NEODYMIUM-IRON-BORON MAGNET MATERIAL, RAW MATERIAL COMPOSITION,PREPARATION METHOD THEREFOR AND USE THEREOF

20220328218 · 2022-10-13

    Inventors

    Cpc classification

    International classification

    Abstract

    Disclosed are a neodymium-iron-boron magnet material, a raw material composition, a preparation method therefor and a use thereof. The raw material composition of the neodymium-iron-boron magnet material comprises the following components by mass percentage: 29.5-32% of R′, wherein R′ is a rare earth element and includes Pr and Nd; and Pr≥17.15%; 0.25-1.05% of Ga; 0.9-1.2% of B; and 64-69% of Fe. Without adding a heavy rare earth element to the neodymium-iron-boron magnet material, the remanence and coercive force of the resulting neodymium-iron-boron magnet material are both relatively high.

    Claims

    1. A raw material composition of neodymium-iron-boron magnet material, which comprises the following components by mass percentage: 29.5-32% of R′, wherein R′ refers to rare earth elements, R′ comprises Pr and Nd; wherein, Pr≥17.15%; 0.25-1.05% of Ga; 0.9-1.2% of B; 64-69% of Fe; the percentage refers to the mass percentage of the content of each component in the total mass of the raw material composition of neodymium-iron-boron magnet material.

    2. The raw material composition according to claim 1, wherein, the content of Pr is 17.15-29% or, the content of Ga is 0.25-1%.

    3. The raw material composition according to claim 1, which comprises the following components by mass percentage: 29.5-32% of R′, R′ refers to rare earth elements, R′ comprises Pr and Nd; wherein, Pr≥17.15%; 0.25-1.05% of Ga; Cu≥0.35%; Al≤0.03%; 0.25-0.3% of Zr; 0.9-1.2% of B; 64-69% of Fe.

    4. The raw material composition according to claim 1, which comprises the following components by mass percentage: 29.5-32% of R′, R′ refers to rare earth elements, R′ comprises Pr and Nd; wherein, Pr≥17.15%; 0.25-1.05% of Ga; Mn≤0.02%; 0.25-0.3% of Zr; 0.9-1.2% of B; 64-69% of Fe.

    5. A preparation method for neodymium-iron-boron magnet material, which employs the raw material composition according to claim 1 for preparing; the preparation method comprises the following steps: subjecting the molten liquid of the raw material composition to melting and casting, hydrogen decrepitation, forming, sintering, and aging treatment.

    6. A neodymium-iron-boron magnet material, which is prepared by the preparation method according to claim 5.

    7. A neodymium-iron-boron magnet material, which comprises the following components by mass percentage: 29.5-32% of R′, R′ comprises Pr and Nd; wherein, Pr≥17.15%; 0.245-1.05% of Ga; 0.9-1.2% of B; 64-69% of Fe; the percentage refers to the mass percentage of the content of each component in the total mass of the neodymium-iron-boron magnet material.

    8. The neodymium-iron-boron magnet material according to claim 7, wherein, the content of Pr is 17.15-29% or, the content of Ga is 0.247-1.03%.

    9. A neodymium-iron-boron magnet material, wherein, in the intergranular triangle region of the neodymium-iron-boron magnet material, the ratio of the total mass of Pr and Ga to the total mass of Nd and Ga≤1.0; at the grain boundary of the neodymium-iron-boron magnet material, the ratio of the total mass of Pr and Ga to the total mass of Nd and Ga≥0.1.

    10. A use of the neodymium-iron-boron magnet material according to claim 7 as an electronic component in a motor.

    11. The raw material composition according to claim 1, wherein, the content of Nd is 1.85-14%; or, the ratio of the mass of Nd to the total mass of R′ is 0.5 or less; or, the content of B is 0.95-1.2%; or, the content of Fe is 65-68.3%; or, R′ further comprises other rare earth elements other than Pr and Nd.

    12. The raw material composition according to claim 1, wherein, R′ further comprises RH, RH refers to heavy rare earth elements; RH comprises one or more of Dy, Tb and Ho; the mass ratio of RH to R′ is <0.253; the content of RH is 1-2.5%.

