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WO2020119133A1 - 一种r-t-b永磁材料及其制备方法 - Google Patents

一种r-t-b永磁材料及其制备方法 Download PDF

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WO2020119133A1
WO2020119133A1 PCT/CN2019/097906 CN2019097906W WO2020119133A1 WO 2020119133 A1 WO2020119133 A1 WO 2020119133A1 CN 2019097906 W CN2019097906 W CN 2019097906W WO 2020119133 A1 WO2020119133 A1 WO 2020119133A1
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magnetic material
permanent magnetic
preparing
material according
alloy
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French (fr)
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严长江
钱尼健
傅万成
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Ningbo Ketian Magnet Co Ltd
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Ningbo Ketian Magnet Co Ltd
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Priority to JP2019561144A priority Critical patent/JP7305554B2/ja
Priority to EP19896995.8A priority patent/EP4002397A4/en
Priority to US16/609,932 priority patent/US11837390B2/en
Publication of WO2020119133A1 publication Critical patent/WO2020119133A1/zh
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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
    • H01F1/0555—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together
    • H01F1/0557—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together sintered
    • 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
    • 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
    • H01F41/0273—Imparting anisotropy

Definitions

  • the invention relates to the technical field of rare earth magnetic material preparation, in particular to an R-T-B-containing permanent magnet material and a preparation method thereof.
  • NdFeB permanent magnet material As the third generation rare earth permanent magnet material, NdFeB permanent magnet material has a high magnetic energy product. Can promote the permanent magnet motor miniaturization, light weight and high efficiency. At present, permanent magnet motors have been used in electric vehicles, hybrid vehicles and energy-saving air-conditioning compressors. In these fields, the working environment temperature of magnetic steel is relatively high, usually in the range of 120 ⁇ 200°C. Therefore, only by increasing the coercive force of the magnet can the work requirements in the field of high temperature be met.
  • the traditional preparation process of sintered NdFeB magnets is rapid solidification, hydrogen breaking, airflow grinding, magnetic field orientation, sintering and tempering.
  • the main way to improve the coercivity of the magnet is to add heavy rare earth to the raw material.
  • This method is relatively simple and easy to operate in production, but a large amount of high-coercive force magnets will cause the remanence of the magnets to deteriorate.
  • conventional commercial 42SH magnets need to add 2-3wt% Dy. Normally adding Dy per unit weight increases the coercive force by 2kOe and the remanence decreases by 0.2 to 0.3kGs.
  • the grain boundary diffusion technology is to use a special process on the magnet such as evaporation (H. Sepehri-Amin, T. Ohkubo, and K.
  • This technology is completed with dense sintered magnets. After the heavy rare earth source is placed on the surface, a long-term diffusion aging treatment is required, and the entire magnet production process has a long cycle. In the technical process, heavy rare earth diffuses from the surface along the grain boundary to the inside, and its diffusion depth is limited. Therefore, only thin-film magnets can be prepared, which also results in poor consistency of the coercivity of the magnet.
  • the purpose of the present invention is to provide an R-T-B permanent magnetic material and its preparation method in view of the deficiencies in the prior art.
  • the first object of the present invention is to provide an R-T-B permanent magnet material.
  • R-T-B permanent magnet material the R-T-B permanent magnet material is RxTyTmqBz;
  • R is LRaHR1-a
  • LR is one or a combination of Pr, Nd and PrNd
  • HR is one or a combination of two of Dy and Tb, 0.95 ⁇ a ⁇ 1;
  • T is one or a combination of Fe and Co
  • Tm is a transition metal
  • the Tm is one or a combination of Zr, Al, Cu, Ga, Sn, Si.
  • the main phase grains of the R-T-B permanent magnetic material have a "core-shell" structure.
  • the concentration of HR in the shell is greater than the concentration of HR in the core.
  • the second object of the present invention is to provide a method for preparing R-T-B permanent magnetic materials.
  • a preparation method of R-T-B permanent magnetic material includes the following steps:
  • Step S2 adding the raw materials to a vacuum melting device for smelting and casting to obtain a first alloy sheet
  • Step S3 plating a heavy rare earth film on the first alloy sheet to obtain a second alloy sheet;
  • Step S4 coarsely crush and grind the second alloy sheet to obtain a fine powder
  • Step S5 granulating and pressing the fine powder to obtain a green body
  • Step S6 Perform diffusion sintering and multi-stage tempering treatment on the green body to obtain R-T-B permanent magnetic material.
  • the R is LR a HR 1-a , LR is one or a combination of Pr, Nd and PrNd, and HR is one or two of Dy and Tb The combination;
  • the Tm is a transition metal, and the Tm is one or a combination of Zr, Al, Cu, Ga, Sn, Si.
  • the raw material is smelted under an inert gas
  • the raw material After melting, the raw material is cast at 1400°C to 1500°C.
  • the inert gas is Ar or He.
  • the thickness of the first alloy sheet is 200-300 ⁇ m.
  • the material of the heavy rare earth film is any one or a combination of Dy and Tb.
  • the thickness of the heavy rare earth film is 0-3 ⁇ m.
  • the heavy rare-earth film is plated on the first alloy sheet using a magnetron sputtering device.
  • the target material used by the magnetron sputtering device is any one of Tb, Dy, and HRE-X alloy.
  • the HRE is any one or a combination of Tb and Dy;
  • the X is any one or a combination of Fe and Cu.
  • the main phase grains of the R-T-B permanent magnetic material have a "core-shell" structure
  • the concentration of HR in the shell is greater than the concentration of HR in the core.
  • step S4 it further includes:
  • Step S41 coarsely crushing the second alloy flakes to obtain coarse powder.
  • the conditions of the coarse crushing are: after the mixed gas of H 2 and Ar is fully reacted, dehydrogenation is performed at 350 to 500° C.;
  • Step S42 grinding the coarse powder obtained in step S41 to obtain the fine powder, the grinding condition is: high-speed grinding in a mixed gas of N 2 and O 2 , and the particle size is 1 to 4 ⁇ m.
