy 0.1％、Pr 0.1％，所述R1为熔炼时添加的稀土元素；R2：Tb 0.6％，所述R2为晶界扩散时添加的稀土元素；Ga 0.15％、Cu 0.07％、B 0.99％和Fe 68.09％，所述钕铁硼磁体材料中不含Co，百分比为各组分含量占所述钕铁硼磁体材料总质量的质量百分比；所述钕铁硼磁体材料包含Nd 2Fe l4B晶粒和其壳层、邻接所述Nd 2Fe l4B晶粒的二颗粒晶界和晶界三角区；其中R1中的重稀土元素主要分布在Nd 2Fe l4B晶粒，R2主要分布在所述壳层、二颗粒晶界和晶界三角区，所述晶界三角区的面积占比为2.45％；所述二颗粒晶界的晶界连续性为98.08％；所述晶界三角区中C和O的质量占比为0.44％；所述二颗粒晶界中C和O的质量占比为0.35％；二颗粒晶界中含有新物相，其化学组成为R 78.50Fe 20.13Cu 1.03M 0.34，R为Nd、Dy和Tb中的一种或多种，M为Ga；所述新物相在所述二颗粒晶界中的面积与所述二颗粒晶界总面积的比为1.62％。
在本发明一较佳实施方式中，所述钕铁硼磁体材料包括如下质量含量的组分：R1：Nd 29.9％、Dy 0.1％，所述R1为熔炼时添加的稀土元素；R2：Tb 0.6％，所述R2为晶界扩散时添加的稀土元素；Ga 0.15％、Cu 0.07％、B 0.99％和Fe 68.19％，所述钕铁硼磁体材料中不含Co，百分比为各组分含量占所述钕铁硼磁体材料总质量的质量百分比。；所述钕铁硼磁体材料包含Nd 2Fe l4B晶粒和其壳层、邻接所述Nd 2Fe l4B晶粒的二颗粒晶界和晶界三角区；其中R1中的重稀土元素主要分布在Nd 2Fe l4B晶粒，R2主要分布在所述壳层、二颗粒晶界和晶界三角区，所述晶界三角区的面积占比为2.67％；所述二颗 粒晶界的晶界连续性为98.13％；所述晶界三角区中C和O的质量占比为0.47％；所述二颗粒晶界中C和O的质量占比为0.37％；二颗粒晶界中含有新物相，其化学组成为R 78.87Fe 19.79Cu 0.99M 0.35，R为Nd、Dy和Tb中的一种或多种，M为Ga；所述新物相在所述二颗粒晶界中的面积与所述二颗粒晶界总面积的比为0.97％。
在本发明一较佳实施方式中，所述钕铁硼磁体材料包括如下质量含量的组分：R1：Nd 30.4％、Dy 0.05％，所述R1为熔炼时添加的稀土元素；R2：Tb 0.3％、Pr 0.2％，所述R2为晶界扩散时添加的稀土元素；Zn 0.2％、Cu 0.15％、B 0.99％和Fe 67.71％，所述钕铁硼磁体材料中不含Co，百分比为各组分含量占所述钕铁硼磁体材料总质量的质量百分比；所述钕铁硼磁体材料包含Nd 2Fe l4B晶粒和其壳层、邻接所述Nd 2Fe l4B晶粒的二颗粒晶界和晶界三角区；其中R1中的重稀土元素主要分布在Nd 2Fe l4B晶粒，R2主要分布在所述壳层、二颗粒晶界和晶界三角区，所述晶界三角区的面积占比为2.65％；所述二颗粒晶界的晶界连续性为98.21％；所述晶界三角区中C和O的质量占比为0.42％；所述二颗粒晶界中C和O的质量占比为0.36％；二颗粒晶界中含有新物相，其化学组成为R 78.14Fe 20.34Cu 1.23M 0.29，R为Nd、Dy和Tb中的一种或多种，M为Zn；所述新物相在所述二颗粒晶界中的面积与所述二颗粒晶界总面积的比为0.25％。
在本发明一较佳实施方式中，所述钕铁硼磁体材料包括如下质量含量的组分：R1：Nd 32.1％、Dy 0.3％，所述R1为熔炼时添加的稀土元素；R2：Tb 0.2％，所述R2为晶界扩散时添加的稀土元素；Zn 0.08％、Bi 0.08％、Cu 0.15％、B 1.1％和Fe 65.99％，所述钕铁硼磁体材料中不含Co，百分比为各组分含量占所述钕铁硼磁体材料总质量的质量百分比；所述钕铁硼磁体材料包含Nd 2Fe l4B晶粒和其壳层、邻接所述Nd 2Fe l4B晶粒的二颗粒晶界和晶界三角区；其中R1中的重稀土元素主要分布在Nd 2Fe l4B晶粒，R2主要分布在所述壳层、二颗粒晶界和晶界三角区，所述晶界三角区的面积占比为3.12％；所述二颗粒晶界的晶界连续性为97.88％；所述晶界三角区中C和O的质量 占比为0.45％；所述二颗粒晶界中C和O的质量占比为0.37％；二颗粒晶界中含有新物相，其化学组成为R 78.68Fe 19.80Cu 1.20M 0.32，R为Nd、Dy和Tb中的一种或多种，M为Zn和Bi；所述新物相在所述二颗粒晶界中的面积与所述二颗粒晶界总面积的比为0.35％。
在本发明一较佳实施方式中，所述钕铁硼磁体材料包括如下质量含量的组分：R1：Nd 28.6％、Dy 0.05％、Pr 0.1％，所述R1为熔炼时添加的稀土元素；R2：Tb 1％，所述R2为晶界扩散时添加的稀土元素；Ga 0.01％、Al 0.03％、Cu 0.03％、B 0.99％和Fe 69.19％，所述钕铁硼磁体材料中不含Co，百分比为各组分含量占所述钕铁硼磁体材料总质量的质量百分比；所述钕铁硼磁体材料包含Nd 2Fe l4B晶粒和其壳层、邻接所述Nd 2Fe l4B晶粒的二颗粒晶界和晶界三角区；其中R1中的重稀土元素主要分布在Nd 2Fe l4B晶粒，R2主要分布在所述壳层、二颗粒晶界和晶界三角区，所述晶界三角区的面积占比为2.79％；所述二颗粒晶界的晶界连续性为98.16％；所述晶界三角区中C和O的质量占比为0.42％；所述二颗粒晶界中C和O的质量占比为0.34％；二颗粒晶界中含有新物相，其化学组成为R 79.41Fe 19.09Cu 1.17M 0.33，R为Nd、Dy和Tb中的一种或多种，M为Ga；所述新物相在所述二颗粒晶界中的面积与所述二颗粒晶界总面积的比为0.78％。
本发明提供的钕铁硼磁体材料合理控制总稀土量TRE、Cu和M(Ga、Zn等)元素的含量范围，并结合重稀土元素特定的加料时机，使得杂相(稀土氧化物和稀土碳化物)更多地分布在二颗粒晶界，而不是团聚在晶界三角区，从而使晶界连续性提高，减少了晶界三角区的面积，有益于获得更高的致密性，从而提高了磁体剩磁Br；也促使Tb元素主要均匀的分布在晶界和主相壳层，提高了磁体矫顽力Hcj。
本发明还提供了一种如上所述的钕铁硼磁体材料在制备磁钢中的应用。
其中，所述磁钢较佳地为54SH、54UH、56SH磁钢。
在符合本领域常识的基础上，上述各优选条件，可任意组合，即得本发明各较佳实例。