    13. The raw material composition according to claim 12, wherein, when RH contains Tb, the content of Tb is 0.5%-2%; or, when RH contains Dy, the content of Dy is 1% or less; or, when RH contains Ho, the content of Ho is 0.8-2%.

    14. The raw material composition according to claim 1, wherein, the raw material composition of neodymium-iron-boron magnet material further comprises Cu; the content of Cu is 0.1-0.8%; or, the raw material composition of neodymium-iron-boron magnet material further comprises Al; the content of Al is 1% or less; or, the raw material composition of neodymium-iron-boron magnet material further comprises Zr; the content of Zr is 0.4% or less; or, the raw material composition of neodymium-iron-boron magnet material further comprises Co; the content of Co is 0.5-2%; or, the raw material composition of neodymium-iron-boron magnet material further comprises Mn; the content of Mn is 0.02% or less; or, the raw material composition of neodymium-iron-boron magnet material further comprises one or more of Zn, Ag, In, Sn, V, Cr, Mo, Ta, Hf and W.

    15. The preparation method for neodymium-iron-boron magnet material according to claim 5, wherein, after sintering and before the aging treatment, a grain boundary diffusion treatment is further carried out.

    16. The neodymium-iron-boron magnet material according to claim 7, wherein, the content of Nd is 1.85-14%; or, the ratio of the mass of Nd to the total mass of R′ is <0.5; or, the content of B is 0.95-1.2%; or, the content of Fe is 64.8-68.2%; or, R′ further comprises other rare earth elements other than Pr and Nd.

    17. The neodymium-iron-boron magnet material according to claim 7, wherein, R′ further comprises RH, RH refers to heavy rare earth elements, RH comprises one or more of Dy, Tb and Ho; the mass ratio of RH and R′ is <0.253; the content of RH is 1-2.5%.

    18. The neodymium-iron-boron magnet material according to claim 17, wherein, when RH comprises Tb, the content of Tb is 0.5-2.01%; or, when RH comprises Dy, the content of Dy is 1.05% or less; or, when RH comprises Ho, the content of Ho is 0.8-2%.

    19. The neodymium-iron-boron magnet material according to claim 7, wherein, the neodymium-iron-boron magnet material further comprises Cu; the content of Cu is 0.1-0.9%; or, the neodymium-iron-boron magnet material further comprises Al; the content of Al is 1.1 wt. % or less; or, the neodymium-iron-boron magnet material further comprises Zr; the content of Zr is 0.4% or less; or, the neodymium-iron-boron magnet material further comprises Co; the content of Co is 0.5-2%; or, the neodymium-iron-boron magnet material further comprises Mn; the content of Mn is 0.02% or less; or, the neodymium-iron-boron magnet material further comprises O; the content of O is 0.13% or less; or, the neodymium-iron-boron magnet material further comprises one or more of Zn, Ag, In, Sn, V, Cr, Mo, Ta, Hf and W.

    20. The neodymium-iron-boron magnet material according to claim 7, wherein, in the intergranular triangle region of the neodymium-iron-boron magnet material, the ratio of the total mass of Pr and Ga to the total mass of Nd and Ga≤1.0; at the grain boundary of the neodymium-iron-boron magnet material, the ratio of the total mass of Pr and Ga to the total mass of Nd and Ga≥0.1.

    Description

    BRIEF DESCRIPTION OF THE DRAWINGS

    [0114] FIG. 1 shows the element distribution diagram formed by FE-EPMA surface scan of the neodymium-iron-boron magnet material prepared in Example 23.

    [0115] FIG. 2 shows the element distribution diagram at the grain boundary of the neodymium-iron-boron magnet material prepared in Example 23, and 1 in the figure shows the point taken by quantitative analysis at the grain boundary.

    [0116] FIG. 3 shows the element distribution diagram of the intergranular triangular region of the neodymium-iron-boron magnet material prepared in Example 23, and 1 in the figure shows the point taken by quantitative analysis in the intergranular triangular region.

    DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

    [0117] The following examples further illustrate the present disclosure, but the present disclosure is not limited thereto. Experiment methods in which specific conditions are not indicated in the following embodiments are selected according to conventional methods and conditions, or according to the product specification. The wt. % in the following tables refers to the mass percentage of the content of each component in the total mass of the raw material composition of neodymium-iron-boron magnet material, and “I” indicates that the element was not added. “Br” refers to the residual magnetic flux density and “Hcj” refers to the intrinsic coercivity.

    [0118] The formulations of the raw material compositions of the neodymium-iron-boron magnet material in the examples and the comparative examples are shown in Table 1 below.

    TABLE-US-00001 TABLE 1 Formulations for the raw material compositions of the neodymium-iron-boron magnet materials in the examples and the comparative examples (wt. %) No. Nd Pr Dy Tb Ho Ga Cu Al Zr Co Mn Zn Mo B Fe 1 13.85 17.15 / / / 0.25 / / / / / / / 0.985 67.765 2 13.85 17.15 / / / 0.27 / / / / / / / 0.985 67.745 3 12.35 18.15 / / / 0.29 / / / / / / / 0.985 68.225 4 12.85 18.15 / / / 0.31 / / / / / / / 0.985 67.705 5 12.35 19.15 / / / 0.33 / / / / / / / 0.985 67.185 6 12.85 19.15 / / / 0.35 / / / / / / / 0.985 66.665 7 11.35 20.15 / / / 0.37 / / / / / / / 0.985 67.145 8 11.35 20.15 / / / 0.39 / / / / / / / 0.985 67.125 9 10.85 21.15 / / / 0.41 / / / / / / / 0.985 66.605 10 10.65 21.15 / / / 0.43 / / / / / / / 0.985 66.785 11 8.85 22.15 / / / 0.45 / / / / / / / 0.95 67.6 12 7.85 23.15 / / / 0.47 / / / / / / / 0.96 67.57 13 6.85 24.15 / / / 0.49 / / / / / / / 0.97 67.54 14 5.85 25.15 / / / 0.6 / / / / / / / 0.98 67.42 15 4.85 26.15 / / / 0.7 / / / / / / / 0.99 67.31 16 3.85 27.15 / / / 0.8 / / / / / / / 0.985 67.215 17 2.85 27.85 / / / 0.9 / / / / / / / 0.985 67.415 18 1.85 28.85 / / / 1.0 / / / / / / / 0.985 67.315 19 13.65 17.15 / / / 0.3 0.1 / / / / / / 0.985 67.815 20 13.35 17.15 / / / 0.47 0.25 / / / / / / 0.985 67.795 21 10.85 21.15 / / / 0.53 0.5 / / / / / / 0.985 65.985 22 10.85 21.15 / / / 1.0 0.7 / / / / / / 0.985 65.315 23 7.85 23.15 / / / 0.49 / 0.2 / / / / / 0.985 