WO2021169892A1 - Matériau d'aimant au néodyme-fer-bore, composition de matière première, son procédé de préparation et son utilisation - Google Patents

Matériau d'aimant au néodyme-fer-bore, composition de matière première, son procédé de préparation et son utilisation Download PDF

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WO2021169892A1
WO2021169892A1 PCT/CN2021/077177 CN2021077177W WO2021169892A1 WO 2021169892 A1 WO2021169892 A1 WO 2021169892A1 CN 2021077177 W CN2021077177 W CN 2021077177W WO 2021169892 A1 WO2021169892 A1 WO 2021169892A1
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content
mass percentage
grain boundary
weight
raw material
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Chinese (zh)
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骆溁
黄佳莹
廖宗博
蓝琴
林玉麟
师大伟
谢菊华
龙严清
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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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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
    • H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
    • H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H01F41/0266—Moulding; Pressing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H01F41/0293—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets diffusion of rare earth elements, e.g. Tb, Dy or Ho, into permanent magnets

Definitions

  • the invention relates to a neodymium iron boron magnet material, raw material composition, preparation method and application.
  • Nd-Fe-B permanent magnet material is based on Nd 2 Fe l4 B compound, which has the advantages of high magnetic properties, small 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 widely used in high-tech fields such as neodymium iron boron rare earth permanent magnets, samarium cobalt rare earth permanent magnets, batteries, etc.
  • Co is an important strategic resource and the price is relatively expensive.
  • the invention aims to overcome the technical problem of the prior art neodymium iron boron magnets by adding Co to increase the Curie temperature and coercivity, while Co faces the expensive defect, and provides a neodymium iron boron magnet material and raw material Composition, preparation method, application.
  • the magnet material of the present invention has the advantages of high remanence and high coercivity.
  • the neodymium iron boron magnet material provided by the present invention adopts the scheme of low content of Co and no heavy rare earth metal added to the smelting metal, and at the same time, the total rare earth content and the content range of Cu, B and M (Ga, Pb, etc.) elements are reasonably controlled, so that the miscellaneous phase More distributed in the two-grain grain boundary, the continuity of the grain boundary is improved, and the area of the triangular area of the grain boundary is reduced, so that the magnet remanence B and coercive force Hcj.
  • a raw material composition of neodymium iron boron magnet material which comprises:
  • R 28-33wt%
  • R is a rare earth element, including R1 for smelting and R2 for grain boundary diffusion, and the content of R2 is 0.2-1wt%;
  • the R1 includes Nd and does not contain RH;
  • the R2 includes Tb;
  • M 0.35wt% or less and not 0wt%
  • the M is one or more of Bi, Sn, Zn, Ga, In, Au and Pb;
  • the RH is a heavy rare earth element
  • the wt% is the mass percentage of each element in the raw material composition.
  • the content of R preferably ranges from 29.5 to 31.5 wt% or 29.8 to 32.8 wt%, such as 31.2 wt%, 32.2 wt%, or 30.9 wt%.
  • the mass percentage preferably ranges from 29.5 to 31.5 wt% or 29.8 to 32.8 wt%, such as 31.2 wt%, 32.2 wt%, or 30.9 wt%.
  • the R1 may also include one or more of Pr, La and Ce; preferably, it includes Pr.
  • 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 Nd, or in the form of a mixture of PrNd, pure Pr and Nd Add to.
  • the content of Pr is preferably 0.1-2wt%, for example 0.2wt% or 0.5wt%, wt % Is the mass percentage of the element in the raw material composition.
  • the content of R2 preferably ranges from 0.2 to 0.8% by weight or 0.5 to 1% by weight, such as 0.6% by weight, 0.9% by weight, 0.94% by weight or 0.7% by weight, and weight% means that the element accounts for the raw material.
  • the mass percentage of the composition preferably ranges from 0.2 to 0.8% by weight or 0.5 to 1% by weight, such as 0.6% by weight, 0.9% by weight, 0.94% by weight or 0.7% by weight, and weight% means that the element accounts for the raw material.
  • the content of Tb preferably ranges from 0.5 to 1% by weight, such as 0.8% by weight, 0.6% by weight, 0.75% by weight, 0.9% by weight or 0.7% by weight.