本发明所用试剂和原料均市售可得。
本发明的积极进步效果在于：本发明中的钕铁硼磁体材料通过多种元素的特定含量之间的配合，在不含Co和大量重稀土元素的前提下，可在现有钕铁硼磁体材料的基础上，提升物相在二颗粒晶界相中的占比，在二颗粒晶界中生成了新物相；相应的增加二颗粒晶界的连续性，减少杂相在晶界三角区的占比、相应的减少了晶界三角区的面积。从而提高了钕铁硼磁体材料的剩磁Br、矫顽力Hcj、及相应的温度稳定性。其中剩磁可达14.31～14.61kGs，矫顽力可达24.11～26.35kOe，且20～120℃Br温度系数α可达-0.105～-0.109之间。
附图说明
图1为实施例4的钕铁硼磁体材料的EPMA微观结构图。图中箭头1所指的点为二颗粒晶界中包含的R xFe 100-x-y-zCu yM z新物相，箭头2所指的位置为晶界三角区，箭头3所指的位置为Nd 2Fe l4B主相。
具体实施方式
下面通过实施例的方式进一步说明本发明，但并不因此将本发明限制在所述的实施例范围之中。下列实施例中未注明具体条件的实验方法，按照常规方法和条件，或按照商品说明书选择。
1、本发明实施例1～10和对比例1～3的钕铁硼磁体材料的原料组合物如下表1所示。
表1钕铁硼磁体材料的原料组合物的配方和含量(wt％)
Figure PCTCN2021077172-appb-000001
Figure PCTCN2021077172-appb-000002
注：“/”是指不含有该元素。wt％为质量百分比。
2、实施例1中钕铁硼磁体材料的制备方法
(1)熔炼和铸造过程：按照表1中的配方，将配制好的除R2(实施例4和8中的R2以PrCu形式添加，实施例4和8中Cu在晶界扩散步骤添加的含量分别为0.05wt％和0.03wt％，Cu在熔炼步骤，添加的含量分别为0.03wt％和0.12wt％)以外的原料放入氧化铝的坩埚中，在高频真空熔炼炉中以0.05Pa的真空和1500℃的条件进行真空熔炼。再中频真空感应速凝甩带炉中通入氩气，进行铸造，再急冷合金，得合金片。
(2)氢破制粉过程：在室温下将放置急冷合金的氢破用炉抽真空，而后向氢破用炉内通入纯度为99.9％的氢气，维持氢气的压力90kPa，充分吸氢后，边抽真空边升温，充分脱氢，之后进行冷却，取出氢破粉碎后的粉末。其中，吸氢的温度为室温，脱氢的温度为550℃。
(3)气流磨制粉过程：在氮气气氛下，在粉碎室压力为0.6MPa的条件下对氢破粉碎后的粉末进行3h的气流磨粉碎，得到细粉。
(4)成型过程：将经气流膜之后的粉末在1.5T以上的磁场强度中成型。
(5)烧结过程：将各成型体搬至烧结炉中进行烧结，烧结在低于0.5Pa的真空下，以1030-1090℃烧结2～5h，得烧结体。
(6)晶界扩散过程：将烧结体表面净化后将R2(例如Tb的合金或氟 化物、Dy的合金或氟化物和PrCu合金中的一种或多种，其中Cu在熔炼步骤和晶界扩散步骤同时添加)涂覆于烧结体的表面，并以850℃的温度扩散5-15h，之后冷却至室温，再以460～560℃的温度进行低温回火处理1～3h。
实施例2～10和对比例1～3中的钕铁硼磁体材料的制备方法中的参数与实施例1相同。其中，实施例4和8中按照表1中的配方将除R2和需要在晶界扩散中添加的Cu以外的原料进行熔炼和铸造。
3、成分测定：对实施例1～10和对比例1～3中的钕铁硼磁体材料使用高频电感耦合等离子体发射光谱仪(ICP-OES)进行测定。测试结果如下表2所示。
表2钕铁硼磁体材料的组分和含量(wt％)
Figure PCTCN2021077172-appb-000003
注：“/”是指不含有该元素。wt％为质量百分比。
效果实施例1
实施例1～9和对比例1～3中钕铁硼磁体材料进行如下检测：
1、磁性能测试：烧结磁铁使用英国Hirs公司的PFM-14磁性能测量仪进行磁性能检测，检测的磁性能包括20℃和120℃时的剩磁、20℃和120℃时的矫顽力、以及相应的剩磁温度系数。其中，计算剩磁温度系数的公式为：(Br 高温-Br 常温)/(Br 常温(高温-常温))×100％，测试结果如下表3所示。
2、FE-EPMA检测：对钕铁硼磁体材料的垂直取向面进行抛光，采用场发射电子探针显微分析仪(FE-EPMA)(日本电子株式会社(JEOL)，8530F)检测。测试晶界三角区的面积占比、二颗粒晶界的连续性、C、O的质量占比以及新物相。
二颗粒晶界的连续性根据EPMA的背散射图片计算得；C、O在二颗粒晶界和晶界三角区的质量占比及新物相是通过EPMA的元素分析测得。
晶界三角区的面积占比(％)指的是：晶界三角区的面积与“晶粒和晶界”总面积之比。
二颗粒晶界的连续性(％)的是：晶界中除空洞外的物相占据的长度(物相例如为富B相、富稀土相、稀土氧化物、稀土碳化物等)与总晶界长度的比值。
晶界三角区中C、O的质量占比(％)指的是：晶界三角区中C和O的质量与晶界中所有元素的总质量的比。
二颗粒晶界中C、O的质量占比(％)指的是：二颗粒晶界中C和O的质量与晶界中所有元素的总质量的比。
新物相在二颗粒晶界中的面积占比(％)指的是：二颗粒晶界中新物相的面积占二颗粒晶界总面积的比。
表3
Figure PCTCN2021077172-appb-000004
Figure PCTCN2021077172-appb-000005
注：“×”指的是二颗粒晶界相中不含化学组成为R xFe 100-x-y-zCu yM z的新物相。
由上述表3可知：本发明在添加少量重稀土元素且不添加Co元素，即可达到与目前添加大量的Co以及重稀土元素相当的水平。另外，由于晶界的稀土含量高，C和O更多的分布在晶界中，并分别是以稀土碳化物和稀土氧化物的形式存在。根据实施例1～10中“晶界三角区中C和O的质量占比”减去“二颗粒晶界中C和O的质量占比(％)”的差值相比对比例1～3均缩小，可得到杂相(稀土碳化物和稀土氧化物)从晶界三角区迁移到二颗粒晶界的结论，这从机理上解释了二颗粒晶界连续性的提升原因。
效果实施例2
如图1所示，为实施例4制得的钕铁硼磁体材料的EPMA微观结构图。图中箭头1所指的点为二颗粒晶界(浅灰色区域)中包含的R xFe 100-x-y-zCu yM z新物相，箭头2所指的位置为晶界三角区(银白色区域)，箭头3所指的位置为Nd 2Fe l4B主相(深灰色区域)。结合表3的数据可进一步看出晶界三角区的面积小于常规的磁体材料。

