CN111243808A - Neodymium-iron-boron material and preparation method and application thereof - Google Patents

Neodymium-iron-boron material and preparation method and application thereof Download PDF

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Publication number
CN111243808A
CN111243808A CN202010132227.7A CN202010132227A CN111243808A CN 111243808 A CN111243808 A CN 111243808A CN 202010132227 A CN202010132227 A CN 202010132227A CN 111243808 A CN111243808 A CN 111243808A
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permanent magnetic
magnetic material
percentage
content
series permanent
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CN111243808B (en
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付刚
黄清芳
黄佳莹
许德钦
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Fujian Jinlong Rare Earth Co ltd
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Xiamen Tungsten Co Ltd
Fujian Changting Jinlong Rare Earth Co Ltd
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Priority to PCT/CN2021/077184 priority patent/WO2021169898A1/en
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
    • H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
    • H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H01F41/0266—Moulding; Pressing

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Hard Magnetic Materials (AREA)

Abstract

The invention discloses a neodymium iron boron material and a preparation method and application thereof. The neodymium iron boron material comprises the following components: r: 28.1-33.1 wt%; cu: not less than 0.4 wt%; al: 0.08-0.125 wt%; b: 0.84-0.945 wt%; fe: 64.6 to 70.1 weight percent; wherein: when the neodymium iron boron material contains Ti, the content of Ti is 0.15-0.255 wt%; when the neodymium iron boron material contains Zr, the content of Zr is 0.19-0.355 wt%; when the neodymium iron boron material contains Nb, the content of Nb is 0.19-0.51 wt%; the neodymium iron boron material does not contain Co; r in grain boundary phase of neodymium iron boron material6Fe13The volume fraction of the Cu phase is more than or equal to 3.5 percent. The permanent magnetic material has excellent magnetic performance, low relative magnetic conductivity and good consistency of magnet performance.

Description

Neodymium-iron-boron material and preparation method and application thereof
Technical Field
The invention relates to a neodymium iron boron material and a preparation method and application thereof.
Background
Because of its excellent magnetic properties, R-T-B sintered magnets (R refers to rare earth elements, T refers to transition metal elements and group iii metal elements, and B refers to boron elements) are widely used in the fields of electronic products, automobiles, wind power, household appliances, elevators, industrial robots, and the like, for example, as energy sources in permanent magnet motors such as hard disks, mobile phones, earphones, elevator traction machines, generators, and the like, and the demand for the performance of magnets, such as remanence and coercive force, is increasing.
In order to improve remanence of R-T-B sintered magnets, it is generally necessary to lower the B content, but when the B content is less than 5.88 at%, R is easily formed as seen from the Nd-Fe-B ternary phase diagram2T17And R is2T17Has no room temperature uniaxial anisotropy, thereby deteriorating the performance of the magnet.
In the prior art, heavy rare earth elements such as Dy, Tb, Gd and the like are generally added to improve the coercive force of the material and improve the temperature coefficient, but the heavy rare earth is high in price, and the method for improving the coercive force of the R-T-B sintered magnet product can increase the raw material cost and is not beneficial to the application of the R-T-B sintered magnet.
Therefore, how to prepare the R-T-B magnet with high coercivity and high remanence by adopting a low B system (B < 5.88 at%) under the condition of not adding or adding a small amount of heavy rare earth is a technical problem to be solved in the field.
Disclosure of Invention
The invention aims to overcome the defect that the consistency of the performance of a magnet is poor when B in an R-T-B series magnet is less than 5.88 at% in the prior art, and provides a neodymium iron boron material and a preparation method and application thereof.
The invention provides an R-T-B series permanent magnetic material, which comprises the following components: r, Cu, B, Al and Fe, and also comprises one or more of Ti, Zr and Nb, and the content is as follows in percentage by weight:
r: 28.1-33.1 wt%; r is a rare earth element at least containing Nd;
Cu：≥0.4wt％；
Al：0.08-0.125wt％；
B：0.84-0.945wt％；
fe: 64.6 to 70.1 weight percent; wherein:
when the R-T-B series permanent magnet material contains Ti, the content of the Ti is 0.15-0.255 wt%;
when the R-T-B series permanent magnet material contains Zr, the content of Zr is 0.19-0.355 wt%;
when the R-T-B series permanent magnet material contains Nb, the content of Nb is 0.19-0.51 wt%;
the R-T-B series permanent magnet material does not contain Co;
the R-T-B series permanent magnetic material comprises R2T14A main phase B, a grain boundary phase and a rare earth-rich phase, wherein the grain boundary phase contains R6Fe13Cu phase, said R6Fe13The volume fraction of the Cu phase is more than or equal to 3.5 percent, and the percentage refers to the R6Fe13Volume of Cu phase in the grain boundary phase and R phase2T14The sum of the volumes of the B main phase and the rare earth-rich phase is a percentage.
In the present invention, preferably, R is6Fe13The volume fraction of the Cu phase is 4.6-8.4%, e.g. 4.6%, 4.7%, 4.8%, 4.9%, 5.1%, 5.3%, 5.6%, 6.7%, 7.6%, 7.8% or 8.4%, the percentages referring to said R6Fe13Volume of Cu phase in the grain boundary phase and R phase2T14The sum of the volumes of the B main phase and the rare earth-rich phase is a percentage.
In the present invention, the content of said R is preferably 28.495-33.006 wt%, for example 28.495 wt%, 28.497 wt%, 28.507 wt%, 29.497 wt%, 29.500 wt%, 29.505 wt%, 29.987 wt%, 30.017 wt%, 30.018 wt%, 30.489 wt%, 30.492 wt%, 30.493 wt%, 30.496 wt%, 30.501 wt%, 30.505 wt%, 31.002 wt%, 31.003 wt%, 31.004 wt%, 31.005 wt%, 31.006 wt%, 31.008 wt%, 31.879 wt%, 31.991 wt%, 32.001 wt%, 32.984 wt%, 33.004 wt% or 33.006 wt%, the percentage referring to the weight percentage in said R-T-B system permanent magnetic material.
In the present invention, the content of Nd is preferably 21.372 to 24.753 wt%, for example, 21.372 wt%, 21.374 wt%, 21.378 wt%, 21.382 wt%, 22.126 wt%, 22.127 wt%, 22.495 wt%, 22.508 wt%, 22.509 wt%, 22.871 wt%, 22.872 wt%, 22.874 wt%, 22.876 wt%, 23.251 wt%, 23.252 wt%, 23.253 wt%, 23.254 wt%, 23.892 wt%, 23.968 wt%, 24.014 wt%, 24.752 wt% or 24.753 wt%, and the percentage refers to the weight percentage in the R-T-B system permanent magnetic material.
In the invention, the R can also comprise Pr and/or heavy rare earth RH.
Wherein, the content of Pr can be less than 0.2 at% or more than 8 at%, and the percentage refers to the atomic percentage in the R-T-B series permanent magnetic material.