  • the percentage of mass preferably ranges from 0.5 to 1% by weight, such as 0.8% by weight, 0.6% by weight, 0.75% by weight, 0.9% by weight or 0.7% by weight. The percentage of mass.
  • the R2 may also include one or more of Pr, Dy, Ho and Gd. These rare earth elements can form a shell layer for diffusing rare earth elements through the principle of grain boundary diffusion.
  • the content of the Pr is preferably 0.2wt% or less and not 0wt%, such as 0.2wt% or 0.1wt%, and wt% means that the element accounts for the raw material composition. The percentage of mass.
  • the content of Dy is preferably less than 0.3% by weight and not 0% by weight, such as 0.1% by weight, 0.05% by weight, or 0.12% by weight.
  • the mass percentage of the raw material composition is preferably less than 0.3% by weight and not 0% by weight, such as 0.1% by weight, 0.05% by weight, or 0.12% by weight.
  • the content range of the Ho is preferably 0.15 wt% or less and not 0 wt%, such as 0.1 wt% or 0.02 wt%, and wt% means that the element accounts for the raw material composition. The percentage of mass.
  • the content of the Gd is preferably 0.15 wt% or less and not 0 wt%, such as 0.1 wt% or 0.06 wt%, and wt% means that the element accounts for the raw material composition The percentage of mass.
  • the content of B is preferably in the range of 0.9 to 0.99 wt% or 0.98 to 1.05 wt%, such as 1 wt%, 1.02 wt% or 1.03 wt%, and wt% is the mass of the element in the raw material composition percentage.
  • the content of Cu is preferably 0.07-0.15wt% or less than 0.08wt%, and not 0wt%, such as 0.12wt%, 0.13wt%, 0.03wt%, 0.05wt%, 0.09wt %, 0.1wt% or 0.07wt%, and wt% is the mass percentage of the element in the raw material composition.
  • the Cu may be added during smelting and/or grain boundary diffusion.
  • the Cu When the Cu is added when it diffuses at the grain boundary, the Cu is added in the form of a PrCu alloy, and the content of Cu is preferably 0.03 to 0.15 wt%, and wt% is the mass percentage of the element in the raw material composition; Wherein, the percentage of Cu in the PrCu is 0.1-17 wt%.
  • the content of M is preferably 0.05 to 0.25 wt% or 0.1 to 0.36 wt%, such as 0.07 wt%, 0.23 wt%, 0.24 wt%, 0.3 wt% or 0.31 wt%, and wt% is the element It accounts for the mass percentage of the raw material composition.
  • the M is one or more of Ga, Zn and Bi.
  • the content of Ga may range from 0.02 to 0.3 wt%, preferably 0.02 to 0.25 wt% or 0.08 to 0.2 wt%, for example, 0.07 wt%, where wt% is an element accounted for The mass percentage of the raw material composition.
  • the content of Zn may range from 0 to 0.25 wt%, preferably 0.01 to 0.21 wt%, for example, 0.13 wt%, and wt% is the amount of the element in the raw material composition. Mass percentage.
  • the content of Bi may range from 0 to 0.25 wt%, such as 0.15 wt% or 0.22 wt%, and wt% is the mass percentage of the element in the raw material composition.
  • the raw material composition also contains Al; the content of Al is preferably 0.03wt% or less, and not 0wt%, for example 0.01wt%, and the weight% is the amount of the element.
  • the mass percentage of the raw material composition preferably 0.03wt% or less, and not 0wt%, for example 0.01wt%, and the weight% is the amount of the element.
  • Al+Ga+Cu is preferably 0.15wt% or less and not 0wt%, such as 0.12wt%; preferably, Al+Ga+Cu It is 0.11 wt% or less and not 0 wt%, and wt% is the mass percentage of the element in the raw material composition.
  • the Co content range is preferably 0.4 wt% or less, and is not 0, for example, 0.1 wt%, 0.2 wt%, 0.3 wt% or 0.15 wt%.
  • the raw material composition contains the following components: in R1: Nd 27.5wt%; in R2: Tb 0.5wt%; B0.9wt%, Cu 0.15wt%, Ga 0.3 wt%, Co 0.1 wt%, the balance is Fe and unavoidable impurities, and wt% is the mass percentage of the element in the raw material composition.