Claims (10)

  1. 一种钕铁硼磁体材料的原料组合物，其特征在于，其包括如下质量含量的组分：
    R：28～33％；所述R为稀土元素，R包括R1和R2，所述R1为熔炼时添加的稀土元素，所述R1包括Nd和Dy；所述R2为晶界扩散时添加的稀土元素，所述R2包括Tb，所述R2的含量为0.2～1％；
    M：≤0.4％、但不为0，所述M为Bi、Sn、Zn、Ga、In、Au和Pb中的一种或多种；
    Cu：≤0.15％、但不为0；
    B：0.9～1.1％；
    Fe：60～70％；
    所述原料组合物中不含Co；百分比为各组分质量占所述原料组合物总质量的质量百分比。
  2. 如权利要求1所述的原料组合物，其特征在于，所述R的含量为29.5～32.6％，较佳地为29.5～31％，百分比为占所述原料组合物总质量的质量百分比；
    和/或，所述原料组合物的R1中，所述Nd的含量为28.5～32.5％，较佳地为28.5～31％，百分比为占所述原料组合物总质量的质量百分比；
    和/或，所述原料组合物的R1中，所述Dy的含量在0.3％以下、但不为0，较佳地为0.05～0.2％，百分比为占所述原料组合物总质量的质量百分比；
    和/或，所述R1还包括Pr、Ho、Tb、Gd和Y中的一种或多种；
    其中，当所述R1包含Pr时，Pr的添加形式较佳地为以PrNd的形式，或者，以纯Pr和纯Nd的混合物的形式，或者，以“PrNd、纯Pr和纯Nd的混合物”联合添加；当以PrNd的形式添加时，Pr：Nd较佳地为25:75或20：80；当以纯净的Pr和Nd的混合物的形式或以PrNd、纯净的Pr和Nd的混合物联合添加时，所述Pr的含量较佳地为0.1～2wt％，其中百分比为占所述原料组合物总质量的质量百分比；
    其中，当所述的R1包含Ho时，所述Ho的含量较佳地为0.1～0.2％，百 分比为占所述原料组合物总质量的质量百分比；
    其中，当所述的R1包含Gd时，所述Gd的含量较佳地为0.1～0.2％，百分比为占所述原料组合物总质量的质量百分比；
    其中，当所述的R1包含Y时，所述Y的含量较佳地为0.1～0.2％，百分比为占所述原料组合物总质量的质量百分比；
    和/或，所述R2的含量为0.2～0.9％，百分比为占所述原料组合物总质量的质量百分比；
    和/或，所述R2中，Tb的含量为0.2％～1％，较佳地为0.5～1％，百分比为占所述原料组合物总质量的质量百分比；
    和/或，所述原料组合物中，所述R2还包括Pr和/或Dy；
    其中，当所述的R2包含Pr时，所述Pr的含量较佳地为0.2％以下、但不为0，百分比为占所述原料组合物总质量的质量百分比；
    其中，当所述R2包含Dy时，所述Dy的含量较佳地为0.3％以下、但不为0，百分比为占所述原料组合物总质量的质量百分比；
    和/或，所述M的含量在0.35％以下、但不为0，较佳地为0.01～0.35％，百分比为占所述原料组合物总质量的质量百分比；
    和/或，所述M的种类为Zn、Ga和Bi中的一种或多种；
    其中，当所述M包含Ga时，所述Ga的含量较佳地在0.35％以下、但不为0，更佳地为0.1～0.35％，百分比为占所述原料组合物总质量的质量百分比；
    其中，当所述M包含Zn时，所述Zn的含量较佳地在0.35％以下、但不为0，更佳地为0.05～0.25％，百分比为占所述原料组合物总质量的质量百分比；
    其中，当所述M包含Bi时，所述Bi的含量较佳地在0.35％以下、但不为0，更佳地为0.05～0.15％，百分比为占所述原料组合物总质量的质量百分比；
    和/或，所述Cu的含量为0.03～0.15％，或者，所述Cu的含量在0.08％ 以下、但不为0，百分比为占所述原料组合物总质量的质量百分比；
    和/或，所述Cu的添加方式包括在熔炼时添加和/或在晶界扩散时添加；
    其中，当所述Cu在晶界扩散时添加，所述晶界扩散时添加的Cu的含量较佳地为0.03～0.15％，百分比为占所述原料组合物总质量的质量百分比；当所述Cu在晶界扩散时添加，所述Cu较佳地以PrCu合金的形式添加；其中所述Cu与所述PrCu的质量百分比较佳地为0.1～17％；
    和/或，所述B的含量为0.97～1.05％，百分比为占所述原料组合物总质量的质量百分比；
    和/或，所述Fe的含量为65～69.5％，百分比为占所述原料组合物总质量的质量百分比；
    和/或，所述原料组合物中还包括Al；所述Al的含量较佳地在0.3％以下、但不为0，更佳地为0.03～0.2％，百分比为占所述原料组合物总质量的质量百分比；
    其中，当所述M包含Ga，且Ga≤0.01％时，较佳地，M元素的组成中Al+Ga+Cu≤0.11％，百分比为占所述原料组合物总质量的质量百分比。
