WO2021244318A1 - 一种r-t-b系永磁材料、原料组合物及其制备方法和应用 - Google Patents

一种r-t-b系永磁材料、原料组合物及其制备方法和应用 Download PDF

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WO2021244318A1
WO2021244318A1 PCT/CN2021/095089 CN2021095089W WO2021244318A1 WO 2021244318 A1 WO2021244318 A1 WO 2021244318A1 CN 2021095089 W CN2021095089 W CN 2021095089W WO 2021244318 A1 WO2021244318 A1 WO 2021244318A1
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rare earth
permanent magnet
percentage
rtb
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French (fr)
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蓝琴
黄佳莹
张艳艳
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厦门钨业股份有限公司
福建省长汀金龙稀土有限公司
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    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
    • H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
    • H01F1/0576—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together pressed, e.g. hot working
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    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
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    • C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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    • C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
    • H—ELECTRICITY
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    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
    • H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
    • H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
    • H—ELECTRICITY
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    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • 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

Definitions

  • the invention relates to an R-T-B series permanent magnet material, a raw material composition, and a preparation method and application thereof.
  • the Nd-Fe-B permanent magnet 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.
  • Co is the most used and most effective element. This is because the addition of Co can reduce the temperature coefficient of the reversible temperature coefficient of magnetic induction, effectively increase the Curie temperature, and can improve the corrosion resistance of the Nd-Fe-B magnet.
  • the addition of Co easily causes a sharp drop in remanence.
  • the added Co is contained not only in the main phase but also in the grain boundary phase, the problem of reduced mechanical strength occurs, and the cost of Co is high.
  • JP2002075717A adds Zr to the Cu-containing RTB rare earth permanent magnet, which makes the RTB rare earth containing Co, Al, Cu and containing Zr, Nb or Hf
  • the fine ZrB compound, NbB compound or HfB compound (hereinafter referred to as MB compound) in the permanent magnet-like magnets are uniformly dispersed and precipitated.
  • the average particle size of the MB compound is 5 ⁇ m or less, and the maximum interval between the MB compounds is 50 ⁇ m or less.
  • JPWO2004030000A1 also adds Zr to the RTB-based rare earth permanent magnet, which uses a double alloy method to make the product of enrichment of Zr in the R 2 T 14 B main phase, and clearly points out that if there is enrichment only in the grain boundary phase The product of Zr cannot solve its technical problems.
  • the technical problem to be solved by the present invention is to overcome the technical problem in the prior art that the RTB-based permanent magnetic material increases the Curie temperature and coercive force by adding Co, while Co faces the expensive defect, and provides an RTB Series permanent magnet materials, raw material compositions, and preparation methods and applications thereof.
  • the present invention does not add or control the content of trace Co, while controlling the content of Cu and Zr elements, the obtained R-T-B series permanent magnet material has the advantages of good squareness, good high temperature performance and excellent mechanical performance.
  • the present invention provides a raw material composition of R-T-B series permanent magnet material, which contains the following components in terms of mass percentage:
  • R 29.5-32%, said R is a rare earth element containing at least Nd, and the content of Pr is 0-17%;
  • the M is one or more of Al, Ga, Ti, Nb, Hf, Si, Sn, Ge, Ag, Au, Bi and Mn;
  • the percentage is the mass percentage of the total mass of the raw material composition of the R-T-B permanent magnet material, and the sum of the contents of each component is 100%.
  • the R may be a rare earth element added during a smelting process and/or a diffusion process, for example, a rare earth element added during a smelting process.
  • the content of R is, for example, 29.8%, 30.5%, 30.6%, 30.7%, 30.8%, 31%, 31.5%, 31.6% or 32%, where the percentage is It is the percentage of the total mass of the raw material composition of the RTB-based permanent magnet material.
  • the Nd content can be conventional in the art, preferably 23.1% to 29.7%, such as 23.1%, 23.6%, 24.3%, 25%, 25.2%, 29% or 29.7% %, where the percentage is the percentage of the total mass of the raw material composition of the RTB-based permanent magnet material.
  • the addition form of Nd in the R can be conventional in the art, for example, in the form of PrNd, or in the form of pure Nd, or in the form of pure Pr and Nd. In the form of a mixture of PrNd, or a combination of PrNd, pure Pr and Nd.
  • the mass ratio of Pr to Nd in PrNd is preferably 25:75, 20:80 or 10:90.
  • the content of Pr is preferably 0-10%, more preferably 0-8%, such as 0, 2.2%, 5.5%, 6.1%, 7.4% or 7.9% , Where the percentage is the percentage of the total mass of the raw material composition of the RTB-based permanent magnet material.
  • the addition form of Pr can be conventional in the art, for example, in the form of PrNd, or in the form of pure Pr, or in the form of pure Pr. In the form of a mixture of Pr and Nd, or a combination of PrNd, pure Pr and Nd.
  • the mass ratio of Pr to Nd in PrNd is preferably 25:75, 20:80 or 10:90.
  • the R may further include a heavy rare earth element.
  • the heavy rare earth element may be a heavy rare earth element added in a smelting process and/or a diffusion process.
  • the heavy rare earth element is a heavy rare earth element added in a smelting process.
  • the type of the heavy rare earth element may be a conventional heavy rare earth type in the art, such as one or more of Dy, Tb, Gd, and Ho.
  • the content of the heavy rare earth elements can be conventional in the art, preferably 0-7% (excluding 0), and more preferably It is 0.1-0.5%, such as 0.1, 0.2%, 0.3% or 0.5%, where the percentage is the percentage of the total mass of the raw material composition of the RTB-based permanent magnet material.
  • the content of the Zr is, for example, 0.15%, 0.2%, 0.3%, 0.35%, or 0.5%, wherein the percentage is the raw material composition of the RTB-based permanent magnet material Percentage of total mass.
  • the content of Cu is, for example, 0.35%, 0.4%, or 0.55%, where the percentage is the percentage of the total mass of the raw material composition of the R-T-B permanent magnetic material.
  • the content of Co is, for example, 0, 0.1% or 0.3%, where the percentage is the percentage of the total mass of the raw material composition of the R-T-B permanent magnetic material.
  • the content of B is, for example, 0.95%, 0.98%, or 1.05%, wherein the percentage is the percentage of the total mass of the raw material composition of the R-T-B permanent magnetic material.
  • the type of M is preferably one or more of Al, Ga, Ti, Nb, and Hf.
  • the content of M is preferably 0-2%, such as 0, 0.07%, 0.08%, 0.1%, 0.75%, 0.58%, 0.7%, 0.9% or 1.2 %, where the percentage is the percentage of the total mass of the raw material composition of the RTB-based permanent magnet material.
  • the content of Al is preferably 0-1% (excluding 0), such as 0.02%, 0.03%, 0.48%, 0.5% Or 0.55%, where the percentage is the percentage of the total mass of the raw material composition of the RTB-based permanent magnet material.
  • the content of Ga is preferably 0-1% (excluding 0), such as 0.05%, 0.1%, 0.2%, or 0.4% , Where the percentage is the percentage of the total mass of the raw material composition of the RTB-based permanent magnet material.
  • the content of Ti is preferably 0.05-0.3%, for example, 0.05%, 0.1%, or 0.3%, where the percentage is based on the RTB It is the percentage of the total mass of the raw material composition of the permanent magnet material.
  • the content of the Nb is preferably 0-0.2% (not including 0), for example, 0.05%, where the percentage is the percentage of the RTB-based permanent magnet material.
  • the content of the Hf is preferably 0-0.2% (not including 0), for example, 0.05%, wherein the percentage is the percentage of the RTB-based permanent magnet material.
  • the definitions of certain components can be as follows, and the definitions of the remaining components are as described in any of the above schemes: the R does not contain Tb.
  • the definitions of some components can be as follows, and the definitions of the remaining components are as described in any of the above schemes: the R does not contain Dy and Tb Other heavy rare earth elements.
  • the definitions of some components can be as follows, and the definitions of other components are as described in any of the above schemes: the R does not contain Ho.
  • the definitions of certain components can be as follows, and the definitions of other components are as described in any of the above schemes: except for unavoidable impurities,
  • the R does not contain rare earth metals other than Nd and Pr.
  • the definition of some components in the raw material composition of the R-T-B permanent magnet material, can be as follows, and the definition of the other components is as described in any of the above schemes: the content of Co is zero.
  • the definitions of certain components can be as follows, and the definitions of the remaining components are as described in any of the above schemes: the content of Co is 0- 0.3% (excluding 0), such as 0.1% or 0.3%, where the percentage is the percentage of the total mass of the raw material composition of the RTB-based permanent magnet material.
  • the M is one or more of Al, Ga, Ti, Nb, and Hf; the content of Al is ⁇ 0.55%; the percentage refers to the mass of the total mass of the raw material composition of the RTB-based permanent magnet material percentage.
  • the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Ga is less than 0.2%; the content of Al is 0.45%-0.54%; the percentage refers to the percentage of the RTB It is the mass percentage of the total mass of the raw material composition of the permanent magnet material.
  • the content of Zr is ⁇ 0.35%; the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Ga is 0.2-0.25%; the content of Al is 0.45%- 0.54%; percentage refers to the mass percentage of the total mass of the raw material composition of the RTB-based permanent magnet material.