Wherein, the content of Pr is preferably 5.0-18.0 wt%, such as 7.121-8.253 wt%, such as 7.121 wt%, 7.125 wt%, 7.371 wt%, 7.373 wt%, 7.378 wt%, 7.492 wt%, 7.509 wt%, 7.619 wt%, 7.621 wt%, 7.625 wt%, 7.629 wt%, 7.750 wt%, 7.752 wt%, 7.753 wt%, 7.756 wt%, 7.987 wt%, 8.023 wt%, 8.252 wt% or 8.253 wt%, the percentage refers to the weight percentage in the R-T-B series permanent magnetic material.
Wherein, when said R further comprises Pr, the atomic percentage of B/(Pr + Nd) is preferably ≧ 0.405, such as 0.405, 0.414, 0.424, 0.426 or 0.428.
Wherein, the RH can be Tb or Dy.
Wherein the RH content may be 1.5-6.0 wt%, such as 1.978 wt% or 1.986 wt%, the percentage referring to the weight percentage in the R-T-B series permanent magnetic material.
In the present invention, the Cu content is preferably 0.4 to 2.05 wt%, for example, 0.402 wt%, 0.409 wt%, 0.452 wt%, 0.453 wt%, 0.503 wt%, 0.504 wt%, 0.552 wt%, 0.553 wt%, 0.605 wt%, 0.652 wt%, 0.705 wt%, 0.709 wt%, 0.793 wt%, 0.805 wt%, 0.808 wt%, 0.809 wt%, 0.987 wt%, 0.989 wt%, 1.012 wt%, 1.402 wt%, 1.404 wt%, 1.509 wt%, 1.804 wt%, 1.987 wt%, or 2.012 wt%, and the percentage means the weight percentage in the R-T-B series permanent magnetic material.
In the present invention, it is preferable that the Cu content is 0.45 wt% or more, for example, 0.45 wt% or more and less than 0.65 wt% or Cu 0.65 wt% or more, and the percentage means the weight percentage in the R-T-B series permanent magnetic material.
In the present invention, it is preferable that the R-T-B based permanent magnetic material does not contain Ga.
In the present invention, the content of Al is preferably 0.081 to 0.124 wt%, for example, 0.081 wt%, 0.082 wt%, 0.083 wt%, 0.089 wt%, 0.091 wt%, 0.092 wt%, 0.093 wt%, 0.1 wt%, 0.101 wt%, 0.103 wt%, 0.104 wt%, 0.106 wt%, 0.111 wt%, 0.112 wt%, 0.113 wt%, 0.115 wt%, 0.122 wt%, or 0.124 wt%, and the percentage refers to the weight percentage in the R-T-B system permanent magnetic material.
In the present invention, the content of B is preferably 0.842 to 0.943 wt%, for example, 0.842 wt%, 0.843 wt%, 0.863 wt%, 0.883 wt%, 0.884 wt%, 0.892 wt%, 0.893 wt%, 0.902 wt%, 0.909 wt%, 0.911 wt%, 0.914 wt%, 0.915 wt%, 0.916 wt%, 0.919 wt%, 0.922 wt%, 0.923 wt%, 0.925 wt%, 0.939 wt%, 0.942 wt%, or 0.943 wt%, and the percentage means the weight percentage in the R-T-B series permanent magnetic material.
In the invention, the content of B is preferably not less than 0.915 wt% or not less than 5.55 at%; more preferably, the content of B is greater than 0.915 wt% and 5.55 at%; wt% means a weight percentage in the R-T-B system permanent magnetic material, and at% means an atomic percentage in the R-T-B system permanent magnetic material.
In the present invention, preferably, the ratio of the atomic percentages of B and TRE is not less than 0.38, such as 0.38, 0.39, 0.40, 0.41 or 0.42; wherein, TRE is total rare earth amount; for example, when the R comprises Nd and Pr, the TRE is the sum of the contents of the Nd and the Pr, and when the R comprises Nd, Pr and heavy rare earth RH, the TRE is the sum of the contents of the Nd, the Pr and the heavy rare earth RH.
In the present invention, the content of Fe is preferably 64.641 to 70.007 wt%, for example, 64.641 wt%, 64.833 wt%, 64.977 wt%, 65.022 wt%, 65.454 wt%, 65.883 wt%, 65.891 wt%, 65.925 wt%, 66.016 wt%, 66.557 wt%, 66.829 wt%, 66.844 wt%, 66.899 wt%, 66.9 wt%, 67.008 wt%, 67.027 wt%, 67.416 wt%, 67.608 wt%, 67.675 wt%, 67.723 wt%, 67.8 wt%, 67.907 wt%, 68.094 wt%, 68.243 wt%, 68.252 wt%, 68.366 wt%, 68.888 wt%, 68.938 wt%, 69.148 wt% or 70.007 wt%, and the percentage means the weight percentage in the R-T-B system permanent magnetic material.
In the present invention, when the R-T-B based permanent magnetic material contains Ti, the content of Ti is preferably 0.152 to 0.253 wt%, for example, 0.152 wt%, 0.154 wt%, 0.197 wt%, 0.204 wt%, 0.205 wt%, 0.206 wt%, or 0.253 wt%, which means a weight percentage in the R-T-B based permanent magnetic material.
In the present invention, when the R-T-B based permanent magnetic material contains Zr, the content of Zr is preferably 0.193 to 0.352 wt%, such as 0.193 wt%, 0.197 wt%, 0.262 wt%, 0.264 wt%, 0.281 wt%, 0.283 wt%, 0.297 wt%, 0.308 wt%, 0.309 wt%, 0.344 wt%, 0.348 wt%, or 0.352 wt%, and the percentage refers to the weight percentage in the R-T-B based permanent magnetic material.
In the present invention, when the R-T-B based permanent magnetic material contains Nb, the content of Nb is preferably 0.197 to 0.505 wt%, for example, 0.197 wt%, 0.198 wt%, 0.200 wt%, 0.203 wt%, 0.297 wt%, 0.298 wt%, 0.397 wt%, 0.398 wt%, or 0.505 wt%, which means the weight percentage in the R-T-B based permanent magnetic material.
In the present invention, when the R-T-B series permanent magnetic material contains Zr, the Zr content is preferably 0.20 wt% Zr ≦ (3.48B-2.67) wt%, for example 0.26 wt% Zr ≦ (3.48B-2.67) wt%, wherein B is the weight percentage of B in the R-T-B series permanent magnetic material; the percentage refers to the weight percentage in the R-T-B series permanent magnet material.
In a preferred embodiment of the present invention, the R-T-B based permanent magnetic material comprises the following components: r: 28.1-33.1 wt%, Al: 0.08 to 0.125 wt%, Cu: not less than 0.45 wt%, B: 0.84-0.945 wt%, Fe: 64.6-70.1 wt%, Ti: 0.15-0.255 wt%, the percentage refers to the weight percentage in the R-T-B series permanent magnetic material.
In a preferred embodiment of the present invention, the R-T-B based permanent magnetic material comprises the following components: r: 28.1-33.1 wt%, Al: 0.08 to 0.125 wt%, Cu: 0.45-0.65 wt%, B: 0.84-0.945 wt%, Fe: 64.6 to 70.1 wt%, Zr: 0.19-0.355 wt%; wherein, preferably, the Zr content is more than or equal to 0.26 percent and less than (3.48B-2.67 percent) by weight; the percentage refers to the weight percentage in the R-T-B series permanent magnet material.