  • step S5 it further includes:
  • Step S51 mixing and stirring the fine powder with organic matter to obtain a mixture
  • Step S52 placing the mixture in step S51 in N 2 to perform magnetic field orientation molding to obtain the green body.
  • the conditions of the diffusion sintering are:
  • the conditions of the multi-stage tempering treatment are:
  • the first level of tempering treatment temperature is 850 ⁇ 950°C, heat preservation is 2 ⁇ 3h;
  • Second-stage tempering treatment temperature is 450 ⁇ 580°C, heat preservation is 1 ⁇ 5h.
  • the present invention adopts the above technical solutions, and compared with the prior art, has the following technical effects:
  • the RTB permanent magnet material and its preparation method of the present invention use a magnetron sputtering device to plate heavy rare earth film on the alloy sheet, and then go through the processes of coarse crushing, grinding fine powder, orientation forming, diffusion sintering and multi-stage tempering treatment Obtain a sintered NdFeB magnet; compared with the grain boundary diffusion, the entire preparation process is relatively simple, without the need for long-term diffusion heat treatment, and the "core-shell" structure can be obtained to greatly improve the coercivity of the magnet, while not being diffused Depth limitation; compared with the traditional process, in the case of the same heavy rare earth content, higher coercive force and magnetic energy product can be obtained, because the heavy rare earth film coated with heavy rare earth film can be evenly distributed after crushing.
  • the sintered heavy rare earth element diffuses from the surface of the magnet to the inside and forms a heavy rare earth enriched shell along the periphery of the main phase grains of each Nd 2 Fe 14 B, so that it can effectively suppress the formation of demagnetization core and avoid Heavy rare earth enters the main phase excessively, and at the same time forms a hard magnetic phase grain with a "core-shell" structure.
  • FIG. 1 is a flow chart of the preparation process of the R-T-B permanent magnetic material according to an exemplary embodiment of the present invention.
  • FIG. 2 is a schematic diagram of a magnetron sputtering apparatus according to an exemplary embodiment of the present invention.
  • FIG. 3 is a backscattered electron image of the R-T-B permanent magnetic material of Experimental Example 2 of the present invention.
  • the reference signs are: 1 for cleaning chamber, 2 for coating chamber, 3 for primary cooling chamber, 4 for secondary cooling chamber, 5 for first alloy sheet, 6 for heavy rare earth or its alloy target, and 7 for transmission Roller.
  • a method for preparing an R-T-B permanent magnetic material of the present invention includes the following steps:
  • Step S2 Add the raw materials to the vacuum melting device for smelting and casting to obtain the first alloy sheet;
  • Step S3 plating a heavy rare earth film on the first alloy sheet to obtain a second alloy sheet;
  • Step S4 coarsely crush and grind the second alloy sheet to obtain a fine powder
  • Step S5 granulate and compact the fine powder to obtain a green body
  • Step S6 Perform diffusion sintering and multi-stage tempering treatment on the green body to obtain R-T-B permanent magnetic material.
  • the above steps are the basic steps for obtaining R-T-B permanent magnet materials.
  • R is LR a HR 1-a
  • LR is one or a combination of Pr, Nd and PrNd
  • HR is one or a combination of two of Dy and Tb, 0.95 ⁇ a ⁇ 1.
  • Tm is a transition metal
  • Tm is one or a combination of Zr, Al, Cu, Ga, Sn, and Si.
  • step S2 the raw material is smelted under an inert gas.
  • the raw materials are cast at 1400°C to 1500°C.
  • the inert gas is Ar or He.
  • the thickness of the first alloy sheet is 200 to 300 ⁇ m.
  • the material of the heavy rare earth film is any one or a combination of Dy and Tb.
  • the thickness of the heavy rare earth film is 0 to 3 ⁇ m.
  • step S3 the heavy rare-earth film is plated on the first alloy sheet using a magnetron sputtering device.
  • the material used by the magnetron sputtering device is any one or a combination of Tb, Dy, and HRE-X alloy.
  • HRE is any one or a combination of Tb and Dy;
  • X is any one or a combination of Fe and Cu.
  • the crystal grains of the R-T-B permanent magnetic material have a "core-shell" structure.
  • the magnetron sputtering device includes a cleaning chamber 1, a coating chamber 2, a primary cooling chamber 3, and a secondary cooling chamber 4 that are provided in this order, wherein the interior of the coating chamber 2 is provided above There is a heavy rare earth or its alloy target 6 for plating the heavy rare earth film on the first alloy sheet 5 in the coating chamber 2.
  • transmission roller shafts 7 are provided for conveying the first alloy sheet 5.
  • step S4 it further includes:
  • Step S41 coarsely crush the second alloy flakes to obtain coarse powder.
  • the conditions for coarse crushing are: after the mixed gas of H 2 and Ar is fully reacted, dehydrogenation is performed at 350 to 500° C.;
  • Step S42 grinding the coarse powder obtained in step S41 to obtain a fine powder, the grinding conditions are: high-speed grinding in a mixed gas of N 2 and O 2 , and the particle size is 1 to 4 ⁇ m.
  • step S41 hydrogen absorption is performed in a mixed gas of H 2 and Ar at 200 to 450°C.
  • step S41 dehydrogenation is performed at 420 to 500°C.
  • step S5 it further includes:
  • Step S51 mixing and stirring the fine powder with the organic matter to obtain a mixture
  • Step S52 Place the mixture in step S51 in N 2 to perform magnetic field orientation molding to obtain a green body.
  • the function of using organic substances is to prevent the oxidation of fine powder.
  • step S52 the orientation magnetic field of the green body is 1.5 to 2T, and the density of the green body is 3.5 to 4.1 g/cm 3 .
  • the direction of the pressure is parallel to the direction of the magnetic field, or the direction of the pressure is perpendicular to the direction of the magnetic field.