  3. 如权利要求1或2所述的原料组合物，其特征在于，所述钕铁硼磁体材料的原料组合物包括如下质量含量的组分：R：29.5～32.6％；R包括R1和R2，所述R1包括Nd和Dy，所述R1为熔炼时添加的稀土元素，所述R2的含量为0.2～0.9％，所述R2包括Tb，所述R2为晶界扩散时添加的稀土元素；M：0.35％以下、但不为0，所述M为Zn、Ga和Bi中的一种或多种；Cu：0.05～0.15％；B：0.97～1.05％；Fe：65～69.5％，所述原组合物中不含Co；百分比为各组分含量占所述原料组合物总质量的质量百分比；
    或者，所述钕铁硼磁体材料的原料组合物包括如下质量含量的组分：R：29.5～31％；R包括R1和R2，所述R1包括Nd和Dy，所述R1为熔炼时添加的稀土元素，所述R2的含量为0.2～0.8％，所述R2包括Tb，所述R2为晶界扩散时添加的稀土元素；M：0.1～0.35％，所述M为Zn、Ga和Bi中的一种或多种；Cu：0.08％以下、但不为0；B：0.97～1.05％；Fe：65～69.5％， 所述原料组合物中不含Co；百分比为各组分含量占所述原料组合物总质量的质量百分比。
  4. 一种钕铁硼磁体材料的制备方法，其采用如权利要求1～3中任一项所述的原料组合物进行，所述制备方法为扩散制法，其中，R1元素在熔炼步骤中添加，R2元素在晶界扩散步骤中添加。
  5. 如权利要求4所述的制备方法，其特征在于，所述制备方法包括如下步骤：将所述钕铁硼磁体材料的原料组合物中除R2以外的元素经熔炼、制粉、成型、烧结得烧结体，再将所述的烧结体与所述R2的混合物经晶界扩散即可；
    其中，所述熔炼的操作较佳地为将所述钕铁硼磁体材料中除R2以外的元素采用铸锭工艺和速凝片工艺进行熔炼浇铸，得到合金片；
    所述熔炼的温度较佳地为1300～1700℃，更佳地为1450～1550℃；
    其中，所述制粉较佳地包括氢破制粉和/或气流磨制粉；
    所述氢破制粉较佳地包括吸氢、脱氢和冷却处理；所述吸氢的温度较佳地为20～200℃；所述脱氢的温度较佳地为400～650℃，更佳地为500～550℃；所述吸氢的压力较佳地为50～600kPa；
    所述气流磨制粉较佳地在0.1～2MPa，更佳地在0.5～0.7MPa的条件下进行气流磨制粉；所述气流磨制粉中的气流较佳地为氮气；所述气流磨制粉的时间较佳地为2～4h；
    其中，所述成型较佳地为磁场成型法，所述的磁场成型法的磁场强度为1.5T以上；
    其中，所述烧结较佳地在真空度低于0.5Pa的条件下进行；
    所述烧结的温度较佳地为1000～1200℃，更佳地为1030-1090℃；
    所述烧结的时间较佳地为0.5～10h，更佳地为2-5h；
    其中，在所述的晶界扩散之前较佳地还包括所述R2的涂覆操作；
    所述R2较佳地以氟化物或低熔点合金的形式涂覆，例如Tb的氟化物；当还包含Dy时，较佳地，Dy以Dy的氟化物的形式涂覆；
    当还包含Pr时，较佳地，Pr以PrCu合金的形式添加；
    当所述R2包含Pr且Pr以PrCu合金的形式参与晶界扩散时，较佳地，所述PrCu合金中，所述Cu与所述PrCu合金的质量比较佳地为0.1～17％；较佳地，所述Cu在所述制备方法中的添加时机为晶界扩散步骤，或者在熔炼步骤和晶界扩散步骤同时添加；
    其中，所述晶界扩散的温度较佳地为800～1000℃；
    所述晶界扩散的时间较佳地为5～20h，更佳地为5～15h；
    其中，所述晶界扩散之后，较佳地还进行低温回火处理；低温回火处理的温度较佳地为460～560℃；低温回火处理的时间较佳地为1～3h。
  6. 一种由如权利要求4或5所述的制备方法制得的钕铁硼磁体材料。
  7. 一种钕铁硼磁体材料，其特征在于，其包括如下质量含量的组分：R：28～33％；所述R包括R1和R2，所述R1包括Nd和Dy，所述R2包括Tb；R2的含量为0.2％～1％；
    M：≤0.4％、但不为0，所述M为Bi、Sn、Zn、Ga、In、Au和Pb中的一种或多种；
    Cu：≤0.15％、但不为0；
    B：0.9～1.1％；
    Fe：60～70％；
    所述钕铁硼磁体材料中不含Co；百分比为各组分质量占所述钕铁硼磁体材料总质量的质量百分比；
    所述钕铁硼磁体材料包含Nd 2Fe l4B晶粒和其壳层、邻接所述Nd 2Fe l4B晶粒的二颗粒晶界和晶界三角区，其中R1中的重稀土元素分布在Nd 2Fe l4B晶粒，R2主要分布在所述壳层、二颗粒晶界和晶界三角区，所述晶界三角区面积占比为2～3.12％；所述二颗粒晶界的晶界连续性为96％以上；所述晶界三角区中C和O的质量占比为0.4～0.5％，所述二颗粒晶界中C和O的质量占比为0.3～0.4％。
  8. 如权利要求7所述的钕铁硼磁体材料，其特征在于，所述晶界三角区 面积占比为2.07～2.84％，较佳地在2.07～2.6％；
    和/或，所述晶界连续性为97％以上，较佳地为在98％以上；
    和/或，所述晶界三角区中C和O的质量占比为0.41～0.48％，较佳地为0.41～0.46％；