In a preferred embodiment of the present invention, the R-T-B based permanent magnetic material comprises the following components: r: 28.1-33.1 wt%, Al: 0.08 to 0.125 wt%, Cu: not less than 0.65 wt%, B: 0.84-0.945 wt%, Fe: 64.6 to 70.1 wt%, Zr: 0.19-0.355 wt%; wherein, preferably, the content of Zr is more than or equal to 0.20 percent and less than (3.48B-2.67 percent) percent by weight; the percentage refers to the weight percentage in the R-T-B series permanent magnet material.
The invention provides a raw material composition of an R-T-B series permanent magnetic material, which comprises the following components: r, Cu, B, Al and Fe, and also comprises one or more of Ti, Zr and Nb, and the content is as follows in percentage by weight:
r: 28.0-33.0 wt%; r is a rare earth element at least containing Nd;
Cu：≥0.4wt％；
Al：0.05-0.07wt％；
B：0.84-0.94wt％；
fe: 64.6 to 70.1 weight percent; wherein:
when the R-T-B series permanent magnet material contains Ti, the content of the Ti is 0.15-0.25 wt%;
when the R-T-B series permanent magnet material contains Zr, the content of Zr is 0.2-0.35 wt%;
when the R-T-B series permanent magnet material contains Nb, the content of Nb is 0.2-0.5 wt%;
the R-T-B series permanent magnet material does not contain Co.
As known to those skilled in the art, the raw material composition of the R-T-B series permanent magnetic material generally refers to raw materials actively added in the preparation process of the permanent magnetic material, and does not include components and/or contents introduced in the preparation process or impurities.
In the present invention, the content of R is preferably 28.5 to 33.0 wt%, for example 28.5 wt%, 29.5 wt%, 30.0 wt%, 30.5 wt%, 31.0 wt%, 32.0 wt%, or 33.0 wt%, which is a weight percentage in the raw material composition of the R-T-B-based permanent magnetic material.
In the present invention, the content of Nd is preferably 17.5 to 26.0 wt%, for example 21.375 wt%, 22.125 wt%, 22.5 wt%, 22.875 wt%, 23.25 wt%, 24.0 wt%, or 24.75 wt%, which is a weight percentage in the raw material composition of the R-T-B-based permanent magnetic material.
In the invention, the R can also comprise Pr and/or heavy rare earth RH.
Wherein, the content of Pr can be less than 0.2 at% or more than 8 at%, and the percentage refers to the atomic percentage in the raw material composition of the R-T-B series permanent magnetic material.
Wherein, the content of Pr is preferably 2.5-12.0 wt%, such as 7.125 wt%, 7.375 wt%, 7.5 wt%, 7.625 wt%, 7.75 wt%, 8.0 wt% or 8.25 wt%, which is the weight percentage in the raw material composition of the R-T-B series permanent magnetic material.
Wherein, when the R also comprises Pr, the atomic percentage of B/(Pr + Nd) is preferably more than or equal to 0.405.
Wherein, the RH can be Tb or Dy.
Wherein the RH may be present in an amount of 1.5-6.0 wt.%, for example 2.0 wt.%, percentages referring to weight percentages in the raw material composition of the R-T-B based permanent magnetic material.
In the present invention, it is preferable that the raw material composition of the R-T-B based permanent magnetic material does not contain Ga.
In the present invention, the content of Al is preferably 0.06 to 0.07 wt%, for example, 0.06 wt% or 0.07 wt%, which is a weight percentage in the raw material composition of the R-T-B based permanent magnetic material.
In the present invention, the content of Cu is preferably 0.4 to 2.0 wt%, for example, 0.4 wt%, 0.45 wt%, 0.5 wt%, 0.55 wt%, 0.6 wt%, 0.65 wt%, 0.7 wt%, 0.8 wt%, 1.0 wt%, 1.4 wt%, 1.5 wt%, 1.8 wt%, or 2.0 wt%, and the percentage means the weight percentage in the raw material composition of the R-T-B-based permanent magnetic material.
In the present invention, it is preferable that the Cu content is 0.4 wt% or more, for example, 0.45 wt% or more and less than 0.65 wt% or Cu 0.65 wt% or more, and the percentage means the weight percentage in the raw material composition of the R-T-B system permanent magnetic material.
In the present invention, the content of B is preferably 0.86 to 0.94 wt%, for example, 0.86 wt%, 0.88 wt%, 0.9 wt%, 0.915 wt%, 0.92 wt%, or 0.94 wt%, which is a weight percentage in the raw material composition of the R-T-B-based permanent magnetic material.
In the invention, the content of B is preferably not less than 0.915 wt% or not less than 5.55 at%; more preferably, the content of B is greater than 0.915 wt% and 5.55 at%; wt% means a weight percentage in the raw material composition of the R-T-B based permanent magnetic material, and at% means an atomic percentage in the raw material composition of the R-T-B based permanent magnetic material.
In the invention, preferably, the atomic percentage ratio of B to TRE is more than or equal to 0.38; wherein, TRE is total rare earth amount; for example, when Nd and Pr are included in the R, the TRE is the sum of the contents of the Nd and the Pr.
In the present invention, the content of Fe is preferably 64.675 to 70.06 wt%, for example, 64.675 wt%, 64.885 wt%, 64.99 wt%, 65.07 wt%, 65.51 wt%, 65.93 wt%, 65.955 wt%, 65.96 wt%, 66.615 wt%, 66.855 wt%, 66.9 wt%, 66.925 wt%, 66.96 wt%, 67.055 wt%, 67.1 wt%, 67.46 wt%, 67.65 wt%, 67.71 wt%, 67.78 wt%, 67.84 wt%, 67.94 wt%, 68.135 wt%, 68.28 wt%, 68.315 wt%, 68.43 wt%, 68.93 wt%, 68.97 wt%, 69.165 wt% or 70.06 wt%, which is a weight percentage in a raw material composition of the R-T-B system permanent magnetic material.
In the present invention, when the R-T-B based permanent magnetic material contains Ti, the content of Ti is preferably 0.2 to 0.25 wt%, for example, 0.2 wt% or 0.25 wt%, and the percentage refers to the weight percentage in the raw material composition of the R-T-B based permanent magnetic material.
In the present invention, when the R-T-B based permanent magnetic material contains Zr, the content of Zr is preferably 0.26 to 0.35 wt%, for example, 0.26 wt%, 0.28 wt%, 0.3 wt%, 0.34 wt%, or 0.35 wt%, and the percentage refers to the weight percentage in the raw material composition of the R-T-B based permanent magnetic material.
In the present invention, when the R-T-B based permanent magnetic material contains Nb, the content of Nb is preferably 0.3 to 0.5 wt%, for example, 0.30 wt%, 0.40 wt%, or 0.5 wt%, and the percentage refers to the weight percentage in the raw material composition of the R-T-B based permanent magnetic material.