  • the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Ga is> 0.25%; the content of Al is 0.45%-0.54%; the content of Ti is ⁇ 0.15% or >0.28%; percentage refers to the mass percentage of the total mass of the raw material composition of the RTB-based permanent magnet material.
  • the R does not contain Tb; the M is one or more of Al, Ga, Ti, Nb, and Hf; the content of Al is less than 0.04%; the percentage refers to the raw material of the RTB-based permanent magnet material The mass percentage of the total mass of the composition.
  • the R contains Tb; the M is one or more of Al, Ga, Ti, Nb, and Hf; the content of Al is less than 0.04%; Al+Cu is greater than or equal to 0.55%; the percentage refers to the proportion of the RTB It is the mass percentage of the total mass of the raw material composition of the permanent magnet material.
  • the R contains Tb; the Zr content is greater than or equal to 0.26%; the M is one or more of Al, Ga, Ti, Nb, and Hf; the Al content is less than 0.04%; the percentage refers to the total The mass percentage of the total mass of the raw material composition of the RTB-based permanent magnet material.
  • the R contains Tb; the Ga content is ⁇ 0.05% or >0.25%; the M is one or more of Al, Ga, Ti, Nb, and Hf; the Al content is ⁇ 0.04%; It refers to the mass percentage of the total mass of the raw material composition of the RTB-based permanent magnet material.
  • the raw material composition of the R-T-B permanent magnet material in terms of mass percentage, contains the following components:
  • R 29.5-32%, said R is a rare earth element containing at least Nd, and the content of Pr is 0-17%;
  • M 0-3%, the M is one or more of Al, Ga, Ti, Nb and Hf;
  • the percentage is the mass percentage of the total mass of the raw material composition of the R-T-B permanent magnet material, and the sum of the contents of each component is 100%.
  • the raw material composition of the RTB-based permanent magnet material can be any one of the following numbers 1-10, wherein the percentage is each component accounting for the raw material composition of the RTB-based permanent magnet material The mass percentage of the total mass, the sum of the content of each component is 100%,
  • the present invention also provides a method for preparing the R-T-B series permanent magnet material, which can be achieved by subjecting the raw material composition of the R-T-B series permanent magnet material to smelting, powdering, molding, sintering and aging treatments.
  • the smelting operation and conditions may be conventional smelting processes in the field.
  • the raw material composition of the RTB-based permanent magnet material is made by ingot casting process and quick-setting flake process. Smelting and casting are performed to obtain alloy flakes.
  • an additional 0-0.3wt% rare earth element ( Generally Nd element), the percentage is the weight percentage of the content of the additional rare earth element to the total content of the raw material composition; in addition, the content of this part of the additional rare earth element is not included in the category of the raw material composition.
  • the melting temperature may be 1300-1600°C.
  • the smelting equipment is generally a high frequency vacuum melting furnace and/or an intermediate frequency vacuum melting furnace.
  • the intermediate frequency vacuum melting furnace is, for example, an intermediate frequency vacuum induction rapid-solidifying belt spinning furnace.
  • the operation and conditions of the powder milling can be conventional powder milling processes in the field, and generally include hydrogen crushing powder milling and/or jet milling powder milling.
  • the hydrogen crushing and pulverizing generally includes hydrogen absorption, dehydrogenation and cooling treatment.
  • the temperature of the hydrogen absorption is generally 20-200°C.
  • the temperature of the dehydrogenation is generally 400-650°C.
  • the pressure of the hydrogen absorption is generally 50-600 kPa.
  • the pressure of the pulverizing chamber of the jet mill is generally 0.1-2 MPa.
  • the gas stream in the gas stream milling powder can be, for example, nitrogen gas and/or argon gas.
  • the efficiency of the jet milling powder may vary according to different equipment, for example, it may be 30-400 kg/h, preferably 200 kg/h.
  • the molding operation and conditions can be conventional molding processes in the art.
  • the magnetic field forming method In the preparation method of the R-T-B series permanent magnet material, the molding operation and conditions can be conventional molding processes in the art.
  • 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 operation and conditions of the sintering treatment may be a conventional sintering process in the field, such as a vacuum sintering process and/or an inert atmosphere sintering process.
  • the vacuum sintering process or the inert atmosphere sintering process are conventional operations in the art.
  • an inert atmosphere sintering process is used, the initial stage of sintering can be performed under the condition of a vacuum degree of less than 5 ⁇ 10 -1 Pa.
  • the inert atmosphere may be an atmosphere containing inert gas conventional in the art, such as helium or argon.
  • the temperature of the sintering treatment may be 1000-1200°C, preferably 1030-1090°C.
  • the sintering treatment time may be 0.5-10h, preferably 2-8h.
  • the temperature of the aging treatment may be 450°C-600°C, for example, 480-510°C.
  • the time of the aging treatment may be 1 to 4 hours, for example, 1 to 3 hours.
  • a grain boundary diffusion treatment is also performed.
  • the grain boundary diffusion treatment can be processed according to a conventional process in the art, for example, the surface of the sintered body obtained by the sintering process is vapor-deposited, coated, or sputtered to attach a substance containing Tb and/or a substance containing Dy. Substances can be subjected to diffusion heat treatment.
  • the Tb-containing substance may be Tb metal, Tb-containing compound (for example, Tb-containing fluoride), or alloy.
  • the substance containing Dy may be Dy metal, a compound containing Dy (for example, a fluoride containing Dy), or an alloy.
  • the temperature of the diffusion heat treatment may be 800-900°C, such as 850°C.
  • the time of the diffusion heat treatment may be 12-48h, such as 24h.
  • the raw material composition of the above-mentioned R-T-B series permanent magnetic material can also be prepared by using a two-phase alloy process to prepare the R-T-B series permanent magnetic material.
  • the dual-phase alloy process can be conventional in the art.
  • the present invention also provides an R-T-B series permanent magnet material prepared by the above-mentioned preparation method.
  • the present invention also provides a R-T-B series permanent magnet material, which contains the following components in terms of mass percentage:
  • R 29.5-32%, said R is a rare earth element containing at least Nd, and the content of Pr is 0-17%;
  • the M is one or more of Al, Ga, Ti, Nb, Hf, Si, Sn, Ge, Ag, Au, Bi and Mn;
  • the percentage is the mass percentage of the total mass of the R-T-B permanent magnet material, and the sum of the content of each component is 100%.
  • Cu and M basically do not enter the main phase, and are mainly distributed at the grain boundary, which replaces part of Fe in the grain boundary.
  • an enriched phase is generated at the grain boundary.
  • the enriched phase helps optimize grain boundary defects, thereby increasing the coercivity of the magnet, improving squareness, and improving high-temperature performance.
  • Co will not be enriched in the grain boundaries, thereby inhibiting intergranular fracture and improving mechanical properties.
  • the R may be a rare earth element added in a smelting process and/or a diffusion process, for example, a rare earth element added in a smelting process.
  • the content of R is, for example, 29.8%, 30.5%, 30.6%, 30.7%, 30.8%, 31%, 31.5%, 31.6% or 32%, wherein the percentage is the percentage of the RTB It is the percentage of the total mass of the permanent magnet material.
  • the Nd content can be conventional in the art, preferably 23.1% to 29.7%, such as 23.1%, 23.6%, 24.3%, 25%, 25.2%, 29% or 29.7%, where the percentage It is a percentage of the total mass of the RTB-based permanent magnet material.
  • the addition form of Nd in the R can be conventional in the art, for example, in the form of PrNd, or in the form of pure Nd, or in the form of a mixture of pure Pr and Nd , Or combined with a mixture of PrNd, pure Pr and Nd.
  • the mass ratio of Pr to Nd in PrNd is preferably 25:75, 20:80 or 10:90.
  • the content of Pr is preferably 0-10%, more preferably 0-8%, such as 0, 2.2%, 5.5%, 6.1%, 7.4% or 7.9%, where the percentage is It accounts for the percentage of the total mass of the RTB-based permanent magnet material.
  • the addition form of Pr can be conventional in the art, for example, in the form of PrNd, or in the form of pure Pr, or in the form of pure Pr and Nd. In the form of a mixture of PrNd, or a combination of PrNd, pure Pr and Nd.
  • the mass ratio of Pr to Nd in PrNd is preferably 25:75, 20:80 or 10:90.
  • the R may further include a heavy rare earth element.
  • the heavy rare earth element may be a heavy rare earth element added in a smelting process and/or a diffusion process.
  • the heavy rare earth element is a heavy rare earth element added in a smelting process.
  • the type of the heavy rare earth element may be a conventional type of heavy rare earth in the art, such as one or more of Dy, Tb, Gd, and Ho.
  • the content of the heavy rare earth elements can be conventional in the art, preferably 0-7% (excluding 0), and more preferably 0.1-0.5 %, such as 0.1, 0.2%, 0.3% or 0.5%, where the percentage is the percentage of the total mass of the RTB-based permanent magnet material.
  • the content of the Zr is, for example, 0.15%, 0.2%, 0.3%, 0.35% or 0.5%, wherein the percentage is a percentage of the total mass of the R-T-B series permanent magnetic material.
  • the content of Cu is, for example, 0.35%, 0.4%, or 0.55%, where the percentage is a percentage of the total mass of the R-T-B-based permanent magnetic material.
  • the content of Co is, for example, 0, 0.1% or 0.3%, where the percentage is a percentage of the total mass of the R-T-B-based permanent magnetic material.