    和/或，所述二颗粒晶界中C和O的质量占比为为0.32～0.39％，较佳地为0.34～0.39％；
    和/或，所述二颗粒晶界中还含有化学组成为R xFe 100-x-y-zCu yM z的物相；其中R包括Nd、Dy和Tb中的一种或多种，所述M为Bi、Sn、Zn、Ga、In、Au和Pb中的一种或多种x为78～80；y为0.8～1.5；z为0.1以下，但不为0；其中，x较佳地为78.1～79.5，y较佳地为0.99～1.33，z较佳地为0.26～0.38；
    其中，所述二颗粒晶界中，所述新物相的面积与所述二颗粒晶界总面积的比较佳地为0.25～1.65％，更佳地为0.5～1.65％；
    和/或，所述钕铁硼磁体材料中，所述R的含量为29.5～32.6％，较佳地为29.5～31％，百分比为占所述钕铁硼磁体材料总质量的质量百分比；
    和/或，所述钕铁硼磁体材料的R1中，所述Nd的含量为28.5～32.5％，较佳地为28.5～31％，百分比为占所述钕铁硼磁体材料总质量的质量百分比；
    和/或，所述钕铁硼磁体材料的R1中，所述Dy的含量在0.3％以下、但不为0，较佳地为0.05～0.2％，百分比为占所述钕铁硼磁体材料总质量的质量百分比；
    和/或，所述R1还包括Pr、Ho、Tb、Gd和Y中的一种或多种；
    其中，当所述R1包含Pr时，Pr的添加形式较佳地为以PrNd的形式，或者，以纯Pr和纯Nd的混合物的形式，或者，以“PrNd、纯Pr和纯Nd的混合物”联合添加；当以PrNd的形式添加时，Pr：Nd较佳地为25:75或20：80；当以纯净的Pr和Nd的混合物的形式或以PrNd、纯净的Pr和Nd的混合物联合添加时，所述Pr的含量较佳地为0.1～2wt％，其中百分比为占所述钕铁硼磁体材料总质量的质量百分比；
    其中，当所述的R1包含Ho时，所述Ho的含量较佳地为0.1～0.2％，百 分比为占所述钕铁硼磁体材料总质量的质量百分比；
    其中，当所述的R1包含Gd时，所述Gd的含量较佳地为0.1～0.2％，百分比为占所述钕铁硼磁体材料总质量的质量百分比；
    其中，当所述的R1包含Y时，所述Y的含量较佳地为0.1～0.2％，百分比为占所述钕铁硼磁体材料总质量的质量百分比；
    和/或，所述R2的含量为0.2～0.9％，百分比为占所述钕铁硼磁体材料总质量的质量百分比；
    和/或，所述R2中，Tb的含量为0.2％～1％，较佳地为0.5～1％，百分比为占所述钕铁硼磁体材料总质量的质量百分比；
    和/或，所述钕铁硼磁体材料中，所述R2还包括Pr和/或Dy；
    其中，当所述的R2包含Pr时，所述Pr的含量较佳地为0.2％以下、但不为0，百分比为占所述钕铁硼磁体材料总质量的质量百分比；
    其中，当所述R2包含Dy时，所述Dy的含量为0.3％以下、但不为0，百分比为占所述钕铁硼磁体材料总质量的质量百分比；
    和/或，所述M的含量在0.35％以下、但不为0，较佳地为0.01～0.35％，百分比为占所述钕铁硼磁体材料总质量的质量百分比；
    和/或，述M的种类为Zn、Ga和Bi中的一种或多种；
    其中，当所述M包含Ga时，所述Ga的含量较佳地在0.35％以下、但不为0，更佳地为0.1～0.35％，百分比为占所述钕铁硼磁体材料总质量的质量百分比；
    其中，当所述M包含Zn时，所述Zn的含量较佳地在0.35％以下、但不为0，更佳地为0.05～0.25％，百分比为占所述钕铁硼磁体材料总质量的质量百分比；
    其中，当所述M包含Bi时，所述Bi的含量较佳地在0.35％以下、但不为0，更佳地为0.05～0.15％，百分比为占所述钕铁硼磁体材料总质量的质量百分比；
    和/或，所述Cu的含量为0.03～0.15％，或者，所述Cu的含量在0.08％ 以下、但不为0，百分比为占所述钕铁硼磁体材料总质量的质量百分比；
    和/或，所述Cu的添加方式包括在熔炼时添加和/或在晶界扩散时添加；
    其中，当所述Cu在晶界扩散时添加，所述晶界扩散时添加的Cu的含量较佳地为0.03～0.15％，百分比为占所述钕铁硼磁体材料总质量的质量百分比；当所述Cu在晶界扩散时添加，所述Cu较佳地以PrCu合金的形式添加，其中所述Cu占所述PrCu的质量百分比较佳地为0.1～17％；
    和/或，所述B的含量为0.97～1.05％，百分比为占所述钕铁硼磁体材料总质量的质量百分比；
    和/或，所述Fe的含量为65～69.5％，百分比为占所述钕铁硼磁体材料总质量的质量百分比；
    和/或，所述钕铁硼磁体材料中还包括Al；所述Al的含量较佳地在0.3％以下、但不为0，更佳地为0.03～0.2％，百分比为占所述钕铁硼磁体材料总质量的质量百分比；
    其中，当所述M包含Ga，且Ga≤0.01％时，较佳地，M元素的组成中Al+Ga+Cu≤0.11％，百分比为占所述钕铁硼磁体材料总质量的质量百分比。