  • the raw material composition contains the following components: in R1: Nd 32wt%; in R2: Tb 0.8wt%; B 1wt%, Cu 0.12wt%, Ga 0.25 wt%, Co 0.2wt%, the balance is Fe and unavoidable impurities, and wt% is the mass percentage of the element in the raw material composition.
  • the raw material composition in terms of weight percentage, includes the following components: in R1: Nd 30.4wt%, Pr 0.2wt%; in R2: Dy 0.1wt%, Tb 0.5wt%; B 0.98wt%, Cu 0.07wt%, Ga 0.1wt%, Co 0.4wt%, the balance is Fe and unavoidable impurities, and the wt% is the mass percentage of the element in the raw material composition.
  • the raw material composition contains the following components: in R1: Nd 30.8wt%, Pr 0.5wt%; in R2: Dy 0.1wt%, Tb 0.6wt%, Pr 0.2wt%; B 1.02wt%, Cu 0.13wt%, Ga 0.07wt%, Co 0.3wt%, the balance is Fe and unavoidable impurities, and wt% is the mass percentage of the element in the raw material composition.
  • the raw material composition contains the following components: in R1: Nd 29.9wt%; in R2: Dy 0.05wt%, Tb 0.75wt%, Ho 0.1wt%, Gd 0.1wt%; B 1.1wt%, Cu 0.03wt%, Zn 0.13wt%, Ga 0.1wt%, Co 0.15wt%, the balance is Fe and unavoidable impurities, and wt% is the element in the raw material composition The percentage of mass.
  • the raw material composition contains the following components: in R1: Nd 28.5wt%; in R2: Dy 0.12wt%, Tb 0.7wt%, Pr 0.1wt%, Ho 0.02wt%, Gd 0.06wt%; B 1.03wt%, Cu 0.05wt%, Bi 0.22wt%, Ga 0.02wt%, Co 0.35wt%, the balance is Fe and unavoidable impurities, and wt% is the element accounted for The mass percentage of the raw material composition.
  • the raw material composition contains the following components: R1: Nd 29wt%; R2: Tb 0.8wt%; B 0.99wt%, Cu 0.09wt%, Zn 0.21wt%, Bi0.15wt%, Al 0.03wt%, Co 0.4wt%, the balance is Fe and unavoidable impurities, and the weight% is the mass percentage of the element in the raw material composition.
  • the raw material composition contains the following components: in R1: Nd 30.5wt%; in R2: Dy 0.1wt%, Tb 0.9wt%; B 1wt%, Cu 0.1wt%, Zn 0.01wt%, Ga 0.3wt%, Al 0.01wt%, Co 0.25wt%, the balance is Fe and unavoidable impurities, and wt% is the mass percentage of the element in the raw material composition.
  • the present invention also provides a neodymium iron boron magnet material, R: 28-33wt%; said R includes R1 and R2, the content of said R2 is 0.2-1wt%; said R1 includes Nd and does not contain RH;
  • M 0.4wt% or less and not 0wt%
  • the M is one or more of Bi, Sn, Zn, Ga, In, Au and Pb;
  • wt% is the mass percentage of each element in 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, and the Nd in R1 is distributed in the Nd 2 Fe 14 B crystal grains, the two-grain grain boundary and the grain boundary triangle area; R2 is mainly distributed in the shell layer, the two-grain grain boundary and the grain boundary triangle area; the grain boundary triangle area
  • the area ratio of the NdFeB magnet material is 2.5-3.5%; the grain boundary continuity of the neodymium iron boron magnet material is more than 97%.
  • R2 is mainly distributed in the shell layer, the two-grain boundary and the grain boundary triangle” can be understood as the main distribution of R2 caused by the conventional grain boundary diffusion process in the field (generally refers to 95 % Or more)
  • a small part will also diffuse into the main phase crystal grains, for example, at the outer edge of the main phase crystal grains.
  • wt% is the mass ratio of the additional rare earth elements to the neodymium iron boron raw material composition.
  • 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 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 (the total area of the crystal grains and the grain boundary).