  • step S6 the conditions of diffusion sintering are:
  • step S6 the conditions of the multi-stage tempering process are:
  • the first level of tempering treatment temperature is 850 ⁇ 950°C, heat preservation is 2 ⁇ 3h;
  • Second-stage tempering treatment temperature is 450 ⁇ 580°C, heat preservation is 1 ⁇ 5h.
  • This embodiment is a specific embodiment of the R-T-B permanent magnet material of the present invention.
  • step S1 raw materials are prepared according to the ratio in Table 1.
  • step S2 the prepared raw materials are added to a vacuum melting device for smelting and casting to obtain a first alloy sheet.
  • the raw material is melted under Ar or He, and then cast at 1460 to 1470°C on a water-cooled copper roll with a linear velocity of 1 m/s to obtain a first alloy sheet with a thickness of about 300 ⁇ m.
  • step S3 the first alloy sheet is plated with a heavy rare earth film according to the coating conditions of Table 2, to obtain a second alloy sheet.
  • step S3 the specific process is as follows:
  • the cleaned first alloy sheet 5 is sent to the coating chamber 2 to set a certain target sputtering current and Time, the heavy rare earth film is plated on the first alloy sheet 5; then it is sent to the primary cooling chamber 3 and the secondary cooling chamber 4 in sequence for cooling.
  • step S4 the second alloy flakes are sequentially coarsely crushed and ground to obtain fine powder.
  • the conditions of coarse crushing are: hydrogen absorption is performed at 200-450°C in a mixed gas of H 2 and Ar, and then dehydrogenation is performed at 450°C to obtain a coarse powder of about 200-500 ⁇ m.
  • the particle size of the fine powder after grinding is shown in Table 3.
  • step S5 the fine powder is sequentially granulated and compression-molded to obtain a green body.
  • step S6 diffusion sintering and multi-stage tempering treatment are performed on the green body to obtain R-T-B permanent magnetic material.
  • Dy or Tb migrates between the grains and undergoes a substitution reaction with the main phase of Nd 2 Fe 14 B in the permanent magnetic material.
  • the reaction formula is HRE+Nd 2 Fe 14 B ⁇ (Nd, HRE ) 2 Fe 14 B+Nd, so that the heavy rare earth is evenly distributed and forms a good "core-shell" structure.
  • the diffusion sintering process is a low-temperature sintering process.
  • the multi-stage tempering treatment is a two-stage tempering treatment, and the conditions are as follows:
  • the first level of tempering treatment the temperature is 900 °C, heat preservation 2h;
  • the second stage of tempering treatment the temperature is 500 °C, heat preservation 4h.
  • This embodiment is a comparative example of the R-T-B permanent magnet material of the present invention.
  • the preparation method of the control example is as follows:
  • step S1 raw materials are prepared according to the ratio of alloy 2 and alloy 5 in Table 1.
  • step S2 the prepared raw materials are added to a vacuum melting device for smelting and casting to obtain a first alloy sheet.
  • the raw material is melted under Ar or He, and then cast at 1460 to 1470°C on a water-cooled copper roll with a linear velocity of 1 m/s to obtain a first alloy sheet with a thickness of about 300 ⁇ m.
  • the control example does not perform step S3.
  • step S4 the second alloy flakes are sequentially coarsely crushed and ground to obtain fine powder.
  • the conditions for coarse crushing are: hydrogen absorption is performed at 200-450°C in a mixed gas of H 2 and Ar, and then dehydrogenation is performed at 450°C to obtain a coarse powder of about 200-500 ⁇ m.
  • the particle size of the fine powder after grinding is shown in Table 5.
  • step S5 the fine powder is sequentially granulated and compression-molded to obtain a green body.
  • step S6 diffusion sintering and multi-stage tempering treatment are performed on the green body to obtain R-T-B permanent magnetic material.
  • the diffusion sintering process is a low-temperature sintering process.
  • the multi-stage tempering treatment is a two-stage tempering treatment, and the conditions are as follows:
  • the first level of tempering treatment the temperature is 900 °C, heat preservation 2h;
  • the second stage of tempering treatment the temperature is 500 °C, heat preservation 4h.
  • This example is a performance test of the experimental example of Example 2 and the comparative example of Example 3.
  • Hysteresis loop analyzer was used to test the performance of 15 experimental examples and 2 control examples. Elemental analysis was performed on 15 experimental examples and 2 control examples using a plasma spectrometer. The test results are shown in Table 7.
  • Example 2 Alloy 2 14.02 21.74 48.66 0.20
  • Example 3 Alloy 3 13.18 26.43 41.59 0.19
  • Example 4 Alloy 4 12.45 30.15 38.58 0.17
  • Example 5 Alloy 5 13.95 22.73 49.25 0.18
  • Example 6 Alloy 1 14.05 21.91 48.76 0.43
  • Example 7 Alloy 2 13.92 23.56 49.34 0.42
  • Example 8 Alloy 3 13.02 28.76 40.57 0.41
  • Example 9 Alloy 1 14.09 24.72 49.02 0.36
  • Example 10 Alloy 2 13.94 26.38 49.56 0.38
  • Example 11 Alloy 3 13.08 31.67 42.39 0.36
  • Example 12 Alloy 4 12.34 35.64 39.21 0.37
  • Example 13 Alloy 5 13.90 27.28 47.68 0.39
  • Example 14 Alloy 1 14.01 27.38 46.75 0.72
  • Example 15 Alloy 2 13.91 27.96 44.89 0.67 Comparative Example 1
  • plating a heavy rare earth film on the first alloy sheet can effectively improve the coercive force of the permanent magnetic material, and the remanence decline is within 0.2 kGs.
  • a second rare-earth film is obtained by coating a layer of heavy rare-earth film on the first alloy plate using a magnetron sputtering device, and the second alloy plate is roughly broken After that, the heavy rare earth can be evenly distributed, so that during the diffusion and sintering process, the heavy rare earth elements diffuse from the outside to the inside of the powder particles, and a heavy rare earth enriched shell layer is formed around all Nd 2 Fe 14 B main phase grains , Thereby forming a hard magnetic phase grain with a "core-shell" structure, which can effectively suppress the formation of demagnetized core, and can avoid the excessive entry of heavy rare earth elements into the main phase, greatly improving the coercivity of RTB permanent magnetic materials Force to obtain RTB permanent magnet materials with high magnetic energy product and high coercive force.