  9. 如权利要求7或8所述的钕铁硼磁体材料，其特征在于，所述钕铁硼磁体材料包括如下质量含量的组分：R：29.5～32.6％；R包括R1和R2，所述R1包括Nd和Dy，所述R1为熔炼时时添加的稀土元素，所述R2的含量为0.2～0.9％，所述R2包括Tb，所述R2为晶界扩散时添加的稀土元素；M：0.35％以下、但不为0，所述M为Zn、Ga和Bi中的一种或多种；Cu：0.05～0.15％；B：0.97～1.05％；Fe：65～69.5％，所述钕铁硼磁体材料中不含Co；百分比为各组分含量占所述钕铁硼磁体材料总质量的质量百分比；所述钕铁硼磁体材料包含Nd 2Fe l4B晶粒和其壳层、邻接所述Nd 2Fe l4B晶粒的二颗粒晶界和晶界三角区，其中R1中的重稀土元素分布在Nd 2Fe l4B晶粒，R2主要分布在所述壳层、二颗粒晶界和晶界三角区，所述晶界三角区面积占比为2～2.84％；所述钕铁硼磁体材料的晶界连续性为97％以上；所述晶界三角区中C和O的质量占比为0.41～0.48％；所述二颗粒晶界中C和O的质量占 比为0.32～0.39％；所述二颗粒晶界中含有新物相，所述新物相的化学组成为：R xFe 100-x-y-zCu yM z，其中，R xFe 100-x-y-zCu yM z中的R包括Nd、Dy和Tb中的一种或多种，所述M为Bi、Sn、Zn、Ga、In、Au和Pb中的一种或多种；x为78.1～79.5，y为0.99～1.33，z为0.26～0.38；所述新物相在所述二颗粒晶界中的面积与所述二颗粒晶界总面积的比为0.25～1.65％；
    或者，所述钕铁硼磁体材料包括如下质量含量的组分：R：29.5～31％；R包括R1和R2，所述R1包括Nd和Dy，所述R1为熔炼时添加的稀土元素，所述R2的含量为0.2～0.8％，所述R2包括Tb，所述R2为晶界扩散时添加的稀土元素；M：0.01～0.35％，所述M为Zn、Ga和Bi中的一种或多种；Cu：0.08％以下、但不为0；B：0.97～1.05％；Fe：65～69.5％，所述钕铁硼磁体材料中不含Co；百分比为各组分含量占所述钕铁硼磁体材料总质量的质量百分比；所述钕铁硼磁体材料包含Nd 2Fe l4B晶粒和其壳层、邻接所述Nd 2Fe l4B晶粒的二颗粒晶界和晶界三角区，其中R1中的重稀土元素分布在Nd 2Fe l4B晶粒，R2主要分布在所述壳层、二颗粒晶界和晶界三角区，所述晶界三角区面积占比为2～2.6％；所述钕铁硼磁体材料的晶界连续性为98％以上；所述晶界三角区中C和O的质量占比为0.41～0.46％；所述二颗粒晶界中C和O的质量占比为0.32～0.39％；所述二颗粒晶界中含有新物相，所述新物相的化学组成为：R xFe 100-x-y-zCu yM z，其中，R xFe 100-x-y-zCu yM z中的R包括Nd、Dy和Tb中的一种或多种，所述M为Bi、Zn、和Ga中的一种或多种；x为78.1～79.5，y为0.99～1.33，z为0.26～0.38；所述新物相在所述二颗粒晶界中的面积与所述二颗粒晶界总面积的比为0.5～1.65％。
  10. 一种如权利要求6～9中任一项所述的钕铁硼磁体材料在制备磁钢中的应用；所述磁钢较佳地为54SH、54UH、56SH高性能磁钢。
PCT/CN2021/077172 2020-02-26 2021-02-22 一种钕铁硼磁体材料、原料组合物及制备方法和应用 WO2021169887A1 (zh)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2022545011A JP7342281B2 (ja) 2020-02-26 2021-02-22 ネオジム鉄ホウ素磁石材料、原料組成物及び製造方法、並びに応用
EP21761557.4A EP4113544A4 (en) 2020-02-26 2021-02-22 NEODYMIUM-IRON-BORONIC MAGNETIC MATERIAL, RAW MATERIAL COMPOSITION, PROCESS FOR THEIR PRODUCTION AND ITS USE
KR1020227024167A KR102631761B1 (ko) 2020-02-26 2021-02-22 네오디뮴철붕소 자성체 재료, 원료조성물과 제조방법 및 응용
US17/785,041 US20230023534A1 (en) 2020-02-26 2021-02-22 Neodymium-iron-boron magnet material, raw material composition preparation method therefor and use thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202010121472.8A CN111243807B (zh) 2020-02-26 2020-02-26 一种钕铁硼磁体材料、原料组合物及制备方法和应用
CN202010121472.8 2020-02-26