  • the calculation method of grain boundary continuity refers to the ratio of the length occupied by phases other than voids in the grain boundary (for example, the B-rich phase and the rare earth-rich phase are equal) to the total grain boundary length. Grain boundary continuity of more than 96% can be called continuous channel.
  • the “mass ratio of carbon and oxygen in the two-grain boundary” and “mass ratio of the carbon and oxygen in the triangular area” can be used to infer that the miscellaneous phase migrates from the triangular area to the two-grain boundary, and thus the area of the triangular area of the grain boundary Decrease.
  • the common forms of C and O in magnets are rare earth carbides and rare earth oxides.
  • the mass of C and O in the two-grain boundary is preferably 0.32-0.36%, such as 0.33%, 0.34% or 0.35%.
  • the quality of C and O in the triangular region of the grain boundary preferably accounts for 0.4-0.46%, for example, 0.44%, 0.42%, 0.41% or 0.45%.
  • the ratio of the mass of C and O in the triangular region of the grain boundary refers to 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 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 C and O elements in rare earth oxides and rare earth carbides are introduced in a conventional manner in the art, generally impurity introduction or atmosphere introduction. Specifically, for example, during jet milling and pressing, lubricants are introduced. During sintering, these additives will be removed by heating, but a small amount of C and O elements will inevitably remain; for another example, a small amount of O element will inevitably be introduced due to the atmosphere during the preparation process.
  • the content of C and O are 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.
  • a new phase is also detected at the two-particle grain boundary, and its chemical composition is R 73.3-74.6 (Fe+Co) 17.7 ⁇ 18.5 Cu 3.5 ⁇ 4.5 M 1.9 ⁇ 2.2 B 1.95 ⁇ 2.2 , where R includes Nd and Tb, and M is one or more of Bi, Sn, Zn, Ga, In, Au and Pb .
  • the structure of the new phase is, for example, R 74.15 (Fe+Co) 17.71 Cu 3.94 M 2.06 B 2.14 , R 74.51 (Fe+Co) 17.80 Cu 3.57 M 2.13 B 1.99 , R 73.67 ( Fe+Co) 17.70 Cu 4.37 M 2.13 B 2.13 , R 73.77 (Fe+Co) 17.76 Cu 4.32 M 1.98 B 2.17 , R 73.66 (Fe+Co) 18.30 Cu 4.02 M 1.92 B 2.10 , R 74.15 (Fe+Co) 17.35 Cu 4.25 M 2.07 B 2.18 , R 73.31 (Fe+Co) 18.03 Cu 4.50 M 2.11 B 2.05 , R 74.23 (Fe+Co) 18.15 Cu 3.52 M 2.08 B 2.02 .
  • the area of the R 73.3 ⁇ 74.6 (Fe+Co) 17.7 ⁇ 18.5 Cu 3.5 ⁇ 4.5 M 1.9 ⁇ 2.2 B 1.95 ⁇ 2.2 phase in the two-grain boundary is preferably 0.2 ⁇ 2.2%, for example 1.88 %, 0.26%, 0.86%, 0.42%, 0.64%, 2.04%, 1.56% and 0.39%.
  • 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.
  • the area of the triangular area of the grain boundary preferably accounts for 1.98-2.9%, such as 2.45%, 2.39%, 1.98%, 2.81%, 2.77%, 2.04%, 2.36% or 2.44%.
  • the grain boundary continuity is preferably 97.4% or more, such as 97.82%, 97.46%, 97.77%, 97.69%, 98.04%, 97.88%, 97.67% or 98.03%.
  • the content of R preferably ranges from 29.5 to 31.5 wt% or 29.8 to 32.8 wt%, for example, 31.2 wt%, 32.2 wt% or 30.9 wt%, and wt% means that the element accounts for the neodymium iron boron material The percentage of mass.
  • the R1 may also include one or more of Pr, La and Ce; preferably, it includes Pr.
  • Pr when the R1 contains Pr, Pr is added in the form of PrNd, or in the form of a mixture of pure Pr and Nd, or in the form of a mixture of PrNd, and pure Pr and Nd.
  • Pr:Nd 25:75 or 20:80.
  • the content of Pr is preferably 0.1-2wt%, for example 0.2wt% or 0.5wt%, wt % Is the mass percentage of the element in the neodymium iron boron magnet material.