  • the content of B is, for example, 0.95%, 0.98%, or 1.05%, where the percentage is a percentage of the total mass of the R-T-B-based permanent magnetic material.
  • the type of M is preferably one or more of Al, Ga, Ti, Nb, and Hf.
  • the content of M is preferably 0-2%, such as 0, 0.07%, 0.08%, 0.1%, 0.75%, 0.58%, 0.7%, 0.9% or 1.2%, where the percentage It is a percentage of the total mass of the RTB-based permanent magnet material.
  • the content of Al is preferably 0-1% (excluding 0), such as 0.02%, 0.03%, 0.48%, 0.5% or 0.55%,
  • the percentage is the percentage of the total mass of the RTB-based permanent magnet material.
  • the content of Ga is preferably 0-1% (excluding 0), such as 0.05%, 0.1%, 0.2% or 0.4%, where the percentage is It accounts for the percentage of the total mass of the RTB-based permanent magnet material.
  • the content of Ti is preferably 0.05-0.3%, such as 0.05%, 0.1%, or 0.3%, where the percentage is based on the RTB-based permanent magnetic material Percentage of total mass.
  • the Nb content is preferably 0-0.2% (not including 0), for example, 0.05%, where the percentage is the total of the RTB-based permanent magnetic material Percentage of quality.
  • the content of the Hf is preferably 0-0.2% (not including 0), for example, 0.05%, where the percentage is based on the total of the RTB-based permanent magnetic material Percentage of quality.
  • the definitions of some components can be as follows, and the definitions of other components are as described in any of the above schemes: the R does not contain Tb.
  • the definitions of certain components can be as follows, and the definitions of other components are as described in any of the above schemes: the R does not contain heavy rare earths other than Dy and Tb element.
  • the definitions of certain components can be as follows, and the definitions of other components are as described in any of the above schemes: the R does not contain Ho.
  • the definitions of certain components can be as follows, and the definitions of other components are as described in any of the above schemes: Except for unavoidable impurities, the R does not contain Rare earth metals other than Nd and Pr.
  • the definition of some components can be as follows, and the definition of the other components is as described in any of the above schemes: the content of Co is zero.
  • the definition of certain components can be as follows, and the definition of the remaining components is as described in any of the above schemes: the content of Co is 0-0.3% (not Contains 0), such as 0.1% or 0.3%, where the percentage is the percentage of the total mass of the RTB-based permanent magnet material.
  • the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Al is ⁇ 0.55%; and the percentage refers to the mass percentage of the total mass of the R-T-B permanent magnet material.
  • the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Ga is less than 0.2%; the content of Al is 0.45%-0.54%; the percentage refers to the percentage of the RTB It is the mass percentage of the total mass of the permanent magnet material.
  • the content of Zr is ⁇ 0.35%; the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Ga is 0.2-0.25%; the content of Al is 0.45%- 0.54%; percentage refers to the mass percentage of the total mass of the RTB-based permanent magnet material.
  • the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Ga is> 0.25%; the content of Al is 0.45%-0.54%; the content of Ti is ⁇ 0.15% or >0.28%; percentage refers to the mass percentage of the total mass of the RTB-based permanent magnet material.
  • the R does not contain Tb; the M is one or more of Al, Ga, Ti, Nb, and Hf; the content of Al is less than 0.04%; the percentage refers to the total mass of the RTB-based permanent magnet material The percentage of mass.
  • the R contains Tb; the M is one or more of Al, Ga, Ti, Nb, and Hf; the content of Al is less than 0.04%; Al+Cu is greater than or equal to 0.55%; the percentage refers to the proportion of the RTB It is the mass percentage of the total mass of the permanent magnet material.
  • the R contains Tb; the Zr content is greater than or equal to 0.26%; the M is one or more of Al, Ga, Ti, Nb, and Hf; the Al content is less than 0.04%; the percentage refers to the total
  • the RTB is the mass percentage of the total mass of permanent magnet materials.
  • the R contains Tb; the Ga content is ⁇ 0.05% or >0.25%; the M is one or more of Al, Ga, Ti, Nb, and Hf; the Al content is ⁇ 0.04%; It refers to the mass percentage of the total mass of the RTB-based permanent magnet material.
  • the R-T-B series permanent magnet material in terms of mass percentage, contains the following components:
  • R 29.5-32%, said R is a rare earth element containing at least Nd, and the content of Pr is 0-17%;
  • M 0-3%, the M is one or more of Al, Ga, Ti, Nb and Hf;
  • the percentage is the mass percentage of the total mass of the R-T-B permanent magnet material, and the sum of the content of each component is 100%.
  • the RTB-based permanent magnet material can be any one of the following numbers 1-12, wherein the percentage is the mass percentage of each component in the total mass of the RTB-based permanent magnet material, and each group The sum of the sub-content is 100%,
  • the present invention also provides an application of the above-mentioned R-T-B series permanent magnetic material as an electronic component.
  • carbon impurities are generally inevitably introduced in the preparation process, and the amount is generally 0-0.10%.
  • the above-mentioned percentage is the mass percentage of the amount of C element in the total amount.
  • percentage refers to mass percentage
  • the reagents and raw materials used in the present invention are all commercially available.
  • the positive progress effect of the present invention lies in: controlling the content of Cu and Zr at the same time, and there is a Zr-rich R p -(Zr x ,Cu y ,M z ) q -Fe 100-pq enriched phase at the grain boundary.
  • the phase helps high-temperature sintering and refines the grain structure, thereby increasing the coercivity of the magnet (H cj ⁇ 16.3kOe), improving the squareness (H k /H cj ⁇ 0.98), and improving the high-temperature performance (Hcj temperature at 80°C)
  • Co since the content of trace Co is not added or controlled, Co will not be enriched in the grain boundaries, thereby inhibiting intergranular fracture and improving the mechanical properties (flexural strength ⁇ 469MPa).
  • FIG. 1 is the FE-EPMA spectrum of the R-T-B series permanent magnetic material prepared in Example 9.
  • Airflow milling process Under the nitrogen atmosphere, the hydrogen crushed powder is pulverized by airflow under the condition of 0.65MPa in the crushing chamber (the efficiency of airflow milling may vary depending on the equipment. For example, it can be 200kg/h) 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 2-8 hours to obtain a sintered body.
  • the sintered body obtained by the sintering treatment in Example 5 was first subjected to grain boundary diffusion treatment, and then subjected to aging treatment. The remaining steps are the same as in Example 5.
  • the grain boundary diffusion treatment process is as follows:
  • the sintered body is processed into a magnet with a thickness of 20mm ⁇ 20mm and a sheet thickness of less than 7mm.
  • the thickness direction is the direction of the magnetic field orientation.
  • raw materials prepared from Dy fluoride are used to spray the magnet on the entire surface.
  • the magnet is dried, it is then subjected to diffusion heat treatment at a temperature of 850°C for 24 hours in a high-purity Ar atmosphere. Cool to room temperature.
  • the sintered body obtained by the sintering treatment in Example 2 was firstly subjected to a grain boundary diffusion treatment, and then subjected to an aging treatment. The remaining steps are the same as in Example 2.
  • the grain boundary diffusion treatment process is as follows:
  • the sintered body is processed into a magnet with a thickness of 20mm ⁇ 20mm and a sheet thickness of less than 7mm.
  • the thickness direction is the direction of the magnetic field orientation.
  • raw materials prepared from Dy fluoride are used to spray the magnet on the entire surface.
  • the magnet is dried, it is then subjected to diffusion heat treatment at a temperature of 850°C for 24 hours in a high-purity Ar atmosphere. Cool to room temperature.
  • Each component of the R-T-B series permanent magnetic material is measured using a high-frequency inductively coupled plasma emission spectrometer (ICP-OES, instrument model: Icap6300). Table 2 below shows the component test results. Taking Example 1 as an example, the types and amounts of elements detected from the R-T-B permanent magnet material are the same as those of the raw material composition disclosed in Table 1.
  • R-T-B series permanent magnet material universal testing machine is used to test the bending strength.
  • the size of the test sample is 20mm ⁇ 7.5mm ⁇ 6.5mm, and 6.5mm is the orientation direction.
  • FIG. 1 The RTB-based permanent magnet material prepared in Example 9 was subjected to FE-EPMA test, and the results are shown in Fig. 1 and Table 4.
  • Figure 1 respectively corresponds to the concentration distribution of Zr and Cu. It can be seen from Figure 1 that there is a Zr-rich phase at the grain boundary, and the content of Cu in the Zr-rich phase is higher than its content in the main phase. The position of arrow 1 in Fig. 1 is the main phase, and the arrow 2 in Fig. 1 is the Zr-rich phase. It can be seen from Table 4 that in the Zr-rich phase, the amount of rare earth is about 18.39 at%, and the ratio of Zr to Cu is 0.9.
  • the content of Cu and Zr is controlled at the same time, and the obtained RTB permanent magnet material has excellent magnetic properties: B r ⁇ 14.09kGs, H cj ⁇ 16.3kOe; H k /H cj ⁇ 0.98; Hcj temperature at 80°C
  • the absolute value of the coefficient is ⁇ 0.738; the absolute value of the Hcj temperature coefficient is ⁇ 0.425 at 150°C.