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Abstract

本发明涉及一种R-T-B永磁材料，所述R-T-B永磁材料为R xT yTm qB z；其中，13≤x≤15.5，0.5≤q≤3，0.85≤z≤1，y＝100-x-q-z；其中，R为LR aHR 1-a，LR为Pr、Nd、PrNd中的一种或几种的组合，HR为Dy、Tb中的一种或两种的组合，0.95≤a≤1；其中，T为Fe、Co中的一种或两种的组合；其中，Tm为过渡金属。还涉及一种R-T-B永磁材料的制备方法。其优点在于，利用磁控溅射装置在合金片上镀重稀土膜，不需要采用长时间的扩散热处理，获得"核-壳"结构大幅度提高磁体的矫顽力；与传统工艺相比，在重稀土含量相同的情况下，矫顽力与磁能积更高。

Description

一种R-T-B永磁材料及其制备方法 技术领域
本发明涉及稀土磁性材料制备技术领域，尤其涉及一种含R-T-B永磁材料及其制备方法。
背景技术
钕铁硼永磁材料作为第三代稀土永磁材料，其具有高磁能积。能够促进永磁电机小型化、轻量化和高效率。目前，永磁电机已经用在电动汽车、混合动力汽车以及节能空调压缩机等领域。这些领域，磁钢的工作环境温度较高，通常在120～200℃。因此只有提高磁体的矫顽力，才能满足高温领域的工作要求。
传统的烧结钕铁硼磁体制备工艺流程为速凝、氢破、气流磨、磁场取向、烧结回火等。该方法中，提高磁体的矫顽力主要途径是在原料里添加重稀土。这种方法比较简单，生产上容易操作，但是高矫顽力牌号的磁体大量添加将导致磁体剩磁恶化，比如常规商业的42SH牌号磁体，需要添加2-3wt％Dy。通常添加每单位重量的Dy，矫顽力提升2kOe，剩磁下降0.2～0.3kGs。由此导致该工艺的另一个大的问题是不能制备高性能高矫顽力磁体，比如磁能积在48MGOe，矫顽力在20kOe及以上的磁体。这样就限制钕铁硼磁体在有轻量化和高效率要求的器件上的应用。大量添加重稀土，不仅不能平衡剩磁和矫顽力之间的矛盾，而且还造成磁钢成本的上升。
目前，行业内开发晶界扩散技术有效避免了上述弊端，成为稀土永磁研究领域的热点。晶界扩散技术就是在磁体上采用特殊的工艺例如蒸镀(H.Sepehri-Amin,T.Ohkubo,and K.Hono，Grain boundary structure and chemistry of Dy-diffusion processed Nd–Fe–B sintered magnets JOURNAL OF APPLIED PHYSICS 107,09A745_2010)、磁控溅射(BinghuiWu,Xuefeng Ding,QingkeZhang et.al,The dual trend of diffusion of heavy rare earth elements during the grain boundary diffusion process for sintered Nd-Fe-B magnets,Scripta Materialia148(2018)29–32)、表面涂覆(Deshan LI,Shunji SUZUKI,Takashi KAWASAKI  et.al，Grain Interface Modification and Magnetic Properties of Nd–Fe–B Sintered Magnets，Japanese Journal of Applied Physics Vol.47,No.10,2008,pp.7876–7878)等工艺，使Dy或Tb先附着在磁体磁体表面上，再进行低温热扩散处理。经过晶界扩散处理，磁体的矫顽力可以提升6～10kOe，而剩磁基本不降低，这样就可以制备磁能积在48MGOe,矫顽力在25kOe左右的磁体，同时磁体中所含重稀土的量还较少。目前这项技术已经在部分较薄的产品中应用，比如变频空调压缩机电机上使用的1.5-3mm厚的磁钢。然而，该方法也存在一定局限性，这项技术都是用已经烧结致密的磁体来完成的，表面布置重稀土源后，要进行长时间的扩散时效处理，整个磁体生产过程周期较长。由于在该技术过程中，重稀土是从表面沿着晶界向内部扩散的，其扩散深度有限，因此只能制备薄片磁体，由此也会导致磁体的矫顽力的一致性较差。
因此，亟需一种减少重稀土使用量的高性能高矫顽力的永磁材料及其制备方法。
发明内容
本发明的目的是针对现有技术中的不足，提供一种R-T-B永磁材料及其制备方法。
本发明的第一个目的为提供一种R-T-B永磁材料。
一种R-T-B永磁材料，所述R-T-B永磁材料为RxTyTmqBz；
其中，13≤x≤15.5，0.5≤q≤3，0.85≤z≤1，y＝100-x-q-z；
其中，R为LRaHR1-a，LR为Pr、Nd、PrNd中的一种或几种的组合，HR为Dy、Tb中的一种或两种的组合，0.95≤a≤1；
其中，T为Fe、Co中的一种或两种的组合；
其中，Tm为过渡金属。
优选地，所述Tm为Zr、Al、Cu、Ga、Sn、Si中的一种或几种的组合。
优选地，所述R-T-B永磁材料的主相晶粒为“核-壳”结构。
优选地，HR在所述壳中的浓度大于HR在所述核中的浓度。
本发明的第二个目的为提供一种R-T-B永磁材料的制备方法。
一种R-T-B永磁材料的制备方法，包括以下步骤：
步骤S1：按照R xT yTm qB z配制原材料，其中，13≤x≤15.5，0.5≤q≤3，0.85≤z≤1，y＝100-x-q-z；