  • the content of R2 preferably ranges from 0.2 to 0.8% by weight or 0.5 to 1% by weight, such as 0.6% by weight, 0.9% by weight, 0.94% by weight, or 0.7% by weight, and weight% means that the element accounts for the neodymium The mass percentage of iron boron material.
  • the content of Tb preferably ranges from 0.5 to 1% by weight, such as 0.8% by weight, 0.6% by weight, 0.75% by weight, 0.9% by weight, or 0.7% by weight.
  • the mass percentage of the material preferably ranges from 0.5 to 1% by weight, such as 0.8% by weight, 0.6% by weight, 0.75% by weight, 0.9% by weight, or 0.7% by weight.
  • the R2 may also include one or more of Pr, Dy, Ho and Gd. These rare earth elements can form a shell layer for diffusing rare earth elements through the principle of grain boundary diffusion.
  • the content range of the Pr is preferably 0.2 wt% or less, and not 0 wt%, such as 0.2 wt% or 0.1 wt%, and wt% means that the element accounts for the neodymium iron boron The mass percentage of the material.
  • the content of Dy is preferably less than 0.3% by weight and not 0% by weight, such as 0.1% by weight, 0.05% by weight, or 0.12% by weight.
  • the mass percentage of the neodymium iron boron material is preferably less than 0.3% by weight and not 0% by weight, such as 0.1% by weight, 0.05% by weight, or 0.12% by weight.
  • the content range of the Ho is preferably 0.15wt% or less and not 0wt%, such as 0.1wt% or 0.02wt%, and the wt% means that the element accounts for the neodymium iron boron The mass percentage of the material.
  • the content range of the Gd is preferably 0.15 wt% or less and not 0 wt%, for example, 0.1 wt% or 0.06 wt%, and wt% means that the element accounts for the neodymium iron boron The mass percentage of the material.
  • the content of B is preferably 0.9 to 0.99 wt% or 0.98 to 1.05 wt%, for example, 1 wt%, 1.02 wt% or 1.03 wt%, and wt% is the amount of the element in the neodymium iron boron material. The mass percentage.
  • the content of Cu is preferably 0.07-0.15wt% or less than 0.08wt%, and not 0wt%, such as 0.12wt%, 0.13wt%, 0.03wt%, 0.05wt%, 0.09wt %, 0.1% by weight or 0.07% by weight, and weight% is the mass percentage of the element in the neodymium iron boron material.
  • the Cu may be added during smelting and/or grain boundary diffusion.
  • the Cu When the Cu is added when it diffuses at the grain boundary, the Cu is added in the form of a PrCu alloy, and the content of Cu is preferably 0.03 to 0.15 wt%, and wt% is the mass percentage of the element in the raw material composition; Wherein, the percentage of Cu in the PrCu is 0.1-17 wt%.
  • the content of M is preferably 0.05 to 0.25 wt% or 0.1 to 0.36 wt%, such as 0.07 wt%, 0.23 wt%, 0.24 wt%, 0.3 wt% or 0.31 wt%, and wt% is the element It accounts for the mass percentage of the neodymium iron boron material.
  • the M is one or more of Ga, Zn and Bi.
  • the content of Ga may range from 0.02 to 0.3 wt%, preferably 0.02 to 0.25 wt% or 0.08 to 0.2 wt%, for example, 0.07 wt%, and wt% is the element accounted for The mass percentage of the neodymium iron boron material.
  • the content of Zn may range from 0 to 0.25 wt%, preferably 0.01 to 0.21 wt%, such as 0.13 wt%, and wt% means that the element accounts for the neodymium iron boron material The percentage of mass.
  • the content of Bi may range from 0 to 0.25 wt%, such as 0.15 wt% or 0.22 wt%, and wt% is the mass percentage of the element in the neodymium iron boron material.
  • the neodymium iron boron material also contains Al; the content of Al is preferably 0.03wt% or less, and not 0wt%, for example, 0.01wt%, and the weight% is the element The mass percentage of the neodymium iron boron material.
  • Al+Ga+Cu is preferably 0.15wt% or less and not 0wt%, such as 0.12wt%; preferably, Al+Ga+Cu It is 0.11 wt% or less and not 0 wt%, and wt% is the mass percentage of the element in the neodymium iron boron material.