Publications (1)

Publication Number Publication Date
WO2021169887A1 true WO2021169887A1 (zh) 2021-09-02

Family

ID=70871497

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2021/077172 WO2021169887A1 (zh) 2020-02-26 2021-02-22 一种钕铁硼磁体材料、原料组合物及制备方法和应用

Country Status (6)

Country Link
US (1) US20230023534A1 (zh)
EP (1) EP4113544A4 (zh)
JP (1) JP7342281B2 (zh)
KR (1) KR102631761B1 (zh)
CN (1) CN111243807B (zh)
WO (1) WO2021169887A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114196864A (zh) * 2021-11-25 2022-03-18 江苏大学 一种Y-Gd基合金及包括该基合金的钕铈铁硼磁体与制备方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111243807B (zh) * 2020-02-26 2021-08-27 厦门钨业股份有限公司 一种钕铁硼磁体材料、原料组合物及制备方法和应用
US20210366635A1 (en) * 2020-05-19 2021-11-25 Shin-Etsu Chemical Co., Ltd. Rare earth sintered magnet and making method
CN112768168B (zh) * 2020-12-25 2023-05-30 福建省长汀金龙稀土有限公司 一种钕铁硼材料及其制备方法
CN112735717B (zh) * 2020-12-25 2023-08-01 福建省长汀金龙稀土有限公司 一种钕铁硼材料及其制备方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5645651A (en) 1982-08-21 1997-07-08 Sumitomo Special Metals Co., Ltd. Magnetic materials and permanent magnets
CN103890868A (zh) * 2011-10-28 2014-06-25 Tdk株式会社 R-t-b系烧结磁铁
US20140326363A1 (en) * 2011-09-09 2014-11-06 Toda Kogyo Corp. R-t-b-based rare earth magnet particles, process for producing the r-t-b-based rare earth magnet particles, and bonded magnet
CN106920669A (zh) * 2015-12-25 2017-07-04 天津三环乐喜新材料有限公司 一种R-Fe-B系烧结磁体的制备方法
CN109964290A (zh) * 2017-01-31 2019-07-02 日立金属株式会社 R－t－b系烧结磁体的制造方法
CN110265201A (zh) * 2018-03-12 2019-09-20 Tdk株式会社 R-t-b系永久磁铁
CN110571007A (zh) 2019-09-03 2019-12-13 厦门钨业股份有限公司 一种稀土永磁材料、原料组合物、制备方法、应用、电机
CN111243807A (zh) * 2020-02-26 2020-06-05 厦门钨业股份有限公司 一种钕铁硼磁体材料、原料组合物及制备方法和应用