In the present invention, when Zr is contained in the raw material composition of the R-T-B series permanent magnetic material, the Zr content is preferably 0.20 wt% or more and less than (3.48B-2.67) wt%, for example 0.26 wt% or less and less than (3.48B-2.67) wt%, wherein B is the weight percentage of B in the raw material composition of the R-T-B series permanent magnetic material; the percentage refers to the weight percentage in the raw material composition of the R-T-B series permanent magnet material.
In a preferred embodiment of the present invention, the raw material composition of the R-T-B series permanent magnetic material comprises the following components: r: 28.0-33.0 wt%, Al: 0.05 to 0.07 wt%, Cu: not less than 0.45 wt%, B: 0.84-0.94 wt%, Fe: 64.6-70.1 wt%, Ti: 0.15-0.25 wt%, the percentage refers to the weight percentage in the raw material composition of the R-T-B series permanent magnetic material.
In a preferred embodiment of the present invention, the raw material composition of the R-T-B series permanent magnetic material comprises the following components: r: 28.0-33.0 wt%, Al: 0.05 to 0.07 wt%, Cu: 0.45-0.65 wt%, B: 0.84-0.94 wt%, Fe: 64.6 to 70.1 wt%, Zr: 0.20-0.35 wt%; wherein, preferably, the Zr content is more than or equal to 0.26 percent and less than (3.48B-2.67 percent) by weight; the percentage refers to the weight percentage in the raw material composition of the R-T-B series permanent magnet material.
In a preferred embodiment of the present invention, the raw material composition of the R-T-B series permanent magnetic material comprises the following components: r: 28.0-33.0 wt%, Al: 0.05 to 0.07 wt%, Cu: not less than 0.65 wt%, B: 0.84-0.94 wt%, Fe: 64.6 to 70.1 wt%, Zr: 0.20-0.35 wt%; wherein, preferably, the content of Zr is more than or equal to 0.20 percent and less than (3.48B-2.67 percent) percent by weight; the percentage refers to the weight percentage in the raw material composition of the R-T-B series permanent magnet material.
The invention also provides a preparation method of the R-T-B series permanent magnetic material, which comprises the following steps:
performing casting, hydrogen fracturing, forming, sintering and aging treatment on the molten liquid of the raw material composition of the R-T-B series permanent magnet material; wherein:
the aging treatment comprises primary aging treatment and secondary aging treatment, wherein the temperature of the primary aging treatment is 830-870 ℃.
Wherein, the melting liquid of the raw material composition of the R-T-B series permanent magnetic material can be prepared by the conventional method in the field, such as: smelting in a high-frequency vacuum induction smelting furnace. The vacuum degree of the smelting furnace can be 5 multiplied by 10-2Pa. The temperature of the smelting can be below 1500 ℃.
Wherein the casting process may be a casting process conventional in the art, such as: in an Ar atmosphere (e.g. 5.5X 10)4Pa Ar atmosphere), passing the melt of the raw material composition of the R-T-B permanent magnetic material through a rotating roller at 10 deg.C2DEG C/sec-104Cooling at a rate of DEG C/sec.
The cooling can be realized by introducing cooling water into the roller.
The roller may be a copper roller.
Preferably, the water inlet temperature of the roller is less than or equal to 25 ℃, such as 23.1 ℃, 23.4 ℃, 23.6 ℃, 23.7 ℃, 23.9 ℃, 24.2 ℃ or 24.5 ℃.
The hydrogen breaking process can be a hydrogen breaking process conventional in the art, and can be performed through hydrogen absorption, dehydrogenation and cooling treatment.
The hydrogen absorption can be carried out under the condition that the hydrogen pressure is 0.15 MPa.
The dehydrogenation can be carried out under the condition of vacuum pumping and temperature rise.
Wherein, after the hydrogen is broken, the raw materials can be crushed by the conventional method in the field. The comminution process may be a comminution process conventional in the art, such as jet milling.
The jet mill pulverization may be performed in a nitrogen atmosphere having an oxidizing gas content of 120ppm or less. The oxidizing gas refers to oxygen or moisture content.
The pressure of the crushing chamber for crushing by the jet mill can be 0.38 MPa.
The jet mill pulverizing time may be 3 hours.
After the pulverization, a lubricant, such as zinc stearate, may be added to the powder as is conventional in the art. The lubricant may be added in an amount of 0.10 to 0.15%, for example 0.12% by weight of the mixed powder.
The forming process may be a forming process conventional in the art, such as magnetic field forming or hot press hot deformation.
Wherein the sintering process may be a sintering process conventional in the art, for example, under vacuum conditions (e.g., at 5 × 10)-3Pa, vacuum), preheating, sintering and cooling.
The temperature of the preheating may be 300-600 ℃. The preheating time can be 1-2 h. Preferably, the preheating is for 1h each at a temperature of 300 ℃ and 600 ℃.
The sintering temperature may be a sintering temperature conventional in the art, such as 1040-.
The sintering time may be a sintering time as conventional in the art, such as 5-10h, for example, further 8 h.
Before cooling, Ar gas can be introduced to ensure that the gas pressure reaches 0.1 MPa.
Wherein, the temperature of the primary aging treatment is preferably 840 ℃ to 870 ℃, such as 840 ℃, 845 ℃, 850 ℃, 860 ℃ or 870 ℃.
In the primary aging treatment, the rate of temperature rise to the temperature of the primary aging treatment is preferably 3to 5 ℃/min. The starting point of the warming may be room temperature.
Wherein the treatment time of the primary aging can be 1-6h, such as 3 h.
Wherein, the temperature of the secondary aging treatment is preferably 430-560 ℃, such as 440-465 ℃, and further such as 440 ℃, 450 ℃, 455 ℃, 460 ℃ or 465 ℃.
In the secondary aging, the heating rate of heating to 430-560 ℃ is preferably 3-5 ℃/min. The starting point of the warming may be room temperature.
The treatment time for the secondary ageing may be 1 to 6 hours, for example 3 hours.
The invention also provides the R-T-B series permanent magnetic material prepared by the method.
The invention also provides application of the R-T-B series permanent magnetic material as an electronic component.
The application field can be the automobile driving field, the wind power field, the servo motor field and the household appliance field (such as an air conditioner).
In the present invention, the room temperature means 25 ℃. + -. 5 ℃.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
(1) the magnetic property is excellent, the R-T-B series permanent magnetic material Br is more than or equal to 12.54kGs, the Hcj is more than or equal to 17.05kOe, after the heavy rare earth element is added, the Hcj can reach 27.01kOe (Tb) and 23.69kOe (Dy), the temperature stability of the magnet is good, and the absolute value of the Br temperature coefficient α%/° C at 20-80 ℃ is less than 0.108.
(2) The demagnetization curve is smooth, no step exists, the relative magnetic conductivity is low, the same-batch range of the coercive force is less than or equal to 1.5kOe, and the consistency of the magnet performance is good.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Example 1
The raw materials used for preparing the R-T-B series permanent magnetic material in this example are shown in table 1, and the preparation process is as follows:
(1) and (3) smelting: according to the formula shown in Table 1, the prepared raw materials are put in oxygenIn a crucible made of aluminum, in a high-frequency vacuum induction melting furnace at a temperature of 5X 10-2Vacuum melting is carried out in vacuum of Pa at the temperature of below 1500 ℃ to obtain molten liquid.