67.325 24 7.85 23.15 / / / 0.51 / 0.45 / / / / / 0.985 67.055 25 5.85 24.15 / 2 / 0.53 / 0.6 / / / / / 1 65.87 26 5.85 24.15 0.3 1.7 / 0.55 / 0.8 / / / / / 1.1 65.55 27 9.85 20.15 0.3 1.2 / 0.57 / / 0.1 / 0.01  / / 1.2 66.62 28 9.85 20.15 0.1 1.4 / 0.28 / / 0.25 / 0.015 / / 1.2 66.755 29 11.15 20.15 / 0.5 / 0.32 / / 0.28 / 0.013 / / 0.985 66.602 30 11.15 20.15 / 0.5 / 0.36 / / 0.3 / 0.018 / / 0.985 66.537 31 6.15 23.15 0.1 1.5 / 0.7 / / 0.35 / / / / 0.985 67.065 32 6.15 23.15 0.2 1.4 / 0.8 / / 0.4 / / / / 0.985 66.915 32.1 7.85 23.15 0.5 / / 0.85 / / 0.25 / 0.01  / / 0.985 66.405 32.2 7.85 23.15 / 1 / 0.95 / / 0.3 / 0.013 / / 0.985 65.752 33 6.85 24.15 0.3 0.7 / 1.0 / / / 1 / / / 0.985 65.015 34 6.85 24.15 0.3 0.7 / 0.25 0.1 0.2 / / / / / 0.985 66.465 35 6.85 24.15 0.3 0.7 / 0.4 0.2 0.4 / / / / / 0.985 66.015 36 5.85 24.15 0.2 0.8 / 0.5 0.4 0.6 / / / / / 0.985 66.515 37 5.85 24.15 0.2 0.8 / 1.0 0.8 1 / / / / / 0.985 65.215 38 12.35 19.15 / / / 0.3 0.2 / 0.1 / / / / 0.985 66.915 39 11.75 19.15 / / / 1.0 0.4 / 0.25 / / / / 0.985 66.465 40 12.35 17.15 0.3 0.7 / 0.3 / 0.05 0.1 / / / / 0.985 68.065 41 12.35 17.15 0.3 0.7 / 0.35 / 0.1 0.25 / / / / 0.985 67.815 42 11.75 19.15 / / / 0.45 / 0.3 0.28 / / / / 0.985 67.085 43 11.75 19.15 / / / 0.6 / 0.6 0.3 / / / / 0.985 66.615 44 12.85 18.15 / / / 0.25 0.35 0.02 0.15 / / / / 0.985 67.245 45 12.85 18.15 / / / 0.28 0.45 0.03 0.25 / / / / 0.985 67.005 46 11.75 19.15 / / / 0.36 0.48 0.1 0.26 / / / / 0.985 66.915 47 11.75 19.15 / / / 0.38 0.5 0.03 0.27 / / / / 0.985 66.935 48 9.85 20.15 0.2 1 / 0.55 0.55 0.02 0.28 / / / / 0.985 66.415 49 9.85 20.15 0.2 1 / 0.6 0.58 0.03 0.29 / / / / 0.985 66.315 49.1 6.15 23.15 / 2 / 0.7 0.35 0.02 0.25 / / / / 0.985 66.395 49.2 6.15 23.15 / 1 / 0.8 0.45 0.02 0.25 / / / / 0.985 67.195 49.3 5.85 25.15 1 / 0.9 0.45 0.03 0.3 / / / / 0.985 65.335 49.4 5.85 25.15 / / / 1 0.5 0.03 0.3 / / / / 0.985 66.185 50 9.55 20.15 0.2 1 1 0.3 / 0.05 / / / 0.02 0.05 0.985 66.695 51 11.75 19.15 / / 1 0.45 / 0.12 / / / 0.05 0.02 0.985 66.475 52 12.85 18.15 / / 1 0.6 / 0.15 / / / 0.05 0.05 0.985 66.165 55 6.85 24.15 / / / 0.1 0.1 0.2 / / / / / 0.985 67.615 56 6.85 24.15 / / / 0.2 0.1 0.2 / / / / / 0.985 67.515 57 15.15 15.85 / / / 0.25 0.1 0.2 / / / / / 0.985 67.465 58 22.15 8.85 / / / 0.25 0.1 0.2 / / / / / 0.985 67.465