步骤S2、将所述原材料加入至真空熔炼装置进行熔炼浇铸，得到第一合金片；
步骤S3、在所述第一合金片上镀重稀土膜，得到第二合金片；
步骤S4、对所述第二合金片进行粗破碎、研磨，得到细粉；
步骤S5、对所述细粉进行造粒、压制成型，得到生坯；
步骤S6、对所述生坯进行扩散烧结和多级回火处理，得到R-T-B永磁材料。
优选地，在所述步骤S1中，所述R为LR aHR 1-a，LR为Pr、Nd、PrNd中的一种或几种的组合，HR为Dy、Tb中的一种或两种的组合；
其中，0.95≤a≤1。
优选地，所述Tm为过渡金属，所述Tm为Zr、Al、Cu、Ga、Sn、Si中的一种或几种的组合。
优选地，在所述步骤S2中，所述原材料在惰性气体下进行熔炼；
所述原材料在熔炼后，在1400℃～1500℃下进行浇铸。
优选地，所述惰性气体为Ar或He。
优选地，所述第一合金片的厚度为200～300μm。
优选地，在所述步骤S3中，所述重稀土膜的材料为Dy、Tb中的任意一种或两种的组合。
优选地，在所述步骤S3中，所述重稀土膜的厚度为0～3μm。
优选地，在所述步骤S3中，使用磁控溅射装置在所述第一合金片镀所述重稀土膜。
优选地，在所述步骤S3中，所述磁控溅射装置使用的靶材料为Tb、Dy、HRE-X合金中的任意一种。
优选地，在所述HRE-X合金中，所述HRE为Tb、Dy中的任意一种或两种的组合；
所述X为Fe、Cu中的任意一种或几种的组合。
优选地，所述R-T-B永磁材料的主相晶粒为“核-壳”结构；
其中，HR在所述壳中的浓度大于HR在所述核中的浓度。
优选地，在所述步骤S4中，还包括：
步骤S41：对所述第二合金片进行粗破碎，得到粗粉，所述粗破碎的条件为：在H 2和Ar的混合气体进行充分反应后，在350～500℃下脱氢；
步骤S42：对所述步骤S41得到的所述粗粉进行研磨，得到所述细粉，所述研磨的条件为：在N 2和O 2的混合气体中进行高速研磨，粒度为1～4μm。
优选地，在所述步骤S5中，还包括：
步骤S51：将所述细粉与有机物混合搅拌，得到混合物；
步骤S52：将所述步骤S51中的所述混合物置于N 2中进行磁场取向成型，得到所述生坯。
优选地，在所述步骤S6中，所述扩散烧结的条件为：
将所述生坯在1000～1055℃下保温6～10h。
优选地，在所述步骤S6中，所述多级回火处理的条件为：
第一级回火处理：温度为850～950℃，保温2～3h；
第二级回火处理：温度为450～580℃，保温1～5h。
本发明采用以上技术方案，与现有技术相比，具有如下技术效果：
本发明的一种R-T-B永磁材料及其制备方法，利用磁控溅射装置在合金片上镀重稀土膜，然后经过粗破碎、研磨细粉、取向成型、扩散烧结和多级回火处理等工序获得烧结钕铁硼磁体；与晶界扩散对比，整个制备流程相对简单，不需要采用长时间的扩散热处理，也可以获得“核-壳”结构大幅度提高磁体的矫顽力，同时不受扩散深度的限制；与传统工艺相比，同样重稀土含量的情况下，可以获得更高的矫顽力与磁能积，这是因为镀有重稀土膜的铸片经过破碎之后重稀土可以均匀分布，烧结后的重稀土元素从磁体表面向内部扩散并沿在各个Nd 2Fe 14B主相晶粒外围形成重稀土富集的壳层，从而达到了既能有效抑制反磁化核的形成又能避免重稀土过度进入主相，同时形成一种具有“核-壳”结构的硬磁性相晶粒。
附图说明
图1是本发明的一个示意性实施例的R-T-B永磁材料的制备工艺流程图。
图2是本发明的一个示意性实施例的磁控溅射装置的示意图。
图3是本发明的实验例2的R-T-B永磁材料的背散射电子图像。
图4是本发明的对照例1的永磁材料的背散射电子图像。
其中的附图标记为：1为清洗室，2为镀膜室，3为一级冷却室，4为二级冷却室，5为第一合金片，6为重稀土或其合金靶，7为传动辊轴。
具体实施方式
下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。
需要说明的是，在不冲突的情况下，本发明中的实施例及实施例中的特征可以相互组合。
下面结合附图和具体实施例对本发明作进一步说明，但不作为本发明的限定。
实施例1
如图1所示，本发明的一种R-T-B永磁材料的制备方法，包括以下步骤：
步骤S1：按照R xT yTm qB z配制原材料，其中，13≤x≤15.5，0.5≤q≤3，0.85≤z≤1，y＝100-x-q-z；
步骤S2、将原材料加入至真空熔炼装置进行熔炼浇铸，得到第一合金片；
步骤S3、在第一合金片上镀重稀土膜，得到第二合金片；
步骤S4、对第二合金片进行粗破碎、研磨，得到细粉；
步骤S5、对细粉进行造粒、压制成型，得到生坯；
步骤S6、对生坯进行扩散烧结和多级回火处理，得到R-T-B永磁材料。
上述步骤是得到R-T-B永磁材料的基础步骤。
其中，在步骤S1中，R为LR aHR 1-a，LR为Pr、Nd、PrNd中的一种或几种的组合，HR为Dy、Tb中的一种或两种的组合，0.95≤a≤1。
其中，Tm为过渡金属，Tm为Zr、Al、Cu、Ga、Sn、Si中的一种或几种的组合。
进一步地，在步骤S2中，原材料在惰性气体下进行熔炼。
进一步地，原材料在熔炼后，在1400℃～1500℃下进行浇铸。
进一步地，惰性气体为Ar或He。
进一步地，第一合金片的厚度为200～300μm。
进一步地，在步骤S3中，重稀土膜的材料为Dy、Tb中的任意一种或两种的组合。
进一步地，在步骤S3中，重稀土膜的厚度为0～3μm。
进一步地，在步骤S3中，使用磁控溅射装置在第一合金片镀所述重稀土膜。
进一步地，在步骤S3中，磁控溅射装置使用的材料为Tb、Dy、HRE-X合金中的任意一种或几种的组合。