  • the Co content range is preferably 0.4 wt% or less, and is not 0, for example, 0.1 wt%, 0.2 wt%, 0.3 wt% or 0.15 wt%.
  • the neodymium iron boron material includes the following components in terms of weight percentage: in R1: Nd 27.5wt%; in R2: Tb 0.5wt%; B0.9wt%, Cu 0.15wt% , Ga 0.3wt%, Co 0.1wt%, the balance is Fe and unavoidable impurities, and wt% is the mass percentage of the element in the neodymium iron boron material;
  • the area ratio of the triangular area of the grain boundary is 2.45%; the continuity of the grain boundary is 97.82%, and the new phase in the two-grain grain boundary is R 74.15 (Fe+Co) 17.71 Cu 3.94 M 2.06 B 2.14 .
  • the neodymium iron boron material includes the following components in terms of weight percentage: in R1: Nd 32wt%; in R2: Tb 0.8wt%; B 1wt%, Cu 0.12wt%, Ga 0.25wt%, Co 0.2wt%, the balance is Fe and unavoidable impurities, and wt% is the mass percentage of the element in the neodymium iron boron material;
  • the area ratio of the triangular area of the grain boundary is 2.39%; the continuity of the grain boundary is 97.46%, and the new phase in the two-grain grain boundary is R 74.51 (Fe+Co) 17.80 Cu 3.57 M 2.13 B 1.99 .
  • the neodymium iron boron material includes the following components in terms of weight percentage: in R1: Nd 30.4wt%, Pr 0.2wt%; in R2: Dy 0.1wt%, Tb 0.5wt% B 0.98wt%, Cu 0.07wt%, Ga 0.1wt%, Co 0.4wt%, the balance is Fe and inevitable impurities, and wt% is the mass percentage of the element in the neodymium iron boron material;
  • the area of the triangular area of the grain boundary accounts for 1.98%; the continuity of the grain boundary is 97.77%, and the new phase in the two-grain grain boundary is R 73.67 (Fe+Co) 17.70 Cu 4.37 M 2.13 B 2.13 .
  • the neodymium iron boron material comprises the following components in terms of weight percentage: in R1: Nd 30.8wt%, Pr 0.5wt%; in R2: Dy 0.1wt%, Tb 0.6wt% , Pr 0.2wt%; B1.02wt%, Cu 0.13wt%, Ga 0.07wt%, Co 0.3wt%, the balance is Fe and inevitable impurities, wt% is the mass percentage of the element in the neodymium iron boron material ;
  • the area ratio of the triangular area of the grain boundary is 2.81%; the continuity of the grain boundary is 97.69%, and the new phase in the two-grain boundary is R 73.77 (Fe+Co) 17.76 Cu 4.32 M 1.98 B 2.17 .
  • the neodymium iron boron material includes the following components in terms of weight percentage: in R1: Nd 29.9wt%; in R2: Dy 0.05wt%, Tb 0.75wt%, Ho 0.1wt% , Gd 0.1wt%; B 1.1wt%, Cu 0.03wt%, Zn 0.13wt%, Ga 0.1wt%, Co 0.15wt%, the balance is Fe and unavoidable impurities, wt% is the element accounted for in the neodymium iron The mass percentage of boron material;
  • the area ratio of the triangular area of the grain boundary is 2.77%; the continuity of the grain boundary is 98.04%, and the new phase in the two-grain grain boundary is R 73.66 (Fe+Co) 18.30 Cu 4.02 M 1.92 B 2.10 .
  • the neodymium iron boron material includes the following components in terms of weight percentage: in R1: Nd 28.5wt%; in R2: Dy 0.12wt%, Tb 0.7wt%, Pr 0.1wt% , Ho 0.02wt%, Gd 0.06wt%; B 1.03wt%, Cu 0.05wt%, Bi 0.22wt%, Ga 0.02wt%, Co 0.35wt%, the balance is Fe and unavoidable impurities, wt% is element Accounting for the mass percentage of the neodymium iron boron material;
  • the area ratio of the triangular area of the grain boundary is 2.04%; the continuity of the grain boundary is 97.88%, and the new phase in the two-grain grain boundary is R 74.15 (Fe+Co) 17.35 Cu 4.25 M 2.07 B 2.18 .