(2) The casting process comprises the following steps: introducing Ar into a smelting furnace after vacuum smelting to ensure that the air pressure reaches 5.5 ten thousand Pa, casting, and passing the molten liquid through a copper roller with the rotation speed of 29 revolutions per minute to prepare a rapid hardening alloy sheet with the thickness of 0.12-0.35mm, wherein in the casting process, chilled water needs to be introduced into the copper roller, and the water inlet temperature is less than or equal to 25 ℃.
(3) Hydrogen crushing and crushing: vacuumizing the hydrogen breaking furnace in which the quenching alloy is placed at room temperature, introducing hydrogen with the purity of 99.9% into the hydrogen breaking furnace, maintaining the hydrogen pressure at 0.15MPa, fully absorbing hydrogen, vacuumizing while heating, fully dehydrogenating, cooling, and taking out the powder after hydrogen breaking and crushing.
(4) A micro-grinding process: the powder after hydrogen crushing was pulverized by jet milling for 3 hours under a nitrogen atmosphere having an oxidizing gas content of 120ppm or less and a pressure in the pulverization chamber of 0.38MPa to obtain a fine powder. The oxidizing gas refers to oxygen or moisture.
(5) Adding zinc stearate into the powder crushed by the jet mill, wherein the adding amount of the zinc stearate is 0.12 percent of the weight of the mixed powder, and then fully mixing the zinc stearate and the mixed powder by using a V-shaped mixer.
(6) Magnetic field forming process: using a magnetic field forming machine of a perpendicular orientation type, in an orientation magnetic field of 1.6T, at 0.35ton/cm2The powder added with zinc stearate was once formed into a cube with a side length of 25mm under the molding pressure of (1), and demagnetized in a magnetic field of 0.2T after the primary molding. The molded article after the primary molding was sealed so as not to contact air, and then subjected to secondary molding (isostatic pressing) at 1.3ton/cm2Secondary forming is performed under pressure of (1).
(7) And (3) sintering: the molded bodies were transferred to a sintering furnace and sintered at 5X 10-3Pa at 300 deg.C and 600 deg.C for 1 hr, sintering at 1090 deg.C for 8 hr, introducing Ar gas to make pressure reach 0.1MPa, and cooling to room temperature.
(8) And (3) aging treatment process: the sintered body is subjected to first-stage aging treatment in high-purity Ar at the temperature rising rate of 3-5 ℃/min from 20 ℃ to 850 ℃, and the method comprises the following specific steps: after heat treatment at 850 ℃ for 3 hours, the mixture was cooled to room temperature and taken out. After that, secondary aging treatment was performed for 3 hours at a temperature as shown in Table 2.
TABLE 1 weight percentages of raw materials in each example and comparative example
Figure BDA0002396104870000121
Figure BDA0002396104870000131
Figure BDA0002396104870000141
Example 2-example 30, comparative examples 1-8
Raw materials were prepared according to the formulation shown in Table 1, and the process conditions were the same as in example 1 except for the conditions shown in Table 2, to obtain R-T-B sintered magnets.
Examples 31 to 34
R-T-B sintered magnets were obtained in the same manner as in example 1 except that the raw materials for examples 31 to 34 were the same as in example 1 and the process conditions were the same as in example 1 except that the conditions shown in Table 2 were changed.
Comparative examples 9 to 11
The raw material of comparative example 9 is the same as example 1, the raw material of comparative example 10 is the same as example 2, and the raw material of comparative example 11 is the same as example 3.
Comparative examples 9 to 11R-T-B sintered magnets were produced under the same process conditions as in example 1 except for the conditions shown in Table 2.
TABLE 2
Figure BDA0002396104870000142
Figure BDA0002396104870000151
Figure BDA0002396104870000161
Effects of the embodiment
(1) Component determination
The sintered magnets of examples 1 to 30 and comparative examples 1 to 8 were measured for specific components using a high frequency inductively coupled plasma emission spectrometer (ICP-OES). The following table shows the results of the component detection.
TABLE 3
Figure BDA0002396104870000162
Figure BDA0002396104870000171
Note: the content of Al in the sintered magnets of examples 1 to 30 and comparative examples 1 to 8 is the sum of the content of Al in the raw material and the content of Al introduced in other raw materials and processes (e.g., a crucible made of alumina during melting).
(2) Detection of magnetic Properties
① microstructure, perpendicular orientation surface of R-T-B permanent magnetic material is polished by FE-EPMA detection, and R in grain boundary is detected by field emission electron probe microanalyzer (FE-EPMA) (JEOL, 8530F)6T13M phase, T refers to Fe, and M refers to Cu. The test results are shown in table 4 below.
② evaluation of magnetic Properties the sintered magnet was tested for magnetic properties using the NIM-10000H model BH bulk rare earth permanent magnet nondestructive testing system from China's institute of metrology, Table 4 below shows the results of the magnetic properties.
Wherein, Br or Hcj both mean values: calculating an average value by testing the remanence or coercive force of 5 parts of rare earth permanent magnetic material samples (10 mm x 10mm cylinders) in the same batch; the volume ratio of 6-13-1 to the whole phase and the temperature coefficient are also average values obtained by measuring the properties of 5 samples (10 mm cylinders 10mm) of the R-T-B series permanent magnetic material in the same batch. The same batch refers to the product obtained in the same period of time according to the starting materials and processes shown in the examples or comparative examples.
TABLE 4
Figure BDA0002396104870000181
Figure BDA0002396104870000191
Note: in Table 4, the 6-13-1 phase means RE6Fe13A Cu phase, wherein: the volume ratio of the 6-13-1 phase to the overall phase is referred to as RE6Fe13The volume ratio of Cu phase in bulk phase, the bulk phase including grain boundary phase and R2T14A main phase B and a rare earth-rich phase; the magnetic properties of the R-T-B series permanent magnet materials in the comparative examples 1-8 are the best properties obtained by the formula of the comparative examples 1-8 after process optimization (water inlet temperature, sintering temperature and aging temperature).
(3) Magnetic property uniformity detection
Squareness: the formula is Hk/Hcj (Hk is the value of the external magnetic field H when B is 90% Br, Hcj is the coercive force).
Relative magnetic permeability: the calculation formula is Br/Hcb (Br is remanence, Hcb is magnetic coercive force).
Squareness and relative permeability are averages obtained by measuring the properties of 5 samples (10 mm cylinders by 10mm) of R-T-B series permanent magnetic material in the same batch.
Max (Max hcj) -Min (hcj): and subtracting the minimum value of the coercive force from the maximum value of the coercive force in the same batch of products, wherein if the minimum value of the coercive force is more than 1.5kOe, the consistency of the magnetic performance is poor. The same batch refers to the product obtained in the same period of time according to the starting materials and processes shown in the examples or comparative examples.