    Example 1

    [0119] The neodymium-iron-boron magnet materials were prepared as follows:

    [0120] (1) Melting and casting process: according to the formulations shown in Table 1, the prepared raw materials were put into a crucible made of alumina and vacuum melted in a high-frequency vacuum induction melting furnace and in a vacuum of 5×10.sup.−2 Pa at a temperature of 1500° C. or less. After vacuum melting, the melting furnace was fed with Ar gas to make the air pressure reach 5.5×10.sup.4 Pa and then casting was carried out, and a cooling rate of 10.sup.2° C./sec-10.sup.4° C./sec was used to obtain the quench alloy.

    [0121] (2) Hydrogen decrepitation process: the melting furnace with quench alloy placed therein was evacuated at room temperature, and then hydrogen gas of 99.9% purity was passed into the furnace for hydrogen decrepitation to maintain the hydrogen pressure at 0.15 MPa; after sufficient hydrogen absorption, it was sufficiently dehydrogenated by heating up while vacuum-pumping; then it was cooled and the powder after hydrogen decrepitation was taken out.

    [0122] (3) Micro-pulverization process: the powder after hydrogen decrepitation was pulverized by jet mill for 3 hours in nitrogen atmosphere with oxidizing gas content of 150 ppm or less and under the condition of the pressure of 0.38 MPa in the pulverization chamber, and fine powder was obtained. The oxidizing gas refers to oxygen or moisture.

    [0123] (4) Zinc stearate was added to the powder after jet mill pulverization, and the addition amount of zinc stearate was 0.12% by weight of the mixed powder, and then it was mixed thoroughly by using a V-mixer.

    [0124] (5) Magnetic field forming process: a rectangular oriented magnetic field forming machine was used to conduct primary forming of the above-mentioned powder with zinc stearate into a cube with sides of 25 mm in an orientation magnetic field of 1.6 T and a forming pressure of 0.35 ton/cm.sup.2; after the primary forming, it was demagnetized in a magnetic field of 0.2 T. In order to prevent the formed body after the primary forming from contacting with air, it was sealed, and then secondary forming was carried out at a pressure of 1.3 ton/cm.sup.2 using a secondary forming machine (isostatic forming machine).

    [0125] (6) Sintering process: each formed body was moved to a sintering furnace for sintering, the sintering was maintained under a vacuum of 5×10.sup.−3 Pa and at a temperature of 300° C. and 600° C. for 1 hour, respectively; then, sintered at a temperature of 1040° C. for 2 hours; and then Ar gas was passed in to make the air pressure reach 0.1 MPa, and cooled to room temperature to obtain sintered body.

    [0126] (7) Aging treatment process: the sintered body was heat treated in high purity Ar gas at a temperature of 500° C. for 3 hours and then cooled to room temperature and taken out.

    Example 53 Using Dy Grain Boundary Diffusion Method

    [0127] The raw material composition of Example 1 in Table 1 was first prepared according to the preparation of the sintered body of Example 1 to obtain a sintered body, followed by grain boundary diffusion, and then aging treatment. Wherein the process of aging treatment is the same as in Example 1, and the processing procedure of grain boundary diffusion is as follows:

    [0128] The sintered body was processed into a magnet with a diameter of 20 mm and a thickness of less than 3 mm, and the thickness direction is the magnetic field orientation direction, after the surface was cleaned, the raw materials formulated with Dy fluoride were used to coat the magnet through a full spray, and the coated magnet was dried, and the metal with Tb element was attached to the magnet surface by sputtering in a high-purity Ar gas atmosphere, diffusion heat treatment was carried out at a temperature of 850° C. for 24 hours. Cooled to room temperature.

    Example 54 Using Tb Grain Boundary Diffusion Method

    [0129] The number 1 in Table 1 was first prepared according to the preparation of the sintered body of Example 1 to obtain a sintered body, followed by grain boundary diffusion, and then aging treatment. Wherein the process of aging treatment is the same as in Example 1, and the processing procedure of grain boundary diffusion is as follows:

    [0130] The sintered body was processed into a magnet with a diameter of 20 mm and a thickness of less than 7 mm, and the thickness direction is the magnetic field orientation direction, after the surface was cleaned, the raw materials formulated with Tb fluoride were used to coat the magnet through a full spray, and the coated magnet was dried, and the metal with Tb element was attached to the magnet surface by sputtering in a high-purity Ar gas atmosphere, diffusion heat treatment was carried out at a temperature of 850° C. for 24 hours. Cooled to room temperature.

    Effect Example

    [0131] The magnetic properties and compositions of the neodymium-iron-boron magnet materials made in Examples 1-54 and Comparative Examples 55-58 were measured, and the crystalline phase structure of the magnets was observed using a field emission electron probe microanalyzer (FE-EPMA).

    [0132] (1) Magnetic properties evaluation: The magnetic properties were examined using the NIM-10000H type BH bulk rare earth permanent magnet nondestructive measurement system in National Institute of Metrology, China. The following Table 2 indicates the magnetic property testing results.