  • the neodymium iron boron material comprises the following components in terms of weight percentage: in R1: Nd 29wt%; in R2: Tb 0.8wt%; B 0.99wt%, Cu 0.09wt%, Zn 0.21wt%, Bi0.15wt%, Al 0.03wt%, Co 0.4wt%, the balance is Fe and unavoidable impurities, and wt% is the mass percentage of the element in the neodymium iron boron material;
  • the area ratio of the triangular area of the grain boundary is 2.36%; the continuity of the grain boundary is 97.67%, and the new phase in the two-grain grain boundary is R 73.31 (Fe+Co) 18.03 Cu 4.50 M 2.11 B 2.05 .
  • the neodymium iron boron material includes the following components in terms of weight percentage: in R1: Nd 30.5wt%; in R2: Dy 0.1wt%, Tb 0.9wt%; B 1wt%, Cu 0.1wt%, Zn 0.01wt%, Ga 0.3wt%, Al 0.01wt%, Co 0.25wt%, the balance is Fe and unavoidable impurities, and wt% is the mass percentage of the element in the neodymium iron boron material;
  • the area of the triangular area of the grain boundary accounts for 2.44%; the continuity of the grain boundary is 98.03%, and the new phase in the two-grain grain boundary is R 74.23 (Fe+Co) 18.15 Cu 3.52 M 2.08 B 2.02 .
  • the present invention also provides a preparation method of neodymium iron boron magnet material, which adopts the raw material composition as described above, the preparation method is a diffusion method, the R1 element is added in the smelting step, and the R2 element It 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 be subjected to grain boundary diffusion treatment.
  • the smelting operation and conditions can be conventional smelting processes in the field.
  • the elements other than R2 in the neodymium iron boron magnet material are smelted and casted by ingot casting process and quick-setting sheet process to obtain alloy flakes.
  • the temperature of the smelting may be 1300 to 1700°C, preferably 1450 to 1550°C, such as 1500°C.
  • the vacuum degree of the melting furnace may be 5 ⁇ 10 -2 Pa.
  • the melting equipment is generally a high-frequency vacuum melting furnace, for example, melting in a high-frequency vacuum induction melting furnace.
  • the operation and conditions of the pulverization can be conventional pulverization processes in the field, and generally include two processes of hydrogen crushing pulverization and jet milling pulverization.
  • 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, such as 25°C.
  • the temperature of the dehydrogenation is generally 400-650°C, and may be 500-550°C, such as 550°C.
  • the pressure of the hydrogen absorption is generally 50 to 600 kPa, such as 90 kPa.
  • the air-jet milling powder is generally carried out under the conditions of 0.1-2 MPa, preferably 0.5-0.7 MPa (for example, 0.6 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, for example, 3 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, for example, 1030 to 1090°C, and for example, 1040°C.
  • the sintering time may be 0.5-10, such as 2-5, and further for example 2h.
  • the grain boundary diffusion treatment can be processed according to a conventional process in the art, such as R2 coating operation.
  • the R2 is generally coated in the form of fluoride or low melting point alloy, such as Tb alloy or fluoride.
  • the R2 further includes Dy, preferably, Dy is coated in the form of an alloy or fluoride of Dy.
  • the R2 also contains Pr, preferably, Pr is added in the form of a PrCu alloy.
  • the Cu may be added in a smelting and/or grain boundary diffusion.
  • the Cu When the Cu is added when it diffuses at the grain boundary, the Cu is added in the form of a PrCu alloy, and the content of Cu is preferably 0.03 to 0.15 wt%, and wt% is the mass percentage of the element in the raw material composition; Wherein, the percentage of Cu in the PrCu is 0.1-17 wt%.
  • 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, for example 5-15h, and for example 18h.
  • a low-temperature tempering treatment is also performed according to the conventional practice in the art.
  • the temperature of the low-temperature tempering treatment is generally 460-560°C, for example 550°C.
  • the time for the low-temperature tempering treatment may be 1 to 3 hours.
  • the invention also provides a neodymium iron boron magnet material prepared by the above-mentioned preparation method.