The following table shows the results of the magnetic property uniformity measurements.
TABLE 5
Figure BDA0002396104870000201
Figure BDA0002396104870000211
Figure BDA0002396104870000221

Claims (10)

1. An R-T-B series permanent magnetic material, comprising: r, Cu, B, Al and Fe, and also comprises one or more of Ti, Zr and Nb, and the content is as follows in percentage by weight:
r: 28.1-33.1 wt%; r is a rare earth element at least containing Nd;
Cu：≥0.4wt％；
Al：0.08-0.125wt％；
B：0.84-0.945wt％；
fe: 64.6 to 70.1 weight percent; wherein:
when the R-T-B series permanent magnet material contains Ti, the content of the Ti is 0.15-0.255 wt%;
when the R-T-B series permanent magnet material contains Zr, the content of Zr is 0.19-0.355 wt%;
when the R-T-B series permanent magnet material contains Nb, the content of Nb is 0.19-0.51 wt%;
the R-T-B series permanent magnet material does not contain Co;
the R-T-B series permanent magnetic material comprises R2T14A main phase B, a grain boundary phase and a rare earth-rich phase, wherein the grain boundary phase contains R6Fe13Cu phase, said R6Fe13The volume fraction of the Cu phase is more than or equal to 3.5 percent, and the percentage refers to the R6Fe13Volume of Cu phase in the grain boundary phase and R phase2T14The sum of the volumes of the B main phase and the rare earth-rich phase is a percentage.
2. The R-T-B series permanent magnetic material according to claim 1, wherein R is6Fe13The volume fraction of the Cu phase is 4.6-8.4%, e.g. 4.6%, 4.7%, 4.8%, 4.9%, 5.1%, 5.3%, 5.6%, 6.7%,7.6%, 7.8% or 8.4%, the percentages referring to said R6Fe13Volume of Cu phase in the grain boundary phase and R phase2T14The percentage of the sum of the volumes of the main phase B and the rare earth-rich phase;
and/or said R content is 28.495-33.006 wt%, such as 28.495 wt%, 28.497 wt%, 28.507 wt%, 29.497 wt%, 29.500 wt%, 29.505 wt%, 29.987 wt%, 30.017 wt%, 30.018 wt%, 30.489 wt%, 30.492 wt%, 30.493 wt%, 30.496 wt%, 30.501 wt%, 30.505 wt%, 31.002 wt%, 31.003 wt%, 31.004 wt%, 31.005 wt%, 31.006 wt%, 31.008 wt%, 31.879 wt%, 31.991 wt%, 32.001 wt%, 32.984 wt%, 33.004 wt% or 33.006 wt%, the percentages referring to the weight percentage in said R-T-B series permanent magnetic material;
and/or said Nd is in an amount of 21.372-24.753 wt%, such as 21.372 wt%, 21.374 wt%, 21.378 wt%, 21.382 wt%, 22.126 wt%, 22.127 wt%, 22.495 wt%, 22.508 wt%, 22.509 wt%, 22.871 wt%, 22.872 wt%, 22.874 wt%, 22.876 wt%, 23.251 wt%, 23.252 wt%, 23.253 wt%, 23.254 wt%, 23.892 wt%, 23.968 wt%, 24.014 wt%, 24.752 wt% or 24.753 wt%, the percentages referring to the weight percentages in said R-T-B based permanent magnetic material;
and/or, the R also comprises Pr and/or heavy rare earth RH; wherein, the content of Pr is preferably 5.0-18.0 wt%, such as 7.121-8.253 wt%, such as 7.121 wt%, 7.125 wt%, 7.371 wt%, 7.373 wt%, 7.378 wt%, 7.492 wt%, 7.509 wt%, 7.619 wt%, 7.621 wt%, 7.625 wt%, 7.629 wt%, 7.750 wt%, 7.752 wt%, 7.753 wt%, 7.756 wt%, 7.987 wt%, 8.023 wt%, 8.252 wt% or 8.253 wt%, the percentage refers to the weight percentage in the R-T-B series permanent magnetic material; the RH can be Tb or Dy in type; the RH content may be 1.5-6.0 wt%, such as 1.978 wt% or 1.986 wt%, percentage referring to the weight percentage in the R-T-B series permanent magnetic material; preferably, when said R further comprises Pr, the atomic percentage of B/(Pr + Nd) is ≧ 0.405, such as 0.405, 0.414, 0.424, 0.426 or 0.428;
and/or the Cu content is 0.4-2.05 wt%, such as 0.402 wt%, 0.409 wt%, 0.452 wt%, 0.453 wt%, 0.503 wt%, 0.504 wt%, 0.552 wt%, 0.553 wt%, 0.605 wt%, 0.652 wt%, 0.705 wt%, 0.709 wt%, 0.793 wt%, 0.805 wt%, 0.808 wt%, 0.809 wt%, 0.987 wt%, 0.989 wt%, 1.012 wt%, 1.402 wt%, 1.404 wt%, 1.509 wt%, 1.804 wt%, 1.987 wt% or 2.012 wt%, the percentages referring to the weight percentage in the R-T-B series permanent magnetic material;
or the content of Cu is more than or equal to 0.45 wt%, such as more than or equal to 0.45 wt% and less than 0.65 wt% or more than or equal to 0.65 wt%, and the percentage refers to the weight percentage in the R-T-B series permanent magnet material;
and/or the R-T-B series permanent magnetic material does not contain Ga;
and/or the Al content is 0.081-0.124 wt%, such as 0.081 wt%, 0.082 wt%, 0.083 wt%, 0.089 wt%, 0.091 wt%, 0.092 wt%, 0.093 wt%, 0.1 wt%, 0.101 wt%, 0.103 wt%, 0.104 wt%, 0.106 wt%, 0.111 wt%, 0.112 wt%, 0.113 wt%, 0.115 wt%, 0.122 wt% or 0.124 wt%, the percentages referring to the weight percentage in the R-T-B series permanent magnetic material;
and/or said B is present in an amount of 0.842 to 0.943 wt%, such as 0.842 wt%, 0.843 wt%, 0.863 wt%, 0.883 wt%, 0.884 wt%, 0.892 wt%, 0.893 wt%, 0.902 wt%, 0.909 wt%, 0.911 wt%, 0.914 wt%, 0.915 wt%, 0.916 wt%, 0.919 wt%, 0.922 wt%, 0.923 wt%, 0.925 wt%, 0.939 wt%, 0.942 wt% or 0.943 wt%, percentages referring to the weight percentages in said R-T-B series permanent magnetic material;
or the content of the B is more than or equal to 0.915 wt% or more than or equal to 5.55 at%; preferably, the amount of B is the greater of 0.915 wt% and 5.55 at%; wt% means a weight percentage in the R-T-B series permanent magnetic material, and at% means an atomic percentage in the R-T-B series permanent magnetic material;
and/or said Fe content is 64.641-70.007 wt%, such as 64.641 wt%, 64.833 wt%, 64.977 wt%, 65.022 wt%, 65.454 wt%, 65.883 wt%, 65.891 wt%, 65.925 wt%, 66.016 wt%, 66.557 wt%, 66.829 wt%, 66.844 wt%, 66.899 wt%, 66.9 wt%, 67.008 wt%, 67.027 wt%, 67.416 wt%, 67.608 wt%, 67.675 wt%, 67.723 wt%, 67.8 wt%, 67.907 wt%, 68.094 wt%, 68.243 wt%, 68.252 wt%, 68.366 wt%, 68.888 wt%, 68.938 wt%, 69.148 wt% or 70.007 wt%, percentages referring to weight percentages in said R-T-B series permanent magnetic material;
and/or, when said R-T-B based permanent magnetic material comprises Ti, said Ti is present in an amount of 0.152-0.253 wt%, such as 0.152 wt%, 0.154 wt%, 0.197 wt%, 0.204 wt%, 0.205 wt%, 0.206 wt% or 0.253 wt%, percentages referring to weight percentages in said R-T-B based permanent magnetic material;
and/or, when said R-T-B based permanent magnetic material comprises Zr, said Zr content is 0.193-0.352 wt%, such as 0.193 wt%, 0.197 wt%, 0.262 wt%, 0.264 wt%, 0.281 wt%, 0.283 wt%, 0.297 wt%, 0.308 wt%, 0.309 wt%, 0.344 wt%, 0.348 wt% or 0.352 wt%, percentage referring to weight percentage in said R-T-B based permanent magnetic material;
and/or, when the R-T-B series permanent magnetic material contains Nb, the content of Nb is 0.197 to 0.505 wt%, such as 0.197 wt%, 0.198 wt%, 0.200 wt%, 0.203 wt%, 0.297 wt%, 0.298 wt%, 0.397 wt%, 0.398 wt% or 0.505 wt%, percentage referring to the weight percentage in the R-T-B series permanent magnetic material;
alternatively, when the R-T-B series permanent magnetic material contains Zr, the Zr content is 0.20 wt% Zr ≦ Zr < (3.48B-2.67) wt%, such as 0.26 wt% Zr ≦ 3.48B-2.67 wt%, percentages referring to weight percentages in the R-T-B series permanent magnetic material.