    TABLE-US-00002 TABLE 2 Absolute Absolute Absolute value of Hcj value of Hcj value of Hcj temperature temperature temperature coefficient at coefficient at coefficient at No. Br(kGs) Hcj(kOe) 80° C. 150° C. 180° C. 1 14.12 18.24 0.689 / / 2 14.09 18.38 0.685 / / 3 14.34 18.07 0.692 / / 4 14.21 18.55 0.672 / / 5 13.90 19.52 0.668 / / 6 13.79 19.88 0.664 / / 7 13.81 20.04 0.648 / / 8 13.79 20.18 0.642 / / 9 13.72 20.79 0.638 / / 10 13.74 20.84 0.632 / / 11 13.91 20.88 0.631 / / 12 13.93 21.27 0.612 / / 13 13.88 21.52 0.609 / / 14 13.73 22.66 0.591 / / 15 13.58 23.55 0.577 / / 16 13.46 24.52 / 0.532 17 13.38 25.01 / 0.518 / 18 13.23 25.8 / 0.513 / 19 14.07 19.03 0.673 / / 20 13.92 20.18 0.649 / / 21 13.05 24.07 / 0.556 / 22 12.45 28.23 / 0.503 / 23 13.98 21.88 0.623 / / 24 13.75 22.61 0.617 / / 25 12.7 30.6 / / 0.437 26 12.5 30.9 / / 0.435 27 13.35 26.2 / 0.513 / 28 13.4 24.64 / 0.530 / 29 13.6 21.75 0.605 / / 30 13.57 22.03 0.619 / / 31 13.82 26.32 / 0.509 / 32 13.75 26.91 / 0.506 / 32.1 13.21 25.65 / 0.518 32.2 12.79 28.89 / 0.496 33 12.7 28.63 / 0.495 / 34 13.3 24.53 / 0.535 / 35 13.1 26.03 / 0.519 / 36 12.95 28.33 / 0.502 / 37 11.72 33.83 / / 0.422 38 13.66 20.47 0.638 / / 39 12.9 25.9 / 0.513 / 40 13.94 21.63 0.623 / / 41 13.9 22.19 0.624 / / 42 13.93 20.97 0.633 / / 43 13.7 22.72 0.611 / / 44 13.68 20.38 0.641 / / 45 13.47 21.17 0.629 / / 46 13.33 22.24 0.617 / / 47 13.51 22.48 0.615 / / 48 13.09 27.27 / 0.516 / 49 13.05 27.79 / 0.512 / 49.1 12.89 31.2 / / 0.439 49.2 13.18 28.28 / 0.492 / 49.3 12.73 28.73 / 0.488 / 49.4 12.68 29.43 / 0.471 / 50 13.43 23.51 0.573 / / 51 12.85 25.57 / 0.518 / 52 12.68 26.37 / 0.512 / 53 13.95 24.5 / 0.535 / 54 13.98 29.3 / 0.472 / 55 13.85 18.69 0.668 / / 56 13.82 18.75 0.666 / / 57 13.95 17.51 0.672 / / 58 14.19 15.79 0.749 / /

    [0133] (2) Composition determination: the components were determined using a high-frequency inductively coupled plasma emission spectrometer (ICP-OES). The following Table 3 shows the results of the composition testing.