  • 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 and/or 52UH high-performance magnetic steel.
  • the reagents and raw materials used in the present invention are all commercially available.
  • the magnet material of the present invention has excellent magnet performance, in which Br ⁇ 14.3kGs, Hcj ⁇ 24.2kOe; 20-120°CBr temperature coefficient ⁇ -0.106%/°C; grain boundary continuity is 97.4% or more, triangle area area Less than 2.9%;
  • the magnet material of the present invention can be used in the manufacture of 54SH and/or 52UH high-performance magnetic steel. Since only a low content of Co is required, the production cost is reduced.
  • FIG. 1 is an EPMA photomicrograph of the neodymium iron boron magnet material prepared in Example 1.
  • FIG. 1 is an EPMA photomicrograph of the neodymium iron boron magnet material prepared in Example 1.
  • 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 1040°C for 2 hours to obtain a sintered body.
  • R2 for example, one or more of Tb alloy or fluoride, Dy alloy or fluoride and PrCu alloy
  • R2 for example, one or more of Tb alloy or fluoride, Dy alloy or fluoride and PrCu alloy
  • Each component of the neodymium iron boron magnet material is measured using a high-frequency inductively coupled plasma emission spectrometer (ICP-OES). Table 2 below shows the component test results.
  • the temperature coefficient of remanence of the neodymium iron boron magnet material of the present invention is equivalent to or even better than that of the comparative example; the coercive force is significantly higher than that of the comparative example (embodiments 1 to 8), because: according to the "grain boundary" in the examples The difference of the “mass ratio of C and O in the triangular area” minus the “mass ratio of C and O in the two-grain boundary (%)” is smaller than the comparison ratio, and it can be obtained that the miscellaneous phase migrates from the triangular area of the grain boundary to The conclusion of the two-grain boundary, which explains the improvement of the continuity of the grain boundary and the reason for the improvement of the magnetic properties from the mechanism. It shows that under the same condition of only low content of Co, if the formula of this application is not used for synergistic cooperation, the effect is poor (Comparative Examples 1 to 5).
  • FIG. 1 it is a scanning photo of the microstructure of the NdFeB magnet prepared in Example 1.
  • the structure of the black area is the shedding of the neodymium-rich phase caused by grinding and polishing when the sample is prepared for scanning electron microscope observation. Makes black holes appear in the picture.
  • point 3 is the main phase of Nd 2 Fe 14 B (dark gray area)
  • point 2 is the grain boundary triangle area (silver-white area)
  • point 1 is the new phase R 73.3 ⁇ 74.6 (Fe+ Co) 17.7 ⁇ 18.5 Cu 3.5 ⁇ 4.5 M 1.9 ⁇ 2.2 B 1.95 ⁇ 2.2 .
  • the results show that the area of the triangular area of the grain boundary is smaller than that of the conventional magnet.

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Abstract

L'invention concerne un matériau d'aimant au néodyme-fer-bore, une composition de matière première, son procédé de préparation et son utilisation, les matières premières comprenant les constituants suivants : R : 28 à 33 % en poids, R représentant des éléments de terres rares, comprenant R1 pour la fusion et R2 pour une diffusion de limite de grain, la teneur en R2 étant de 0,2 à 1 % en poids, et R1 comprenant du Nd, et étant dépourvu de RH ; R2 comprend : du Tb ; du B : de 0,9 à 1,5 % en poids ; du Cu : en une proportion inférieure ou égale à 0,15 % en poids mais différente de 0 % en poids ; M : en une proportion inférieure ou égale à 0,35 % en poids mais différente de 0 % en poids, et M représentant un ou plusieurs constituants parmi Bi, Sn, Zn, Ga, In, Au et Pb ; du Fe : de 60 à 70,55 % en poids ; RH représente un élément des terres rares ; du Co : en une proportion < 0,5 % en poids mais différente de 0 % en poids. Le présent matériau magnétique présente les avantages d'une rémanence élevée, d'une coercitivité élevée et d'une bonne performance à haute température.
PCT/CN2021/077177 2020-02-26 2021-02-22 Matériau d'aimant au néodyme-fer-bore, composition de matière première, son procédé de préparation et son utilisation WO2021169892A1 (fr)

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