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Abstract

提供了一种R-T-B系永磁材料、原料组合物及其制备方法和应用。R-T-B系永磁材料的原料组合物，以质量百分比计，其包含下述组分：R，29.5-32％，R为至少包含Nd的稀土元素，并且，Pr的含量为0-17％；Zr，0.15-0.50％；Cu，0.35-0.55％；Co，0-0.3％；M，0-3％，M为Al、Ga、Ti、Nb、Hf、Si、Sn、Ge、Ag、Au、Bi和Mn中的一种或多种；B，0.95-1.05％；Fe，64-70％；百分比为占R-T-B系永磁材料的原料组合物总质量的质量百分比，各组分含量之和为100％。R-T-B系永磁材料具有方形度佳、高温性能好及机械性能优异的优势。

Description

一种R-T-B系永磁材料、原料组合物及其制备方法和应用 技术领域
本发明涉及一种R-T-B系永磁材料、原料组合物及其制备方法和应用。
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。
现有技术中，在制作耐热、耐蚀型烧结Nd-Fe-B磁体时，Co是用得最多而且最有效的元素。这是因为添加Co能够降低磁感可逆温度系数温度系数，有效提高居里温度，并且可以提高Nd-Fe-B磁体抗腐蚀性能。但是，Co的加入容易造成剩磁急剧下降，同时，由于所添加的Co不仅包含于主相，还包含于晶界相，从而产生使机械强度降低的问题，并且Co的成本较高。
为了提高磁特性、抑制晶粒长大并改善烧结温度幅度，JP2002075717A在含有Cu的R-T-B系稀土类永久磁铁中添加Zr，其使含有Co、Al、Cu并含有Zr、Nb或Hf的R-T-B系稀土类永久磁铁中细微的ZrB化合物、NbB化合物或HfB化合物(以下称M-B化合物)均匀分散的析出来，其中，M-B化合物的平均粒径在5μm以下，M-B化合物之间的最大间隔在50μm以下。JPWO2004030000A1同样在R-T-B系稀土类永久磁铁中添加Zr，其通过双合金的方法使R 2T 14B主相内存在富集Zr的生成物，并且明确指出，若仅在晶界相内存在富集Zr的生成物，则无法解决其技术问题。
发明内容
本发明的所要解决的技术问题在于克服现有技术中R-T-B系永磁材料通过添加Co来提高居里温度和矫顽力、而Co又面临价格昂贵的缺陷的技术 问题，而提供了一种R-T-B系永磁材料、原料组合物及其制备方法和应用。本发明不添加或控制微量Co含量，同时控制Cu、Zr元素的含量，得到的R-T-B系永磁材料具有方形度佳、高温性能好及机械性能优异的优势。
本发明提供了一种R-T-B系永磁材料的原料组合物，以质量百分比计，其包含下述组分：
R，29.5-32％，所述R为至少包含Nd的稀土元素，并且，Pr的含量为0-17％；
Zr，0.15-0.50％；
Cu，0.35-0.55％；
Co，0-0.3％；
M，0-3％，所述M为Al、Ga、Ti、Nb、Hf、Si、Sn、Ge、Ag、Au、Bi和Mn中的一种或多种；
B，0.95-1.05％；
Fe，64-70％；
百分比为占所述R-T-B系永磁材料的原料组合物总质量的质量百分比，各组分含量之和为100％。
所述R-T-B系永磁材料的原料组合物中，所述R可为熔炼工艺和/或扩散工艺中添加的稀土元素，例如为熔炼工艺中添加的稀土元素。
所述R-T-B系永磁材料的原料组合物中，所述R的含量例如为29.8％、30.5％、30.6％、30.7％、30.8％、31％、31.5％、31.6％或32％，其中百分比为占所述R-T-B系永磁材料的原料组合物总质量的百分比。
所述R-T-B系永磁材料的原料组合物中，所述Nd含量可为本领域常规，优选为23.1-29.7％，例如23.1％、23.6％、24.3％、25％、25.2％、29％或29.7％，其中百分比为占所述R-T-B系永磁材料的原料组合物总质量的百分比。
所述R-T-B系永磁材料的原料组合物中，所述R中的Nd的添加形式可为本领域常规，例如以PrNd的形式，或者，以纯净的Nd的形式，或者以纯净的Pr和Nd的混合物的形式，或者以PrNd、纯净的Pr和Nd的混合物 联合添加。当以PrNd的形式添加时，PrNd中Pr与Nd的质量比优选为25:75、20：80或10：90。
所述R-T-B系永磁材料的原料组合物中，所述Pr的含量优选为0-10％，进一步优选为0-8％，例如0、2.2％、5.5％、6.1％、7.4％或7.9％，其中百分比为占所述R-T-B系永磁材料的原料组合物总质量的百分比。
所述R-T-B系永磁材料的原料组合物中，当所述R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，以纯净的Pr的形式，或者，以纯净的Pr和Nd的混合物的形式，或者以PrNd、纯净的Pr和Nd的混合物联合添加。当以PrNd的形式添加时，PrNd中Pr与Nd的质量比优选为25:75、20：80或10：90。
所述R-T-B系永磁材料的原料组合物中，所述R还可包含重稀土元素。所述重稀土元素可为熔炼工艺和/或扩散工艺中添加的重稀土元素，较佳地，所述重稀土元素为熔炼工艺中添加的重稀土元素。
所述R-T-B系永磁材料的原料组合物中，所述重稀土元素的种类可为本领域常规的重稀土种类，例如Dy、Tb、Gd和Ho中的一种或多种。
所述R-T-B系永磁材料的原料组合物中，当所述R包含重稀土元素时，所述重稀土元素的含量可为本领域常规，优选为0-7％(不包含0)，进一步优选为0.1-0.5％，例如0.1、0.2％、0.3％或0.5％，其中百分比为占所述R-T-B系永磁材料的原料组合物总质量的百分比。
所述R-T-B系永磁材料的原料组合物中，所述Zr的含量例如为0.15％、0.2％、0.3％、0.35％或0.5％，其中百分比为占所述R-T-B系永磁材料的原料组合物总质量的百分比。
所述R-T-B系永磁材料的原料组合物中，所述Cu的含量例如为0.35％、0.4％或0.55％，其中百分比为占所述R-T-B系永磁材料的原料组合物总质量的百分比。
所述R-T-B系永磁材料的原料组合物中，所述Co的含量例如为0、0.1％或0.3％，其中百分比为占所述R-T-B系永磁材料的原料组合物总质量的百 分比。
所述R-T-B系永磁材料的原料组合物中，所述B的含量例如为0.95％、0.98％或1.05％，其中百分比为占所述R-T-B系永磁材料的原料组合物总质量的百分比。
所述R-T-B系永磁材料的原料组合物中，所述M的种类优选为Al、Ga、Ti、Nb和Hf中的一种或多种。
所述R-T-B系永磁材料的原料组合物中，所述M的含量优选为0-2％，例如0、0.07％、0.08％、0.1％、0.75％、0.58％、0.7％、0.9％或1.2％，其中百分比为占所述R-T-B系永磁材料的原料组合物总质量的百分比。
所述R-T-B系永磁材料的原料组合物中，当所述M包含Al时，所述Al的含量优选为0-1％(不包含0)，例如0.02％、0.03％、0.48％、0.5％或0.55％，其中百分比为占所述R-T-B系永磁材料的原料组合物总质量的百分比。
所述R-T-B系永磁材料的原料组合物中，当所述M包含Ga时，所述Ga的含量优选为0-1％(不包含0)，例如0.05％、0.1％、0.2％或0.4％，其中百分比为占所述R-T-B系永磁材料的原料组合物总质量的百分比。
所述R-T-B系永磁材料的原料组合物中，当所述M包含Ti时，所述Ti的含量优选为0.05-0.3％，例如0.05％、0.1％或0.3％，其中百分比为占所述R-T-B系永磁材料的原料组合物总质量的百分比。
所述R-T-B系永磁材料的原料组合物中，当所述M包含Nb时，所述Nb的含量优选为0-0.2％(不包含0)，例如0.05％，其中百分比为占所述R-T-B系永磁材料的原料组合物总质量的百分比。
所述R-T-B系永磁材料的原料组合物中，当所述M包含Hf时，所述Hf的含量优选为0-0.2％(不包含0)，例如0.05％，其中百分比为占所述R-T-B系永磁材料的原料组合物总质量的百分比。
在某一方案中，所述R-T-B系永磁料的原料组合物中，某些组分的定义可如下所述，其余组分的定义如上任一方案所述：所述R不包含Tb。
在某一方案中，所述R-T-B系永磁材料的原料组合物中，某些组分的定 义可如下所述，其余组分的定义如上任一方案所述：所述R不包含Dy和Tb以外的重稀土元素。
在某一方案中，所述R-T-B系永磁材料的原料组合物中，某些组分的定义可如下所述，其余组分的定义如上任一方案所述：所述R不包含Ho。
在某一方案中，所述R-T-B系永磁材料的原料组合物中，某些组分的定义可如下所述，其余组分的定义如上任一方案所述：除不可避免的杂质以外，所述R不含Nd和Pr以外的稀土金属。
在某一方案中，所述R-T-B系永磁材料的原料组合物中，某些组分的定义可如下所述，其余组分的定义如上任一方案所述：所述Co的含量为0。
在某一方案中，所述R-T-B系永磁材料的原料组合物中，某些组分的定义可如下所述，其余组分的定义如上任一方案所述：所述Co的含量为0-0.3％(不包含0)，例如0.1％或0.3％，其中百分比为占所述R-T-B系永磁材料的原料组合物总质量的百分比。
在某一方案中，所述R-T-B系永磁材料的原料组合物中，某些组分的定义可如下所述，其余组分的定义如上任一方案所述：
所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Al的含量为≥0.55％；百分比是指占所述R-T-B系永磁材料的原料组合物总质量的质量百分比。
在某一方案中，所述R-T-B系永磁材料的原料组合物中，某些组分的定义可如下所述，其余组分的定义如上任一方案所述：
所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Ga的含量为＜0.2％；所述Al的含量为0.45％-0.54％；百分比是指占所述R-T-B系永磁材料的原料组合物总质量的质量百分比。