其中，在HRE-X合金中，HRE为Tb、Dy中的任意一种或两种的组合；
X为Fe、Cu中的任意一种或几种的组合。
进一步地，R-T-B永磁材料的晶粒为“核-壳”结构。
进一步地，如图2所示，磁控溅射装置包括顺次设置的清洗室1、镀膜室2、一级冷却室3和二级冷却室4，其中，在镀膜室2的内部的上方设置有重稀土或者其合金靶6，用于在镀膜室2内的第一合金片5镀重稀土膜。在清洗室1、镀膜室2、一级冷却室3和二级冷却室4中，均设置有传动辊轴7，用于输送第一合金片5。
进一步地，在步骤S4中，还包括：
步骤S41：对第二合金片进行粗破碎，得到粗粉，粗破碎的条件为：在H 2和Ar的混合气体进行充分反应后，在350～500℃下脱氢；
步骤S42：对步骤S41得到的粗粉进行研磨，得到细粉，研磨的条件为：在N 2和O 2的混合气体中进行高速研磨，粒度为1～4μm。
进一步地，在步骤S41中，于200～450℃下在H 2和Ar的混合气体进行吸氢。
进一步地，在步骤S41中，在420～500℃下脱氢。
进一步地，在步骤S5中，还包括：
步骤S51：将细粉与有机物混合搅拌，得到混合物；
步骤S52：将步骤S51中的混合物置于N 2中进行磁场取向成型，得到生坯。
其中，使用有机物的作用为防止细粉氧化。
进一步地，在步骤S52中，生坯的取向磁场为1.5～2T，生坯的密度为 3.5～4.1g/cm 3。
进一步地，在取向成型过程中，压力的方向平行于磁场的方向，或，压力的方向垂直于磁场的方向。
进一步地，在步骤S6中，扩散烧结的条件为：
将生坯在1000～1055℃下保温6～10h。
进一步地，在步骤S6中，多级回火处理的条件为：
第一级回火处理：温度为850～950℃，保温2～3h；
第二级回火处理：温度为450～580℃，保温1～5h。
实施例2
本实施例为本发明的R-T-B永磁材料的具体实施例。
本实施例的制备方法如下：
在步骤S1中，按照表1中的比例配制原材料。
表1原材料成分表(at.％)
  Pr Nd Dy Tb Al Cu Ga Zr Fe Co B
合金1 3.53 10.35 0.00 0.00 0.25 0.15 0.30 0.12 Bal. 1.00 5.40
合金2 3.48 10.19 0.20 0.00 0.73 0.21 0.47 0.07 Bal. 1.11 5.50
合金3 3.26 9.57 1.21 0.00 0.49 0.10 0.38 0.11 Bal. 1.12 5.42
合金4 3.26 9.57 1.33 0.00 1.22 0.21 0.38 0.12 Bal. 1.12 5.42
合金5 0.00 13.18 0.00 0.41 0.48 0.21 0.09 0.07 Bal. 0.55 5.68
在步骤S2中，将配制好的原材料加入至真空熔炼装置进行熔炼浇铸，得到第一合金片。
其中，原材料在Ar或He下进行熔炼，然后在1460～1470℃下浇铸到线速度为1m/s的水冷铜辊上，得到厚度为300μm左右的第一合金片。
在步骤S3中，按照表2的镀膜条件对第一合金片进行镀重稀土膜，得到第二合金片。
表2镀重稀土膜条件
  合金 靶材 膜厚(μm)
实验例1 合金1 Dy 0.5
实验例2 合金2 Dy 0.5
实验例3 合金3 Dy 0.5
实验例4 合金4 Dy 0.5
实验例5 合金5 Dy 0.5
实验例6 合金1 Dy 85-Fe 15 1.5
实验例7 合金2 Dy 85-Fe 15 1.5
实验例8 合金3 Dy 85-Fe 15 1.5
实验例9 合金1 Tb 1
实验例10 合金2 Tb 1
实验例11 合金3 Tb 1
实验例12 合金4 Tb 1
实验例13 合金5 Tb 1
实验例14 合金1 Tb 75-Cu 25 2
实验例15 合金2 Tb 75-Cu 25 2
在步骤S3中，其具体过程如下：
将第一合金片5送至清洗室1内，对第一合金片5的表面进行离子清洗；清洗后的第一合金片5送至镀膜室2内，设定一定的靶材溅射电流以及时间，在第一合金片5上镀重稀土膜；然后顺次送至一级冷却室3和二级冷却室4内进行冷却。
在步骤S4中，对第二合金片依次进行粗破碎、研磨，得到细粉。
其中，粗破碎的条件为：于200～450℃下在H 2和Ar的混合气体进行吸氢，然后在450℃下脱氢，得到200～500μm左右的粗粉。
其中，研磨后的细粉的粒度如表3所示。
表3细粉粒度
  粒度
实验例1 2.8
实验例2 2.5
实验例3 2.6
实验例4 2.1
实验例5 2.2
实验例6 2.8
实验例7 2.5
实验例8 2.6
实验例9 2.8
实验例10 2.5
实验例11 2.6
实验例12 2.1
实验例13 2.2
实验例14 2.8
实验例15 2.5
在步骤S5中，对细粉依次进行造粒、压制成型，得到生坯。
在步骤S6中，对生坯进行扩散烧结和多级回火处理，得到R-T-B永磁材料。
具体地，扩散烧结的条件如表4所示。
表4扩散烧结条件
  温度(℃) 时间(h)
实验例1 1055 8
实验例2 1050 8
实验例3 1045 8
实验例4 1000 8
实验例5 1010 8
实验例6 1045 8
实验例7 1040 8
实验例8 1035 8
实验例9 1055 8
实验例10 1050 8
实验例11 1045 8
实验例12 1040 8
实验例13 1055 8
实验例14 1045 8
实验例15 1040 8