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MY142024A (en) * 2005-03-23 2010-08-16 Shinetsu Chemical Co Rare earth permanent magnet
JP4895027B2 (ja) * 2006-03-27 2012-03-14 Ｔｄｋ株式会社 Ｒ−ｔ−ｂ系焼結磁石及びｒ−ｔ−ｂ系焼結磁石の製造方法
CN101266856A (zh) * 2007-12-28 2008-09-17 烟台正海磁性材料有限公司 耐蚀性优异的高性能R-Fe-B系烧结磁体及其制造方法
JP5288277B2 (ja) * 2009-08-28 2013-09-11 日立金属株式会社 Ｒ−ｔ−ｂ系永久磁石の製造方法
JP6037128B2 (ja) * 2013-03-13 2016-11-30 戸田工業株式会社 Ｒ−ｔ−ｂ系希土類磁石粉末、ｒ−ｔ−ｂ系希土類磁石粉末の製造方法、及びボンド磁石
JP6303480B2 (ja) * 2013-03-28 2018-04-04 Tdk株式会社 希土類磁石
CN103258633B (zh) * 2013-05-30 2015-10-28 烟台正海磁性材料股份有限公司 一种R-Fe-B系烧结磁体的制备方法
WO2015037041A1 (ja) * 2013-09-13 2015-03-19 株式会社 東芝 永久磁石、モータ、および発電機
CN103745823A (zh) * 2014-01-24 2014-04-23 烟台正海磁性材料股份有限公司 一种R-Fe-B系烧结磁体的制备方法
JP6582940B2 (ja) * 2015-03-25 2019-10-02 Tdk株式会社 Ｒ−ｔ−ｂ系希土類焼結磁石及びその製造方法
CN106328367B (zh) * 2016-08-31 2017-11-24 烟台正海磁性材料股份有限公司 一种R‑Fe‑B系烧结磁体的制备方法
CN106158347B (zh) * 2016-08-31 2017-10-17 烟台正海磁性材料股份有限公司 一种制备R‑Fe‑B类烧结磁体的方法
JP6743650B2 (ja) * 2016-10-27 2020-08-19 日立金属株式会社 Ｒ−ｔ−ｂ系焼結磁石の製造方法
CN108962524B (zh) * 2018-06-08 2020-11-17 深圳市瑞达美磁业有限公司 一种烧结取向磁体渗透处理用组合物、用途及方法
CN108899149A (zh) * 2018-08-29 2018-11-27 南京理工大学 一种重稀土Dy高效扩散制备高矫顽力钕铁硼磁体的方法
JP7167673B2 (ja) * 2018-12-03 2022-11-09 Tdk株式会社 Ｒ‐ｔ‐ｂ系永久磁石の製造方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5645651A (en) 1982-08-21 1997-07-08 Sumitomo Special Metals Co., Ltd. Magnetic materials and permanent magnets
US20140326363A1 (en) * 2011-09-09 2014-11-06 Toda Kogyo Corp. R-t-b-based rare earth magnet particles, process for producing the r-t-b-based rare earth magnet particles, and bonded magnet
CN103890868A (zh) * 2011-10-28 2014-06-25 Tdk株式会社 R-t-b系烧结磁铁
CN106920669A (zh) * 2015-12-25 2017-07-04 天津三环乐喜新材料有限公司 一种R-Fe-B系烧结磁体的制备方法
CN109964290A (zh) * 2017-01-31 2019-07-02 日立金属株式会社 R－t－b系烧结磁体的制造方法
CN110265201A (zh) * 2018-03-12 2019-09-20 Tdk株式会社 R-t-b系永久磁铁
CN110571007A (zh) 2019-09-03 2019-12-13 厦门钨业股份有限公司 一种稀土永磁材料、原料组合物、制备方法、应用、电机
CN111243807A (zh) * 2020-02-26 2020-06-05 厦门钨业股份有限公司 一种钕铁硼磁体材料、原料组合物及制备方法和应用

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4113544A4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114196864A (zh) * 2021-11-25 2022-03-18 江苏大学 一种Y-Gd基合金及包括该基合金的钕铈铁硼磁体与制备方法

Also Published As

Publication number Publication date
CN111243807A (zh) 2020-06-05
KR20220108182A (ko) 2022-08-02
US20230023534A1 (en) 2023-01-26
CN111243807B (zh) 2021-08-27
JP7342281B2 (ja) 2023-09-11
JP2023508229A (ja) 2023-03-01
EP4113544A1 (en) 2023-01-04
EP4113544A4 (en) 2023-08-16
KR102631761B1 (ko) 2024-01-31

Similar Documents

Publication Publication Date Title
JP7220330B2 (ja) Ｒ－ｔ－ｂ系永久磁石材料、製造方法、並びに応用
WO2021169887A1 (zh) 一种钕铁硼磁体材料、原料组合物及制备方法和应用
WO2021169886A1 (zh) 一种钕铁硼磁体材料、原料组合物及制备方法和应用
WO2021169893A1 (zh) 一种钕铁硼磁体材料、原料组合物及制备方法和应用
WO2021169891A1 (zh) 钕铁硼磁体材料、原料组合物、制备方法、应用
WO2021169888A1 (zh) 钕铁硼磁体材料、原料组合物及制备方法和应用
WO2021169890A1 (zh) 钕铁硼磁体材料、原料组合物、制备方法、应用
WO2021169889A1 (zh) 钕铁硼磁体材料、原料组合物、制备方法、应用
WO2021244315A1 (zh) 钕铁硼磁体材料、原料组合物及其制备方法和应用
WO2021218701A1 (zh) 一种钕铁硼磁体材料、原料组合物及制备方法、应用
WO2021244311A1 (zh) 钕铁硼磁体材料、原料组合物及其制备方法和应用
WO2021169892A1 (zh) 钕铁硼磁体材料、原料组合物、制备方法、应用
WO2021218699A1 (zh) 钕铁硼磁体材料、原料组合物、制备方法、应用
WO2021218700A1 (zh) 钕铁硼磁体材料、原料组合物及其制备方法和应用
CN108806911B (zh) 一种钕铁硼磁体及其制备方法
TWI776781B (zh) 一種雙殼層釹鐵硼磁體及其製備方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 21761557

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 20227024167

Country of ref document: KR

Kind code of ref document: A

ENP Entry into the national phase

Ref document number: 2022545011

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2021761557

Country of ref document: EP

Effective date: 20220926