在某一方案中，所述R-T-B系永磁材料的原料组合物中，某些组分的定义可如下所述，其余组分的定义如上任一方案所述：
所述Zr的含量≥0.35％；所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Ga的含量为0.2-0.25％；所述Al的含量为0.45％-0.54％；百分比是指占所述R-T-B系永磁材料的原料组合物总质量的质量百分比。
在某一方案中，所述R-T-B系永磁材料的原料组合物中，某些组分的定义可如下所述，其余组分的定义如上任一方案所述：
所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Ga的含量为＞0.25％；所述Al的含量为0.45％-0.54％；所述Ti的含量为＜0.15％或＞0.28％；百分比是指占所述R-T-B系永磁材料的原料组合物总质量的质量百分比。
在某一方案中，所述R-T-B系永磁材料的原料组合物中，某些组分的定义可如下所述，其余组分的定义如上任一方案所述：
所述R不含Tb；所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Al的含量<0.04％；百分比是指占所述R-T-B系永磁材料的原料组合物总质量的质量百分比。
在某一方案中，所述R-T-B系永磁材料的原料组合物中，某些组分的定义可如下所述，其余组分的定义如上任一方案所述：
所述R含Tb；所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Al的含量<0.04％；Al+Cu≥0.55％；百分比是指占所述R-T-B系永磁材料的原料组合物总质量的质量百分比。
在某一方案中，所述R-T-B系永磁材料的原料组合物中，某些组分的定义可如下所述，其余组分的定义如上任一方案所述：
所述R含Tb；所述Zr的含量≥0.26％；所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Al的含量<0.04％；百分比是指占所述R-T-B系永磁材料的原料组合物总质量的质量百分比。
在某一方案中，所述R-T-B系永磁材料的原料组合物中，某些组分的定义可如下所述，其余组分的定义如上任一方案所述：
所述R包含Tb；所述Ga的含量＜0.05％或＞0.25％；所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Al的含量<0.04％；百分比是指占所述R-T-B系永磁材料的原料组合物总质量的质量百分比。
在某一方案中，所述R-T-B系永磁材料的原料组合物，以质量百分比计，其包含下述组分：
R，29.5-32％，所述R为至少包含Nd的稀土元素，并且，Pr的含量为0-17％；
Zr，0.15-0.50％；
Cu，0.35-0.55％；
Co，0-0.3％；
M，0-3％，所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；
B，0.95-1.05％；
Fe，64-70％；
百分比为占所述R-T-B系永磁材料的原料组合物总质量的质量百分比，各组分含量之和为100％。
在某一方案中，所述R-T-B系永磁材料的原料组合物可为下述编号1-10中的任意一种，其中，百分比为各组分占所述R-T-B系永磁材料的原料组合物总质量的质量百分比，各组分含量之和为100％，
Figure PCTCN2021095089-appb-000001
“/”是指不含有该元素。
本发明还提供了一种R-T-B系永磁材料的制备方法，将上述R-T-B系永磁材料的原料组合物经熔炼、制粉、成型、烧结处理和时效处理，即可。
所述R-T-B系永磁材料的制备方法中，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R-T-B系永磁材料的原料组合物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，一般会在熔炼过程中在原料组合物的配方基础中额外添加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含量占所述原料组合物的总含量的重量百分比；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R-T-B系永磁材料的制备方法中，所述熔炼的温度可为1300-1600℃。
所述R-T-B系永磁材料的制备方法中，所述熔炼的设备一般为高频真空熔炼炉和/或中频真空熔炼炉，所述中频真空熔炼炉例如中频真空感应速凝甩带炉。
所述R-T-B系永磁材料的制备方法中，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℃。所述吸氢的压力一般为50-600kPa。
所述气流磨制粉磨室压力一般在0.1-2MPa。所述气流磨制粉中的气流例如可为氮气和/或氩气。所述气流磨制粉的效率可根据设备不同有所差别，例如可为30-400kg/h，优选200kg/h。
所述R-T-B系永磁材料的制备方法中，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。
所述R-T-B系永磁材料的制备方法中，所述烧结处理的操作和条件可为本领域常规的烧结工艺，例如真空烧结工艺和/或惰性气氛烧结工艺。所述真空烧结工艺或所述惰性气氛烧结工艺均为本领域常规操作。当采用惰性气氛烧结工艺时，烧结开始阶段可在真空度低于5×10 -1Pa的条件下进行。所述惰性气氛可为本领域常规的含有惰性气体的气氛，例如氦气、氩气。
所述R-T-B系永磁材料的制备方法中，所述烧结处理的温度可为1000-1200℃，较佳地为1030-1090℃。
所述R-T-B系永磁材料的制备方法中，所述烧结处理的时间可为0.5-10h，较佳地为2-8h。
所述R-T-B系永磁材料的制备方法中，所述时效处理的温度可为450℃-600℃,例如480-510℃。
所述R-T-B系永磁材料的制备方法中，所述时效处理的时间可为1-4h，例如1-3h。
其中，较佳地，所述烧结处理之后、所述时效处理之前，还进行晶界扩散处理。
其中，所述晶界扩散处理可按本领域常规的工艺进行处理，例如，在所述烧结处理得到的烧结体的表面蒸镀、涂覆或溅射附着含有Tb的物质和/或含有Dy的物质，经扩散热处理，即可。
所述晶界扩散处理中，所述含有Tb的物质可为Tb金属、含有Tb的化合物(例如含有Tb的氟化物)或合金。
所述晶界扩散处理中，所述含有Dy的物质可为Dy金属、含有Dy的化合物(例如含有Dy的氟化物)或合金。
所述晶界扩散处理中，所述扩散热处理的温度可为800-900℃，例如850℃。
所述晶界扩散处理中，所述扩散热处理的时间可为12-48h，例如24h。
除上述制备方法外，还可将上述R-T-B系永磁材料的原料组合物采用双相合金工艺制备R-T-B系永磁材料。所述双相合金工艺可为本领域常规。
本发明还提供了一种由如上所述的制备方法制得的R-T-B系永磁材料。
本发明还提供了一种R-T-B系永磁材料，以质量百分比计，其包含下述组分：
R，29.5-32％，所述R为至少包含Nd的稀土元素，并且，Pr的含量为0-17％；
Zr，0.15-0.50％；
Cu，0.35-0.55％；
Co，0-0.3％；
M，0-3％，所述M为Al、Ga、Ti、Nb、Hf、Si、Sn、Ge、Ag、Au、Bi和Mn中的一种或多种；
B，0.95-1.05％；
Fe，64-70％；
百分比为占所述R-T-B系永磁材料总质量的质量百分比，各组分含量之和为100％。
所述R-T-B系永磁材料中Cu和M基本不进入主相，主要分布在晶界处，会在晶界中取代部分Fe。通过控制R、B、Zr和Cu的含量，在晶界处生成富集相，该富集相有助于优化晶界缺陷，从而提升磁体矫顽力，改善方形度，高温性能得到改善。同时，由于不添加或控制微量Co含量，Co不会在晶界中富集，从而抑制沿晶断裂，提高了机械性能。所述富集相的组成为R p-(Zr x,Cu y,M z) q-Fe 100-p-q，其中：R为至少包含Nd的稀土元素；M为Ga、Al、Ti、Nb、Hf、Si、Sn、Ge、Ag、Au、Bi和Mn中的一种或多种；p、q、x、y及z满足下述条件：15≤p≤25(at％)；4≤q≤12(at％)；x/(y+z)＝0.7-1.2，at％为原子百分比。
所述R-T-B系永磁材料中，所述R可为熔炼工艺和/或扩散工艺中添加的稀土元素，例如为熔炼工艺中添加的稀土元素。
所述R-T-B系永磁材料中，所述R的含量例如为29.8％、30.5％、30.6％、30.7％、30.8％、31％、31.5％、31.6％或32％，其中百分比为占所述R-T-B系永磁材料总质量的百分比。
所述R-T-B系永磁材料中，所述Nd含量可为本领域常规，优选为23.1-29.7％，例如23.1％、23.6％、24.3％、25％、25.2％、29％或29.7％，其中百分比为占所述R-T-B系永磁材料总质量的百分比。
所述R-T-B系永磁材料中，所述R中的Nd的添加形式可为本领域常规，例如以PrNd的形式，或者，以纯净的Nd的形式，或者以纯净的Pr和Nd的混合物的形式，或者以PrNd、纯净的Pr和Nd的混合物联合添加。当以 PrNd的形式添加时，PrNd中Pr与Nd的质量比优选为25:75、20：80或10：90。
所述R-T-B系永磁材料中，所述Pr的含量优选为0-10％，进一步优选为0-8％，例如0、2.2％、5.5％、6.1％、7.4％或7.9％，其中百分比为占所述R-T-B系永磁材料总质量的百分比。
所述R-T-B系永磁材料中，当所述R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，以纯净的Pr的形式，或者，以纯净的Pr和Nd的混合物的形式，或者以PrNd、纯净的Pr和Nd的混合物联合添加。当以PrNd的形式添加时，PrNd中Pr与Nd的质量比优选为25:75、20：80或10：90。