在扩散烧结过程中，Dy或Tb在晶粒间进行迁移，与永磁材料中的主相的Nd 2Fe 14B发生置换反应，其反应公式为HRE+Nd 2Fe 14B→(Nd，HRE) 2Fe 14B+Nd，从而使重稀土均匀分布并形成良好的“核-壳”结构。
此外，在本实施例中，扩散烧结过程为低温烧结过程。
多级回火处理为二级回火处理，其条件如下：
第一级回火处理：温度为900℃，保温2h；
第二级回火处理：温度为500℃，保温4h。
实施例3
本实施例为本发明的R-T-B永磁材料的对照例。
对照例的制备方法如下：
在步骤S1中，按照表1中的合金2和合金5的比例配制原材料。
在步骤S2中，将配制好的原材料加入至真空熔炼装置进行熔炼浇铸，得到 第一合金片。
其中，原材料在Ar或He下进行熔炼，然后在1460～1470℃下浇铸到线速度为1m/s的水冷铜辊上，得到厚度为300μm左右的第一合金片。
对照例不进行步骤S3。
在步骤S4中，对第二合金片依次进行粗破碎、研磨，得到细粉。
其中，粗破碎的条件为：于200～450℃下在H 2和Ar的混合气体进行吸氢，然后在450℃下脱氢，得到200～500μm左右的粗粉。
其中，研磨后的细粉的粒度如表5所示。
表5细粉粒度
  粒度
对照例1 2.6
对照例2 2.6
在步骤S5中，对细粉依次进行造粒、压制成型，得到生坯。
在步骤S6中，对生坯进行扩散烧结和多级回火处理，得到R-T-B永磁材料。
具体地，扩散烧结的条件如表6所示。
表6扩散烧结条件
  温度(℃) 时间(h)
对照例1 1050 8
对照例2 1055 8
此外，在本实施例中，扩散烧结过程为低温烧结过程。
多级回火处理为二级回火处理，其条件如下：
第一级回火处理：温度为900℃，保温2h；
第二级回火处理：温度为500℃，保温4h。
实施例4
本实施例为实施例2的实验例和实施例3的对照例的性能检测。
使用磁滞回线分析仪对15个实验例和2个对照例进行性能检测。使用等离子光谱仪对15个实验例和2个对照例进行元素分析。检测结果如表7所示。
表7检测结果
  合金 Br(kGs) Hcj(kOe) (BH)m ΔHRE(wt.％)
实施例1 合金1 14.15 19.36 49.35 0.19
实施例2 合金2 14.02 21.74 48.66 0.20
实施例3 合金3 13.18 26.43 41.59 0.19
实施例4 合金4 12.45 30.15 38.58 0.17
实施例5 合金5 13.95 22.73 49.25 0.18
实施例6 合金1 14.05 21.91 48.76 0.43
实施例7 合金2 13.92 23.56 49.34 0.42
实施例8 合金3 13.02 28.76 40.57 0.41
实施例9 合金1 14.09 24.72 49.02 0.36
实施例10 合金2 13.94 26.38 49.56 0.38
实施例11 合金3 13.08 31.67 42.39 0.36
实施例12 合金4 12.34 35.64 39.21 0.37
实施例13 合金5 13.90 27.28 47.68 0.39
实施例14 合金1 14.01 27.38 46.75 0.72
实施例15 合金2 13.91 27.96 44.89 0.67
对比例1 合金2 14.10 18.90 48.96 0.00
对比例2 合金5 14.04 20.65 48.70 0.00
如上表可知，在第一合金片上镀重稀土膜，可以有效提高永磁材料的矫顽力，且剩磁下降是在0.2kGs内。
以合金2为例进行说明，从实验例2、7、10和15以及对照例1来看，镀0.5μm Dy时，矫顽力提高了2.84kOe，剩磁降低0.08kGs；镀Dy-Fe时，矫顽力提高了4.66kOe，剩磁降低0.18kGs；镀Tb时，矫顽力提高了7.48kOe，剩磁降低0.16kGs；镀Tb-Cu时，矫顽力提高了9.06kOe，剩磁降低0.19kGs。从以上可知，使用Tb靶提升的矫顽力幅度相对更高，而剩磁仅下降不到0.2kGs。
以合金5为例进行说明，从实验例5和13以及对照例2来看，镀Dy时，矫顽力提高了2.08kOe，剩磁降低0.09kGs；镀Tb时，矫顽力提高了6.63kOe，剩磁降低0.14kGs。
此外，将实验例1与对照例1进行对比可知，在Dy含量相近的情况下，实验例1的磁体的剩磁和矫顽力均比对照例1高，其原因在于，经过镀膜和扩散烧结，改变了重稀土的分布，从而提高了剩磁和矫顽力。
如图3和图4分别是实验例2和对照例1的永磁材料的背散射电子图像，其中灰色区域为2-14-1相颗粒，灰色衬度为电子浓度。在图3中，灰色衬度有两种，+1位置处为浅灰色，+2位置处为深灰色，浅灰色代表电子浓度高，深灰色代表电子浓度低，即表明重稀土分布不均匀，呈现“核-壳”结构。而在图4中，灰色衬度只有一种，即表示重稀土分布均匀。由图3可知，重稀土主要分布在晶 粒边界上，亦即重稀土在壳中的浓度高于重稀土在核中的浓度，即分布在“核-壳”的“壳”上，提高了晶粒边界上的磁晶各向异性场，降低了晶粒边界的反磁化概率，从而提高了永磁材料的矫顽力。
由上述检测结果可知，通过本发明的R-T-B永磁材料的制备方法，利用磁控溅射装置在第一合金片上镀上一层重稀土膜得到第二合金片，将第二合金片进行粗破碎后，使得重稀土能够均匀分布，从而在扩散烧结过程中，使得重稀土元素从粉末颗粒的外部向内部扩散，并在所有Nd 2Fe 14B主相晶粒外围形成重稀土富集的壳层，从而形成一种具有“核-壳”结构的硬磁性相晶粒，既能有效抑制反磁化核的形成，又能避免重稀土元素过度进入主相，大幅度提高R-T-B永磁材料的矫顽力，从而获得高磁能积高矫顽力的R-T-B永磁材料。