3. The R-T-B system permanent magnetic material according to claim 1 or 2, wherein the R-T-B system permanent magnetic material comprises the following components: r: 28.1-33.1 wt%, Al: 0.08 to 0.125 wt%, Cu: not less than 0.45 wt%, B: 0.84-0.945 wt%, Fe: 64.6-70.1 wt%, Ti: 0.15-0.255 wt%, the percentage refers to the weight percentage in the R-T-B series permanent magnetic material;
or, the R-T-B series permanent magnetic material comprises the following components: r: 28.1-33.1 wt%, Al: 0.08 to 0.125 wt%, Cu: 0.45-0.65 wt%, B: 0.84-0.945 wt%, Fe: 64.6 to 70.1 wt%, Zr: 0.19-0.355 wt%; wherein, preferably, the Zr content is more than or equal to 0.26 percent and less than (3.48B-2.67 percent) by weight; the percentage refers to the weight percentage in the R-T-B series permanent magnetic material;
or, the R-T-B series permanent magnetic material comprises the following components: r: 28.1-33.1 wt%, Al: 0.08 to 0.125 wt%, Cu: not less than 0.65 wt%, B: 0.84-0.945 wt%, Fe: 64.6 to 70.1 wt%, Zr: 0.19-0.355 wt%; wherein, preferably, the content of Zr is more than or equal to 0.20 percent and less than (3.48B-2.67 percent) percent by weight; the percentage refers to the weight percentage in the R-T-B series permanent magnet material.
4. A raw material composition of an R-T-B series permanent magnetic material is characterized by comprising: r, Cu, B, Al and Fe, and also comprises one or more of Ti, Zr and Nb, and the content is as follows in percentage by weight:
r: 28.0-33.0 wt%; r is a rare earth element at least containing Nd;
Cu：≥0.4wt％；
Al：0.05-0.07wt％；
B：0.84-0.94wt％；
fe: 64.6 to 70.1 weight percent; wherein:
when the R-T-B series permanent magnet material contains Ti, the content of the Ti is 0.15-0.25 wt%;
when the R-T-B series permanent magnet material contains Zr, the content of Zr is 0.2-0.35 wt%;
when the R-T-B series permanent magnet material contains Nb, the content of Nb is 0.2-0.5 wt%;
the R-T-B series permanent magnet material does not contain Co.
5. The R-T-B-based permanent magnetic material according to claim 4, wherein the amount of R is 28.5 to 33.0 wt%, such as 28.5 wt%, 29.5 wt%, 30.0 wt%, 30.5 wt%, 31.0 wt%, 32.0 wt% or 33.0 wt%, which is a weight percentage in a raw material composition of the R-T-B-based permanent magnetic material;
and/or the Nd content is 17.5-26.0 wt%, such as 21.375 wt%, 22.125 wt%, 22.5 wt%, 22.875 wt%, 23.25 wt%, 24.0 wt% or 24.75 wt%, the percentage referring to the weight percentage in the raw material composition of the R-T-B series permanent magnetic material;
and/or, the R also comprises Pr and/or heavy rare earth RH; wherein, the content of Pr is preferably 2.5-12.0 wt%, such as 7.125 wt%, 7.375 wt%, 7.5 wt%, 7.625 wt%, 7.75 wt%, 8.0 wt% or 8.25 wt%, and the percentage refers to the weight percentage in the raw material composition of the R-T-B series permanent magnetic material; the RH can be Tb or Dy in type; the RH may be present in an amount of 1.5-6.0 wt.%, for example 2.0 wt.%, percentages referring to weight percentages in the raw material composition of the R-T-B based permanent magnetic material; when the R also comprises Pr, the atomic percentage of B/(Pr + Nd) is preferably more than or equal to 0.405;
and/or the raw material composition of the R-T-B series permanent magnetic material does not contain Ga;
and/or the Al content is 0.06-0.07 wt%, such as 0.06 wt% or 0.07 wt%, the percentage refers to the weight percentage in the raw material composition of the R-T-B series permanent magnetic material;
and/or the Cu content is 0.4-2.0 wt%, such as 0.4 wt%, 0.45 wt%, 0.5 wt%, 0.55 wt%, 0.6 wt%, 0.65 wt%, 0.7 wt%, 0.8 wt%, 1.0 wt%, 1.4 wt%, 1.5 wt%, 1.8 wt%, or 2.0 wt%, the percentage referring to the weight percentage in the raw material composition of the R-T-B series permanent magnetic material;
or the content of Cu is more than or equal to 0.4 wt%, such as more than or equal to 0.45 wt% and less than 0.65 wt% or more than or equal to 0.65 wt%, and the percentage refers to the weight percentage in the raw material composition of the R-T-B series permanent magnetic material;
and/or the content of B is 0.86-0.94 wt%, such as 0.86 wt%, 0.88 wt%, 0.9 wt%, 0.915 wt%, 0.92 wt% or 0.94 wt%, the percentage refers to the weight percentage in the raw material composition of the R-T-B series permanent magnetic material;
or the content of the B is more than or equal to 0.915 wt% or more than or equal to 5.55 at%; preferably, the amount of B is the greater of 0.915 wt% and 5.55 at%; wt% means a weight percentage in a raw material composition of the R-T-B system permanent magnetic material, at% means an atomic percentage in a raw material composition of the R-T-B system permanent magnetic material;
and/or the content of Fe is 64.675-70.06 wt%, such as 64.675 wt%, 64.885 wt%, 64.99 wt%, 65.07 wt%, 65.51 wt%, 65.93 wt%, 65.955 wt%, 65.96 wt%, 66.615 wt%, 66.855 wt%, 66.9 wt%, 66.925 wt%, 66.96 wt%, 67.055 wt%, 67.1 wt%, 67.46 wt%, 67.65 wt%, 67.71 wt%, 67.78 wt%, 67.84 wt%, 67.94 wt%, 68.135 wt%, 68.28 wt%, 68.315 wt%, 68.43 wt%, 68.93 wt%, 68.97 wt%, 69.165 wt% or 70.06 wt%, the percentage referring to the weight percentage in the raw material composition of the R-T-B system permanent magnetic material;
and/or, when said R-T-B based permanent magnetic material comprises Ti, said Ti content is 0.2-0.25 wt%, such as 0.2 wt% or 0.25 wt%, percentage referring to the weight percentage in the raw material composition of said R-T-B based permanent magnetic material;