    TABLE-US-00003 TABLE 3 Composition test results (wt. %) No. Nd Pr Dy Tb Ho Ga Cu Al Zr Co Mn Zn Mo B Fe 1 13.848 17.151 / / / 0.248 / / / / / / / 0.984 67.769 2 13.856 17.150 / / / 0.268 / / / / / / / 0.987 67.784 3 12.451 18.132 / / / 0.291 / / / / / / / 0.983 68.143 4 12.89 18.148 / / / 0.312 / / / / / / / 0.983 67.667 5 12.345 19.149 / / / 0.332 / / / / / / / 0.986 67.188 6 12.851 19.149 / / / 0.352 / / / / / / / 0.984 66.664 7 11.355 20.147 / / / 0.371 / / / / / / / 0.987 67.14 8 11.352 20.148 / / / 0.392 / / / / / / / 0.983 67.125 9 10.851 21.146 / / / 0.413 / / / / / / / 0.983 66.607 10 10.651 21.148 / / / 0.433 / / / / / / / 0.986 66.782 11 8.851 22.148 / / / 0.452 / / / / / / / 0.949 67.6 12 7.852 23.149 / / / 0.472 / / / / / / / 0.956 67.571 13 6.853 24.151 / / / 0.492 / / / / / / / 0.969 67.535 14 5.852 25.152 / / / 0.589 / / / / / / / 0.982 67.425 15 4.852 26.151 / / / 0.712 / / / / / / / 0.991 67.294 16 3.848 27.152 / / / 0.82 / / / / / / / 0.985 67.195 17 2.848 27.851 / / / 0.912 / / / / / / / 0.984 67.405 18 1.852 28.852 / / / 1.03 / / / / / / / 0.987 67.279 19 13.651 17.149 / / / 0.301 0.1  / / / / / / 0.983 67.816 20 13.348 17.147 / / / 0.471 0.25  / / / / / / 0.983 67.801 21 10.848 21.148 / / / 0.531 0.5  / / / / / / 0.984 65.989 22 10.849 21.148 / / / 1.02 0.7  / / / / / / 0.987 65.296 23 7.849 23.148 / / / 0.491 / 0.202 / / / / / 0.983 67.327 24 7.849 23.147 / / / 0.512 / 0.451 / / / / / 0.983 67.058 25 5.848 24.148 / 2.001 / 0.531 / 0.603 / / / / / 1.02 65.849 26 5.848 24.148 0.301 1.701 / 0.551 / 0.801 / / / / / 1.11 65.54 27 9.848 20.148 0.302 1.21  / 0.572 / / 0.1 / 0.01  / / 1.19 66.62 28 9.848 20.149 0.101 1.42  / 0.281 / / 0.25 / 0.015 / / 1.18 66.756 29 11.149 20.154 / 0.502 / 0.323 / / 0.28 / 0.013 / / 0.984 66.595 30 11.148 20.151 / 0.503 / 0.361 / / 0.3 / 0.018 / / 0.987 66.532 31 6.147 23.152 0.101 1.492 / 0.703 / / 0.35 / / / / 0.983 67.072 32 6.148 23.152 0.202 1.402 / 0.804 / / 0.4 / / / / 0.983 66.909 32.1 7.846 23.152 0.51  / / 0.848 / / 0.248 / 0.02  / / 0.984 66.392 32.2 7.851 23.15 / 1.02  / 0.951 / / 0.301 / 0.014 / / 0.984 65.729 33 6.847 24.151 0.303 0.702 / 1.03 / / / 1 / / / 0.986 64.981 34 6.846 24.152 0.301 0.703 / 0.252 0.102 0.202 / / / / / 0.984 66.458 35 6.848 24.151 0.302 0.704 / 0.402 0.205 0.402 / / / / / 0.984 66.002 36 5.845 24.152 0.202 0.802 / 0.502 0.405 0.602 / / / / / 0.987 66.503 37 5.85 24.152 0.203 0.802 / 1.03 0.803 1.02 / / / / / 0.983 65.157 38 12.347 19.153 / / / 0.302 0.202 / 0.1 / / / / 0.983 66.913 39 11.748 19.151 / / / 1.02 0.402 / 0.25 / / / / 0.984 66.445 40 12.347 17.149 0.301 0.703 / 0.303 / 0.04 0.1 / / / / 0.987 68.07 41 12.35 17.145 0.301 0.705 / 0.351 / 0.102 0.25 / / / / 0.983 67.813 42 11.746 19.146 / / / 0.451 / 0.301 0.28 / / / / 0.983 67.093 43 11.748 19.149 / / / 0.602 / 0.601 0.3 / / / / 0.986 66.614 44 12.848 18.148 / / / 0.251 0.352 0.02 0.15 / / / / 0.984 67.247 45 12.848 18.146 / / / 0.281 0.451 0.03 0.25 / / / / 0.987 67.007 46 11.751 19.149 / / / 0.362 0.481 0.101 0.26 / / / / 0.984 66.912 47 11.752 19.148 / / / 0.38 0.502 0.02 0.27 / / / / 0.987 66.941 48 9.852 20.147 0.202 1.01  / 0.55 0.552 0.02 0.28 / / / / 0.983 66.404 49 9.851 20.146 0.203 1.02  / 0.6 0.581 0.03 0.29 / / / / 0.983 66.296 49.1 6.149 23.151 / 2.01  / 0.701 0.351 0.01 0.251 / / / / 0.984 66.393 49.2 6.151 23.151 / 1.02  / 0.791 0.452 0.01 0.252 / / / / 0.986 67.187 49.3 5.852 25.152 1.03  / / 0.892 0.451 0.03 0.301 / / / / 0.984 65.308 49.4 5.851 25.152 / / / 1.02 0.501 0.04 0.302 / / / / 0.984 66.15 50 9.549 20.148 0.203 1.03  1.02 0.3 / 0.05 / / / 0.01 0.06 0.986 66.644 51 11.747 19.148 / / 1.01 0.45 / 0.12 / / / 0.06 0.03 0.984 66.451 52 12.848 18.146 / / 0.99 0.6 / 0.15 / / / 0.04 0.03 0.987 66.209 53 13.849 17.152 0.421 / / 0.247 / / / / / / / 0.984 67.347 54 13.848 17.151 / 0.501 / 0.249 / / / / / / / 0.984 67.267 55 6.846 24.148 / / / 0.1 0.101 0.2 / / / / / 0.984 67.621 56 6.845 24.148 / / / 0.2 0.103 0.2 / / / / / 0.987 67.517 57 15.148 15.849 / / / 0.25 0.102 0.2 / / / / / 0.983 67.468 58 22.146 8.849 / / / 0.25 0.102 0.2 / / / / / 0.983 67.47