以上所述仅为本发明较佳的实施例，并非因此限制本发明的实施方式及保护范围，对于本领域技术人员而言，应当能够意识到凡运用本发明说明书及图示内容所作出的等同替换和显而易见的变化所得到的方案，均应当包含在本发明的保护范围内。

Claims (20)

  1. 一种R-T-B永磁材料，其特征在于，所述R-T-B永磁材料为R xT yTm qB z；
    其中，13≤x≤15.5，0.5≤q≤3，0.85≤z≤1，y＝100-x-q-z；
    其中，R为LR aHR 1-a，LR为Pr、Nd、PrNd中的一种或几种的组合，HR为Dy、Tb中的一种或两种的组合，0.95≤a≤1；
    其中，T为Fe、Co中的一种或两种的组合；
    其中，Tm为过渡金属。
  2. 根据权利要求1所述的R-T-B永磁材料，其特征在于，所述Tm为Zr、Al、Cu、Ga、Sn、Si中的一种或几种的组合。
  3. 根据权利要求1所述的R-T-B永磁材料，其特征在于，所述R-T-B永磁材料的主相晶粒为“核-壳”结构。
  4. 根据权利要求3所述的R-T-B永磁材料，其特征在于，HR在所述壳中的浓度大于HR在所述核中的浓度。
  5. 一种R-T-B永磁材料的制备方法，用于制备如权利要求1～5任一所述的R-T-B永磁材料，其特征在于，包括以下步骤：
    步骤S1：按照R xT yTm qB z配制原材料，其中，13≤x≤15.5，0.5≤q≤3，0.85≤z≤1，y＝100-x-q-z；
    步骤S2、将所述原材料加入至真空熔炼装置进行熔炼浇铸，得到第一合金片；
    步骤S3、在所述第一合金片上镀重稀土膜，得到第二合金片；
    步骤S4、对所述第二合金片进行粗破碎、研磨，得到细粉；
    步骤S5、对所述细粉进行造粒、压制成型，得到生坯；
    步骤S6、对所述生坯进行扩散烧结和多级回火处理，得到R-T-B永磁材料。
  6. 根据权利要求5所述的R-T-B永磁材料的制备方法，其特征在于，在所述步骤S1中，所述R为LR aHR 1-a，LR为Pr、Nd、PrNd中的一种或几种的组合，HR为Dy、Tb中的一种或两种的组合；
    其中，0.95≤a≤1。
  7. 根据权利要求5所述的R-T-B永磁材料的制备方法，其特征在于，所述Tm为过渡金属，所述Tm为Zr、Al、Cu、Ga、Sn、Si中的一种或几种的组合。
  8. 根据权利要求6所述的R-T-B永磁材料的制备方法，其特征在于，在所述 步骤S2中，所述原材料在惰性气体下进行熔炼；
    所述原材料在熔炼后，在1400℃～1500℃下进行浇铸。
  9. 根据权利要求8所述的R-T-B永磁材料的制备方法，其特征在于，所述惰性气体为Ar或He。
  10. 根据权利要求5所述的R-T-B永磁材料的制备方法，其特征在于，所述第一合金片的厚度为200～300μm。
  11. 根据权利要求5所述的R-T-B永磁材料的制备方法，其特征在于，在所述步骤S3中，所述重稀土膜的材料为Dy、Tb中的任意一种或两种的组合。
  12. 根据权利要求5所述的R-T-B永磁材料的制备方法，其特征在于，在所述步骤S3中，所述重稀土膜的厚度为0～3μm。
  13. 根据权利要求5所述的R-T-B永磁材料的制备方法，其特征在于，在所述步骤S3中，使用磁控溅射装置在所述第一合金片镀所述重稀土膜。
  14. 根据权利要求13所述的R-T-B永磁材料的制备方法，其特征在于，在所述步骤S3中，所述磁控溅射装置使用的靶材料为Tb、Dy、HRE-X合金中的任意一种。
  15. 根据权利要求14所述的R-T-B永磁材料的制备方法，其特征在于，在所述HRE-X合金中，所述HRE为Tb、Dy中的任意一种或两种的组合；
    所述X为Fe、Cu中的任意一种或几种的组合。
  16. 根据权利要求6所述的R-T-B永磁材料的制备方法，其特征在于，所述R-T-B永磁材料的主相晶粒为“核-壳”结构；
    其中，HR在所述壳中的浓度大于HR在所述核中的浓度。
  17. 根据权利要求5所述的R-T-B永磁材料的制备方法，其特征在于，在所述步骤S4中，还包括：
    步骤S41：对所述第二合金片进行粗破碎，得到粗粉，所述粗破碎的条件为：在H 2和Ar的混合气体进行充分反应后，在350～500℃下脱氢；
    步骤S42：对所述步骤S41得到的所述粗粉进行研磨，得到所述细粉，所述研磨的条件为：在N 2和O 2的混合气体中进行高速研磨，粒度为1～4μm。
  18. 根据权利要求5所述的永磁材料的制备方法，其特征在于，在所述步骤S5中，还包括：
    步骤S51：将所述细粉与有机物混合搅拌，得到混合物；
    步骤S52：将所述步骤S51中的所述混合物置于N 2中进行磁场取向成型，得到所述生坯。
  19. 根据权利要求5所述的R-T-B永磁材料的制备方法，其特征在于，在所述步骤S6中，所述扩散烧结的条件为：
    将所述生坯在1000～1055℃下保温6～10h。
  20. 根据权利要求5所述的R-T-B永磁材料的制备方法，其特征在于，在所述步骤S6中，所述多级回火处理的条件为：
    第一级回火处理：温度为850～950℃，保温2～3h；
    第二级回火处理：温度为450～580℃，保温1～5h。
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