所述R-T-B系永磁材料中，所述R还可包含重稀土元素。所述重稀土元素可为熔炼工艺和/或扩散工艺中添加的重稀土元素，较佳地，所述重稀土元素为熔炼工艺中添加的重稀土元素。
所述R-T-B系永磁材料中，所述重稀土元素的种类可为本领域常规的重稀土种类，例如Dy、Tb、Gd和Ho中的一种或多种。
所述R-T-B系永磁材料中，当所述R包含重稀土元素时，所述重稀土元素的含量可为本领域常规，优选为0-7％(不包含0)，进一步优选为0.1-0.5％，例如0.1、0.2％、0.3％或0.5％，其中百分比为占所述R-T-B系永磁材料总质量的百分比。
所述R-T-B系永磁材料中，所述Zr的含量例如为0.15％、0.2％、0.3％、0.35％或0.5％，其中百分比为占所述R-T-B系永磁材料总质量的百分比。
所述R-T-B系永磁材料中，所述Cu的含量例如为0.35％、0.4％或0.55％，其中百分比为占所述R-T-B系永磁材料总质量的百分比。
所述R-T-B系永磁材料中，所述Co的含量例如为0、0.1％或0.3％，其中百分比为占所述R-T-B系永磁材料总质量的百分比。
所述R-T-B系永磁材料中，所述B的含量例如为0.95％、0.98％或1.05％，其中百分比为占所述R-T-B系永磁材料总质量的百分比。
所述R-T-B系永磁材料中，所述M的种类优选为Al、Ga、Ti、Nb和Hf中的一种或多种。
所述R-T-B系永磁材料中，所述M的含量优选为0-2％，例如0、0.07％、0.08％、0.1％、0.75％、0.58％、0.7％、0.9％或1.2％，其中百分比为占所述R-T-B系永磁材料总质量的百分比。
所述R-T-B系永磁材料中，当所述M包含Al时，所述Al的含量优选为0-1％(不包含0)，例如0.02％、0.03％、0.48％、0.5％或0.55％，其中百分比为占所述R-T-B系永磁材料总质量的百分比。
所述R-T-B系永磁材料中，当所述M包含Ga时，所述Ga的含量优选为0-1％(不包含0)，例如0.05％、0.1％、0.2％或0.4％，其中百分比为占所述R-T-B系永磁材料总质量的百分比。
所述R-T-B系永磁材料中，当所述M包含Ti时，所述Ti的含量优选为0.05-0.3％，例如0.05％、0.1％或0.3％，其中百分比为占所述R-T-B系永磁材料总质量的百分比。
所述R-T-B系永磁材料中，当所述M包含Nb时，所述Nb的含量优选为0-0.2％(不包含0)，例如0.05％，其中百分比为占所述R-T-B系永磁材料总质量的百分比。
所述R-T-B系永磁材料中，当所述M包含Hf时，所述Hf的含量优选为0-0.2％(不包含0)，例如0.05％，其中百分比为占所述R-T-B系永磁材料总质量的百分比。
在某一方案中，所述R-T-B系永磁料中，某些组分的定义可如下所述，其余组分的定义如上任一方案所述：所述R不包含Tb。
在某一方案中，所述R-T-B系永磁材料中，某些组分的定义可如下所述，其余组分的定义如上任一方案所述：所述R不包含Dy和Tb以外的重稀土元素。
在某一方案中，所述R-T-B系永磁材料中，某些组分的定义可如下所述，其余组分的定义如上任一方案所述：所述R不包含Ho。
在某一方案中，所述R-T-B系永磁材料中，某些组分的定义可如下所述，其余组分的定义如上任一方案所述：除不可避免的杂质以外，所述R不含Nd和Pr以外的稀土金属。
在某一方案中，所述R-T-B系永磁材料中，某些组分的定义可如下所述，其余组分的定义如上任一方案所述：所述Co的含量为0。
在某一方案中，所述R-T-B系永磁材料中，某些组分的定义可如下所述，其余组分的定义如上任一方案所述：所述Co的含量为0-0.3％(不包含0)，例如0.1％或0.3％，其中百分比为占所述R-T-B系永磁材料总质量的百分比。
在某一方案中，所述R-T-B系永磁材料中，某些组分的定义可如下所述，其余组分的定义如上任一方案所述：
所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Al的含量为≥0.55％；百分比是指占所述R-T-B系永磁材料总质量的质量百分比。
在某一方案中，所述R-T-B系永磁材料中，某些组分的定义可如下所述，其余组分的定义如上任一方案所述：
所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Ga的含量为＜0.2％；所述Al的含量为0.45％-0.54％；百分比是指占所述R-T-B系永磁材料总质量的质量百分比。
在某一方案中，所述R-T-B系永磁材料中，某些组分的定义可如下所述，其余组分的定义如上任一方案所述：
所述Zr的含量≥0.35％；所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Ga的含量为0.2-0.25％；所述Al的含量为0.45％-0.54％；百分比是指占所述R-T-B系永磁材料总质量的质量百分比。
在某一方案中，所述R-T-B系永磁材料中，某些组分的定义可如下所述，其余组分的定义如上任一方案所述：
所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Ga的含量为＞0.25％；所述Al的含量为0.45％-0.54％；所述Ti的含量为＜0.15％或＞0.28％；百分比是指占所述R-T-B系永磁材料总质量的质量百分比。
在某一方案中，所述R-T-B系永磁材料中，某些组分的定义可如下所述，其余组分的定义如上任一方案所述：
所述R不含Tb；所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Al的含量<0.04％；百分比是指占所述R-T-B系永磁材料总质量的质量百分比。
在某一方案中，所述R-T-B系永磁材料中，某些组分的定义可如下所述，其余组分的定义如上任一方案所述：
所述R含Tb；所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Al的含量<0.04％；Al+Cu≥0.55％；百分比是指占所述R-T-B系永磁材料总质量的质量百分比。
在某一方案中，所述R-T-B系永磁材料中，某些组分的定义可如下所述，其余组分的定义如上任一方案所述：
所述R含Tb；所述Zr的含量≥0.26％；所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Al的含量<0.04％；百分比是指占所述R-T-B系永磁材料总质量的质量百分比。
在某一方案中，所述R-T-B系永磁材料中，某些组分的定义可如下所述，其余组分的定义如上任一方案所述：
所述R包含Tb；所述Ga的含量＜0.05％或＞0.25％；所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Al的含量<0.04％；百分比是指占所述R-T-B系永磁材料总质量的质量百分比。
在某一方案中，所述R-T-B系永磁材料，以质量百分比计，其包含下述组分：
R，29.5-32％，所述R为至少包含Nd的稀土元素，并且，Pr的含量为0-17％；
Zr，0.15-0.50％；
Cu，0.35-0.55％；
Co，0-0.3％；
M，0-3％，所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；
B，0.95-1.05％；
Fe，64-70％；
百分比为占所述R-T-B系永磁材料总质量的质量百分比，各组分含量之和为100％。
在某一方案中，所述R-T-B系永磁材料可为下述编号1-12中的任意一种，其中，百分比为各组分占所述R-T-B系永磁材料总质量的质量百分比，各组分含量之和为100％，
Figure PCTCN2021095089-appb-000002
“/”是指不含有该元素。
本发明还提供了一种如上所述的R-T-B系永磁材料作为电子元器件的应用。
本发明中，在制备工艺中一般会不可避免的引入碳杂质，用量一般为0-0.10％，上述百分比为C元素的用量占总量的质量百分比。
本发明中，如无特殊说明，涉及的“百分比”指质量百分比。
在不违背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：同时控制Cu、Zr元素的含量，在晶界处 存在富含Zr的R p-(Zr x,Cu y,M z) q-Fe 100-p-q富集相，该相有助于高温烧结，细化晶粒组织，从而提升磁体矫顽力(H cj≥16.3kOe)，改善方形度(H k/H cj≥0.98)，高温性能得到改善(80℃时Hcj温度系数绝对值≤0.738；150℃时Hcj温度系数绝对值≤0.425)。同时，由于不添加或控制微量Co含量，Co不会在晶界中富集，从而抑制沿晶断裂，提高了机械性能(抗弯强度≥469MPa)。
附图说明
图1为实施例9制得的R-T-B系永磁材料的FE-EPMA图谱。
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、R-T-B系永磁材料的原料组合物
实施例1-10及对比例1-5中R-T-B系永磁材料的原料组合物的配方如表1所示。
表1 实施例1-10、对比例1-5中R-T-B系永磁材料的原料组合物的组分和含量(％)
Figure PCTCN2021095089-appb-000003
Figure PCTCN2021095089-appb-000004
注：“/”是指不含有该元素。
实施例1-10以及对比例1-5中R-T-B系永磁材料的制备方法如下：
(1)熔炼和铸造过程：按照表1中的配方，将配制好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0.65MPa的条件下对氢破粉碎后的粉末进行气流磨粉碎(气流磨制粉的效率可根据设备不同有所差别，例如可为200kg/h)，得到细粉。
(4)成型过程：将经气流磨之后的粉末在1.5T以上的磁场强度中压制成型。
(5)烧结处理过程：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2-8h，得烧结体。