and/or, when the R-T-B series permanent magnetic material contains Zr, the content of Zr is 0.26-0.35 wt%, such as 0.26 wt%, 0.28 wt%, 0.3 wt%, 0.34 wt% or 0.35 wt%, and the percentage refers to the weight percentage in the raw material composition of the R-T-B series permanent magnetic material;
and/or, when the R-T-B series permanent magnetic material contains Nb, the content of Nb is 0.3-0.5 wt%, such as 0.30 wt%, 0.40 wt% or 0.5 wt%, and the percentage refers to the weight percentage in the raw material composition of the R-T-B series permanent magnetic material;
alternatively, when Zr is contained in the raw material composition of the R-T-B series permanent magnetic material, the Zr content is 0.20 wt% or more and less than Zr (3.48B-2.67) wt%, for example 0.26 wt% or less and less than Zr (3.48B-2.67) wt%, and the percentage refers to the weight percentage in the raw material composition of the R-T-B series permanent magnetic material.
6. The R-T-B series permanent magnetic material according to claim 4 or 5, wherein the raw material composition of the R-T-B series permanent magnetic material comprises the following components: r: 28.0-33.0 wt%, Al: 0.05 to 0.07 wt%, Cu: not less than 0.45 wt%, B: 0.84-0.94 wt%, Fe: 64.6-70.1 wt%, Ti: 0.15-0.25 wt%, the percentage refers to the weight percentage in the raw material composition of the R-T-B series permanent magnetic material;
or the raw material composition of the R-T-B series permanent magnet material comprises the following components: r: 28.0-33.0 wt%, Al: 0.05 to 0.07 wt%, Cu: 0.45-0.65 wt%, B: 0.84-0.94 wt%, Fe: 64.6 to 70.1 wt%, Zr: 0.20-0.35 wt%; wherein, preferably, the Zr content is more than or equal to 0.26 percent and less than (3.48B-2.67 percent) by weight; the percentage refers to the weight percentage in the raw material composition of the R-T-B series permanent magnetic material;
or the raw material composition of the R-T-B series permanent magnet material comprises the following components: r: 28.0-33.0 wt%, Al: 0.05 to 0.07 wt%, Cu: not less than 0.65 wt%, B: 0.84-0.94 wt%, Fe: 64.6 to 70.1 wt%, Zr: 0.20-0.35 wt%; wherein, preferably, the content of Zr is more than or equal to 0.20 percent and less than (3.48B-2.67 percent) percent by weight; the percentage refers to the weight percentage in the raw material composition of the R-T-B series permanent magnet material.
7. A preparation method of an R-T-B series permanent magnetic material is characterized by comprising the following steps:
casting, hydrogen fracturing, forming, sintering and aging a melt of a raw material composition of the R-T-B system permanent magnetic material according to any one of claims 4 to 6; wherein:
the aging treatment comprises primary aging treatment and secondary aging treatment, wherein the temperature of the primary aging treatment is 830-870 ℃.
8. The method for producing an R-T-B-based permanent magnetic material according to claim 7, wherein the melt of the raw material composition of the R-T-B-based permanent magnetic material is produced by: smelting in a high-frequency vacuum induction smelting furnace; the vacuum degree of the smelting furnace can be 5 multiplied by 10-2Pa; the smelting temperature can be below 1500 ℃;
and/or the casting process is carried out according to the following steps: in Ar atmosphere, at 102DEG C/sec-104Cooling at the speed of DEG C/second; the cooling can be realized by introducing cooling water into the roller, and preferably, the water inlet temperature of the roller is less than or equal to 25 ℃, such as 23.1 ℃, 23.4 ℃, 23.6 ℃, 23.7 ℃, 23.9 ℃, 24.2 ℃ or 24.5 ℃;
and/or the hydrogen cracking process is carried out according to the following steps: performing hydrogen absorption, dehydrogenation and cooling treatment;
and/or crushing is carried out after the hydrogen crushing, and the crushing process is preferably jet milling; the jet mill pulverization can be carried out in a nitrogen atmosphere with an oxidizing gas content of less than 120 ppm; the pressure of a crushing chamber for crushing by the jet mill can be 0.38 MPa; the jet mill can be used for crushing for 3 hours;
and/or the forming method is a magnetic field forming method or a hot-pressing hot-deformation method;
and/or the sintering process is carried out according to the following steps: preheating, sintering and cooling under a vacuum condition to obtain the product; the preheating temperature can be 300-600 ℃, the preheating time can be 1-2h, and preferably, the preheating is carried out for 1h at the temperature of 300 ℃ and 600 ℃; the sintering temperature may be 1040-; the sintering time may be 5-10h, for example 8 h;
and/or the temperature of the primary aging treatment is 840 ℃ and 870 ℃, such as 840 ℃, 845 ℃, 850 ℃, 860 ℃ or 870 ℃;
and/or in the primary aging treatment, the temperature rise rate of raising the temperature to the temperature of the primary aging treatment is 3-5 ℃/min;
and/or the time of the primary aging treatment is 1-6h, such as 3 h;
and/or the temperature of the secondary aging treatment is 430-560 ℃, such as 440-465 ℃, and further such as 440 ℃, 450 ℃, 455 ℃, 460 ℃ or 465 ℃;
and/or in the secondary aging treatment, the temperature rise rate of raising the temperature to the temperature of the secondary aging treatment is 3-5 ℃/min;
and/or the treatment time of the secondary ageing is 1-6h, for example 3 h.
9. The R-T-B series permanent magnetic material prepared by the preparation method of the R-T-B series permanent magnetic material according to claim 7 or 8.
10. Use of the R-T-B series permanent magnetic material according to any one of claims 1 to 3 and 9 as an electronic component.
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