    [0134] FE-EPMA inspection: the perpendicularly oriented surface of the magnet material of Example 23 was polished and inspected using a field emission electron probe micro-analyzer (FE-EPMA) (Japan Electronics Corporation (JEOL), 8530F). The main elements analyzed are Pr, Nd, Ga, Zr, O, and the elements at the grain boundary and the intergranular triangular region were quantitatively analyzed.

    [0135] FIG. 1 shows the distribution diagram of each element in the neodymium-iron-boron magnet material. From FIG. 1, it can be seen that the Pr and Nd elements are mainly distributed in the main phase, some rare earths also appear in the grain boundary, and the element Ga is also distributed in the main phase and the crystal phase, the element Zr is distributed at the grain boundary.

    [0136] FIG. 2 shows the element distribution at the grain boundary of the neodymium-iron-boron magnet material of Example 23, and the elements at the grain boundary were quantitatively analyzed by taking the point marked by 1 in FIG. 2, the results are shown in Table 4 below:

    TABLE-US-00004 TABLE 4 Pr Nd Ga Zr O Fe (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) 37.8 28.2 5.26 0.08 0.69 Bal

    [0137] From the above data, it can be clearly seen that Pr and Nd exist in the form of rare earth rich phases and oxides in the grain boundaries, α-Pr and α-Nd, Pr.sub.2O.sub.3, Nd.sub.2O.sub.3 and NdO, respectively, and Ga occupies a certain content of about 5.26 wt. % at the grain boundaries in addition to the main phase, Zr is dispersed in the whole region as a high melting point element.

    [0138] FIG. 3 shows the element distribution of the intergranular triangular region of the neodymium-iron-boron magnet materials of Example 23, and the elements in the intergranular triangular region were quantitatively analyzed by taking the point marked by 1 in FIG. 3, and the results are shown in Table 5 below:

    TABLE-US-00005 TABLE 5 Pr Nd Ga Zr O Fe (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) (wt. %) 27.8 29.5 4.95 0.039 0.95 Bal

    [0139] In the intergranular triangular region, Pr and Nd elements are distributed in it, in the formulations with high Pr, it is clearly found that the content of Pr is obviously lower than that of Nd in the intergranular triangular region, although some rare earths are enriched here, the enrichment degree of Pr is less than that of Nd, which is one of the reasons why high Pr and Ga work together to improve the coercivity. At the same time, there is a partial distribution of O and Ga therein.