(6)时效处理过程：烧结体在高纯度Ar中，以3-5℃/min的升温速率从20℃升温至500℃，以500℃温度进行3小时热处理后，冷却至室温后取出。
实施例11
取实施例5中经烧结处理获得的烧结体，先进行晶界扩散处理，再进行时效处理。其余步骤均同实施例5。晶界扩散处理过程具体如下：
将烧结体加工成20mm×20mm、片料厚度小于7mm的磁铁，厚度方向为磁场取向方向，表面洁净化后，分别使用Dy氟化物配制成的原料，全面喷雾涂覆在磁铁上，将涂覆后的磁铁干燥，然后在高纯度Ar气氛中，以850℃的温度扩散热处理24小时。冷却至室温。
实施例12
取实施例2中经烧结处理获得的烧结体，先进行晶界扩散处理，再进行时效处理。其余步骤均同实施例2。晶界扩散处理过程具体如下：
将烧结体加工成20mm×20mm、片料厚度小于7mm的磁铁，厚度方向为磁场取向方向，表面洁净化后，分别使用Dy氟化物配制成的原料，全面喷雾涂覆在磁铁上，将涂覆后的磁铁干燥，然后在高纯度Ar气氛中，以850℃的温度扩散热处理24小时。冷却至室温。
效果实施例1
分别取实施例1-12以及对比例1-5中R-T-B系永磁材料，测定其磁性能和成分，观察其磁体的微观结构。
(1)R-T-B系永磁材料的各成分使用高频电感耦合等离子体发射光谱仪(ICP-OES，仪器型号：Icap6300)进行测定。下表2所示为成分检测结果。以实施例1为例，R-T-B系永磁材料检测所得元素种类、用量均与表1中公开的原料组合物的元素种类、用量相同。
表2 实施例1-12、对比例1-5中R-T-B系永磁材料的组分和含量(％)
Figure PCTCN2021095089-appb-000005
Figure PCTCN2021095089-appb-000006
注：“/”是指不含有该元素。
(2)磁性能评价：R-T-B系永磁材料使用中国计量院的NIM-10000H型BH大块稀土永磁无损测量系统进行磁性能检测(测试样品为直径D10mm×厚度5mm圆片)；磁性能检测结果如表3所示。
力学性能评价：R-T-B系永磁材料万能试验机进行抗弯强度检测，测试样品尺寸为20mm×7.5mm×6.5mm，6.5mm为取向方向。
表3
Figure PCTCN2021095089-appb-000007
Figure PCTCN2021095089-appb-000008
(3)微观结构的测定：对R-T-B系永磁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。首先通过FE-EPMA面扫描确定永磁材料中Zr、Cu等元素的分布。然后通过FE-EPMA单点定量分析确定Zr、Cu等元素的含量，测试条件为加速电压15kv，探针束流50nA。
取实施例9制得的R-T-B系永磁材料进行FE-EPMA测试，结果如图1和表4表所示。其中，图1分别对应Zr和Cu的浓度分布图。由图1可知，在晶界处存在Zr富集相，Cu在该Zr富集相中的含量高于其在主相中的含量。如图1中箭头1位置为主相，如图1中箭头2为Zr富集相。由表4可知，该Zr富集相中，稀土量约为18.39at％，Zr与Cu的比例为0.9。同样的，对其他实施例进行FE-EPMA检测，均可观测到存在晶界处R p-(Zr x,Cu y,M z) q-Fe 100-p-q富集相，15≤p≤25(at％)；4≤q≤12(at％)；x/(y+z)＝0.7-1.2。(at％是指原子百分数)。
表4
Figure PCTCN2021095089-appb-000009
表4中，各元素的含量指原子百分比(at％)。
具体实施例与对比例分析如下：
(1)本发明中同时控制Cu和Zr的含量，得到的R-T-B系永磁材料磁性能优异：B r≥14.09kGs，H cj≥16.3kOe；H k/H cj≥0.98；80℃时Hcj温度系数绝对值≤0.738；150℃时Hcj温度系数绝对值≤0.425。力学性能优异：抗弯强度≥469MPa(实施例1-12)。
(2)基于本发明的配方，原料Zr、B、Co或Pr用量的改变，R-T-B永磁材料的磁性能以及机械性能明显下降，尤其是H cj、80℃时Hcj温度系数绝对值和抗弯强度(对比例1-5)；
(3)发明人在研究过程中发现，同时控制Cu、Zr元素的含量，能够在晶界处存在富含Zr的R p-(Zr x,Cu y,M z) q-Fe 100-p-q富集相，该相有助于高温烧结，细化晶粒组织，从而提升磁体矫顽力，改善方形度，高温性能得到改善。同时，由于不添加或控制微量Co含量，Co不会在晶界中富集，从而抑制沿晶断裂，提高了机械性能。

Claims (10)

  1. 一种R-T-B系永磁材料的原料组合物，其特征在于，以质量百分比计，其包含下述组分：
    R，29.5-32％，所述R为至少包含Nd的稀土元素，并且，Pr的含量为0-17％；
    Zr，0.15-0.50％；
    Cu，0.35-0.55％；
    Co，0-0.3％；
    M，0-3％，所述M为Al、Ga、Ti、Nb、Hf、Si、Sn、Ge、Ag、Au、Bi和Mn中的一种或多种；
    B，0.95-1.05％；
    Fe，64-70％；
    百分比为占所述R-T-B系永磁材料的原料组合物总质量的质量百分比，各组分含量之和为100％。
  2. 如权利要求1所述的R-T-B系永磁材料的原料组合物，其特征在于，所述R为熔炼工艺和/或扩散工艺中添加的稀土元素；例如为熔炼工艺中添加的稀土元素；
    和/或，所述R的含量为29.8％、30.5％、30.6％、30.7％、30.8％、31％、31.5％、31.6％或32％；
    和/或，所述Nd含量为23.1-29.7％，例如23.1％、23.6％、24.3％、25％、25.2％、29％或29.7％；
    和/或，所述Pr的含量为0-10％，优选为0-8％，例如0、2.2％、5.5％、6.1％、7.4％或7.9％；
    和/或，所述R还包含重稀土元素；其中：
    较佳地，所述重稀土元素为熔炼工艺和/或扩散工艺中添加的重稀土元素，更佳地，所述重稀土元素为熔炼工艺中添加的重稀土元素；
    较佳地，所述重稀土元素为Dy、Tb、Gd和Ho中的一种或多种；
    较佳地，所述重稀土元素的含量为0-7％，但不包含0，优选为0.1-0.5％， 例如0.1、0.2％、0.3％或0.5％；
    和/或，所述Zr的含量为0.15％、0.2％、0.3％、0.35％或0.5％；
    和/或，所述Cu的含量为0.35％、0.4％或0.55％；
    和/或，所述Co的含量为0、0.1％或0.3％；
    和/或，所述B的含量为0.95％、0.98％或1.05％；
    和/或，所述M的种类为Al、Ga、Ti、Nb和Hf中的一种或多种；
    和/或，所述M的含量为0-2％，例如0、0.07％、0.08％、0.1％、0.75％、0.58％、0.7％、0.9％或1.2％；
    和/或，当所述M包含Al时，所述Al的含量为0-1％、但不包含0，例如0.02％、0.03％、0.48％、0.5％或0.55％；
    和/或，当所述M包含Ga时，所述Ga的含量为0-1％、但不包含0，例如0.05％、0.1％、0.2％或0.4％；
    和/或，当所述M包含Ti时，所述Ti的含量为0.05-0.3％，例如0.05％、0.1％或0.3％；
    和/或，当所述M包含Nb时，所述Nb的含量为0-0.2％、但不包含0，例如0.05％；
    和/或，当所述M包含Hf时，所述Hf的含量为0-0.2％、但不包含0，例如0.05％。
  3. 如权利要求1或2所述的R-T-B系永磁材料的原料组合物，其特征在于，所述R不包含Tb；
    或者，所述R不包含Dy和Tb以外的重稀土元素；
    或者，所述R不包含Ho；
    或者，除不可避免的杂质以外，所述R不含Nd和Pr以外的稀土金属；
    或者，所述Co的含量为0；
    或者，所述Co的含量为0-0.3％、但不包含0；例如所述Co的含量为0.1％或0.3％；
    或者，所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Al的含 量为≥0.55％；
    或者，所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Ga的含量为＜0.2％；所述Al的含量为0.45％-0.54％；
    或者，所述Zr的含量≥0.35％；所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Ga的含量为0.2-0.25％；所述Al的含量为0.45％-0.54％；所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Ga的含量为＞0.25％；所述Al的含量为0.45％-0.54％；所述Ti的含量为＜0.15％或＞0.28％；
    或者，所述R不含Tb；所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Al的含量<0.04％；
    或者，所述R含Tb；所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Al的含量<0.04％；Al+Cu≥0.55％；
    或者，所述R含Tb；所述Zr的含量≥0.26％；所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Al的含量<0.04％；
    或者，所述R包含Tb；所述Ga的含量＜0.05％或＞0.25％；所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Al的含量<0.04％；
    或者，所述R-T-B系永磁材料的原料组合物，以质量百分比计，其包含下述组分：R，29.5-32％，所述R为至少包含Nd的稀土元素，并且，Pr的含量为0-17％；Zr，0.15-0.50％；Cu，0.35-0.55％；Co，0-0.3％；M，0-3％，所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；B，0.95-1.05％；Fe，64-70％；百分比为占所述R-T-B系永磁材料的原料组合物总质量的质量百分比，各组分含量之和为100％；
    或者，所述R-T-B系永磁材料的原料组合物可为下述编号1-10中的任意一种，其中，百分比为各组分占所述R-T-B系永磁材料的原料组合物总质量的质量百分比，各组分含量之和为100％，
    Figure PCTCN2021095089-appb-100001
    Figure PCTCN2021095089-appb-100002
    “/”是指不含有该元素。
  4. 一种R-T-B系永磁材料的制备方法，其特征在于，将如权利要求1-3任一项所述的R-T-B系永磁材料的原料组合物经熔炼、制粉、成型、烧结处理和时效处理，即可。
  5. 如权利要求4所述的R-T-B系永磁材料的制备方法，其特征在于，所述熔炼包括以下步骤：所述R-T-B系永磁材料的原料组合物采用铸锭工艺和速凝片工艺进行熔炼浇铸，得到合金片；
    和/或，所述熔炼的温度为1300～1600℃；
    和/或，所述熔炼的设备为高频真空熔炼炉和/或中频真空熔炼炉；
    和/或，所述制粉包括氢破制粉和/或气流磨制粉；
    其中，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℃；所述吸氢的压力较佳地为50～600kPa；
    所述气流磨制粉磨室压力较佳地在0.1～2MPa；所述气流磨制粉中的气流较佳地为氮气和/或氩气；所述气流磨制粉的效率较佳地为30-400kg/h，例如200kg/h；
    和/或，所述成型为磁场成型法，所述的磁场成型法的磁场强度较佳地在1.5T以上；
    和/或，所述烧结处理为真空烧结工艺和/或惰性气氛烧结工艺；
    其中，当采用惰性气氛烧结工艺时，烧结开始阶段可在真空度低于5×10 -1Pa的条件下进行；所述惰性气氛较佳地为氦气、氩气；
    和/或，所述烧结处理的温度为1000-1200℃，较佳地为1030-1090℃；
    和/或，所述烧结处理的时间为0.5-10h，较佳地为2-8h；
    和/或，所述时效处理的温度为450℃-600℃，例如480-510℃；
    和/或，所述时效处理的时间可为1-4h，例如1～3h；
    和/或，所述烧结处理之后、所述时效处理之前，还进行晶界扩散处理；
    当进行晶界扩散处理时，所述晶界扩散处理较佳地包括以下步骤：在所述烧结处理得到的烧结体的表面蒸镀、涂覆或溅射附着含有Tb的物质和/或含有Dy的物质，经扩散热处理，即可；所述含有Tb的物质可为Tb金属、含有Tb的化合物(例如含有Tb的氟化物)或合金；所述含有Dy的物质可为Dy金属、含有Dy的化合物(例如含有Dy的氟化物)或合金；所述扩散热处理的温度可为800-900℃，例如850℃；所述扩散热处理的时间可为12-48h，例如24h。
  6. 一种由如权利要求4或5所述的制备方法制得的R-T-B系永磁材料。
  7. 一种R-T-B系永磁材料，其特征在于，以质量百分比计，其包含下述组分：
    R，29.5-32％，所述R为至少包含Nd的稀土元素，并且，Pr的含量为0-17％；
    Zr，0.15-0.50％；
    Cu，0.35-0.55％；
    Co，0-0.3％；
    M，0-3％，所述M为Al、Ga、Ti、Nb、Hf、Si、Sn、Ge、Ag、Au、Bi和Mn中的一种或多种；
    B，0.95-1.05％；
    Fe，64-70％；
    百分比为占所述R-T-B系永磁材料总质量的质量百分比，各组分含量之和为100％。
  8. 如权利要求7所述的R-T-B系永磁材料，其特征在于，所述R-T-B 系永磁材料的晶界处生成组成为R p-(Zr x,Cu y,M z) q-Fe 100-p-q的富集相，其中，R为至少包含Nd的稀土元素；M为Ga、Al、Ti、Nb、Hf、Si、Sn、Ge、Ag、Au、Bi和Mn中的一种或多种；p、q、x、y及z满足下述条件：15≤p≤25(at％)；4≤q≤12(at％)；x/(y+z)＝0.7-1.2，at％为原子百分比；
    和/或，所述R为熔炼工艺和/或扩散工艺中添加的稀土元素；例如为熔炼工艺中添加的稀土元素；
    和/或，所述R的含量为29.8％、30.5％、30.6％、30.7％、30.8％、31％、31.5％、31.6％或32％；
    和/或，所述Nd含量为23.1-29.7％，例如23.1％、23.6％、24.3％、25％、25.2％、29％或29.7％；
    和/或，所述Pr的含量为0-10％，优选为0-8％，例如0、2.2％、5.5％、6.1％、7.4％或7.9％；
    和/或，所述R还包含重稀土元素；其中：
    较佳地，所述重稀土元素为熔炼工艺和/或扩散工艺中添加的重稀土元素，更佳地，所述重稀土元素为熔炼工艺中添加的重稀土元素；
    较佳地，所述重稀土元素为Dy、Tb、Gd和Ho中的一种或多种；
    较佳地，所述重稀土元素的含量为0-7％，但不包含0，优选为0.1-0.5％，例如0.1、0.2％、0.3％或0.5％；
    和/或，所述Zr的含量为0.15％、0.2％、0.3％、0.35％或0.5％；
    和/或，所述Cu的含量为0.35％、0.4％或0.55％；
    和/或，所述Co的含量为0、0.1％或0.3％；
    和/或，所述B的含量为0.95％、0.98％或1.05％；
    和/或，所述M的种类为Al、Ga、Ti、Nb和Hf中的一种或多种；
    和/或，所述M的含量为0-2％，例如0、0.07％、0.08％、0.1％、0.75％、0.58％、0.7％、0.9％或1.2％；
    和/或，当所述M包含Al时，所述Al的含量为0-1％、但不包含0，例如0.02％、0.03％、0.48％、0.5％或0.55％；
    和/或，当所述M包含Ga时，所述Ga的含量为0-1％、但不包含0，例如0.05％、0.1％、0.2％或0.4％；
    和/或，当所述M包含Ti时，所述Ti的含量为0.05-0.3％，例如0.05％、0.1％或0.3％；
    和/或，当所述M包含Nb时，所述Nb的含量为0-0.2％、但不包含0，例如0.05％；
    和/或，当所述M包含Hf时，所述Hf的含量为0-0.2％、但不包含0，例如0.05％。
  9. 如权利要求7或8所述的R-T-B系永磁材料，其特征在于，所述R不包含Tb；
    或者，所述R不包含Dy和Tb以外的重稀土元素；
    或者，所述R不包含Ho；
    或者，除不可避免的杂质以外，所述R不含Nd和Pr以外的稀土金属；
    或者，所述Co的含量为0；
    或者，所述Co的含量为0-0.3％、但不包含0；例如所述Co的含量为0.1％或0.3％；
    或者，所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Al的含量为≥0.55％；
    或者，所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Ga的含量为＜0.2％；所述Al的含量为0.45％-0.54％；
    或者，所述Zr的含量≥0.35％；所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Ga的含量为0.2-0.25％；所述Al的含量为0.45％-0.54％；所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Ga的含量为＞0.25％；所述Al的含量为0.45％-0.54％；所述Ti的含量为＜0.15％或＞0.28％；
    或者，所述R不含Tb；所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Al的含量<0.04％；
    或者，所述R含Tb；所述M为Al、Ga、Ti、Nb和Hf中的一种或多种； 所述Al的含量<0.04％；Al+Cu≥0.55％；
    或者，所述R含Tb；所述Zr的含量≥0.26％；所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Al的含量<0.04％；
    或者，所述R包含Tb；所述Ga的含量＜0.05％或＞0.25％；所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；所述Al的含量<0.04％；
    或者，所述R-T-B系永磁材料，以质量百分比计，其包含下述组分：R，29.5-32％，所述R为至少包含Nd的稀土元素，并且，Pr的含量为0-17％；Zr，0.15-0.50％；Cu，0.35-0.55％；Co，0-0.3％；M，0-3％，所述M为Al、Ga、Ti、Nb和Hf中的一种或多种；B，0.95-1.05％；Fe，64-70％；百分比为占所述R-T-B系永磁材料总质量的质量百分比，各组分含量之和为100％；
    或者，所述R-T-B系永磁材料可为下述编号1-12中的任意一种，其中，百分比为各组分占所述R-T-B系永磁材料总质量的质量百分比，各组分含量之和为100％，
    Figure PCTCN2021095089-appb-100003
    “/”是指不含有该元素。
  10. 一种如权利要求6-9任一项所述的R-T-B系永磁材料作为电子元器件的应用。
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