WO2024001041A1 - 改性烧结钕铁硼永磁材料及其制备方法 - Google Patents

改性烧结钕铁硼永磁材料及其制备方法 Download PDF

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WO2024001041A1
WO2024001041A1 PCT/CN2022/135691 CN2022135691W WO2024001041A1 WO 2024001041 A1 WO2024001041 A1 WO 2024001041A1 CN 2022135691 W CN2022135691 W CN 2022135691W WO 2024001041 A1 WO2024001041 A1 WO 2024001041A1
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alloy
permanent magnet
magnet material
sintered ndfeb
ndfeb permanent
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French (fr)
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安小鑫
郝忠彬
刘小浪
洪群峰
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Zhejiang Dongyang Dmegc Rare Earth Magnet Co Ltd
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Zhejiang Dongyang Dmegc Rare Earth Magnet Co Ltd
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Priority to EP22871161.0A priority Critical patent/EP4322184A4/en
Priority to US18/031,617 priority patent/US20250118465A1/en
Publication of WO2024001041A1 publication Critical patent/WO2024001041A1/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
    • H01F1/057—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
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
    • H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
    • H01F1/0576—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together pressed, e.g. hot working
    • 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

  • This application is based on the Chinese application with CN application number 202210761631.
  • the present invention relates to the technical field of rare earth permanent magnet materials, and specifically to a modified sintered neodymium iron boron permanent magnet material and a preparation method thereof.
  • Permanent magnetic materials have the property of not being easily demagnetized after being magnetized, and are widely used in various fields of industry and life. According to the magnetic energy product size, temperature resistance characteristics and cost of the permanent magnet material, relatively suitable and cost-effective permanent magnet materials can be selected according to the requirements and characteristics of different application fields.
  • permanent magnet ferrite has low magnetic properties (its maximum magnetic energy product (BH) max is less than 5MGOe) but is cheap and dominates the low-end application market.
  • BH maximum magnetic energy product
  • sintered NdFeB has the characteristics of high magnetic energy product ((BH)max is 30 ⁇ 55MGOe) and high coercive force. It has excellent performance and cost advantages in high-performance applications. Therefore, since its discovery, sintered NdFeB permanent magnet materials have quickly replaced the second-generation SmCo series rare earth permanent magnet materials and become the main choice for high-end applications such as computers, information, communications, home appliances, transportation, and office automation.
  • the main purpose of the present invention is to provide a modified sintered NdFeB permanent magnet material and a preparation method thereof, so as to solve the problems of poor high temperature resistance and high cost of the sintered NdFeB permanent magnet material in the prior art, and at the same time make up for the There is a performance gap between the existing bonded NdFeB and sintered NdFeB to solve the problem that existing permanent magnet material products cannot meet the market demand with a maximum magnetic energy product between 5 and 30 MGOe.
  • the modified sintered NdFeB permanent magnet material includes a first alloy, and the first alloy has a chemical formula represented by Formula (I): (Pr 0.25 Nd 0.75 ) a (LRE) b TM c Fe 100%-abcd B d (I), where LRE is a rare earth element, and LRE is selected from one or more of Gd, Y and Ce elements, and Containing at least Gd element, TM is selected from one or more of Al, Cu, Co, Ga, Nb, Zr and Ti elements, a is 5 to 20%, b is 13 to 28%, c is 0.4 to 5.5% , d is 0.9 ⁇ 1%.
  • Formula (I) (Pr 0.25 Nd 0.75 ) a (LRE) b TM c Fe 100%-abcd B d (I)
  • LRE is a rare earth element
  • LRE is selected from one or more of Gd, Y and Ce elements
  • TM
  • a is 7 to 16%
  • b is 16 to 26%
  • c is 0.7 to 3.3%
  • d is 0.92 to 0.98%.
  • the modified sintered NdFeB permanent magnet material also includes a second alloy, and the second alloy has the chemical formula shown in Formula (II): (Pr 0.25 Nd 0.75 ) x TM' y Fe 100%-xyz B z (II) , wherein, TM' is selected from one or more of Al, Cu, Co, Ga, Nb, Zr and Ti elements, x is 35 to 45%, y is 0.5 to 9%, and z is 0.5 to 0.9%; Preferably, x is 38-42%, y is 1.6-4.5%, and z is 0.6-0.8%.
  • Formula (II) (Pr 0.25 Nd 0.75 ) x TM' y Fe 100%-xyz B z (II) , wherein, TM' is selected from one or more of Al, Cu, Co, Ga, Nb, Zr and Ti elements, x is 35 to 45%, y is 0.5 to 9%, and z is 0.5 to 0.9%; Preferably,
  • the weight percentage of the second alloy does not exceed 30 wt%.
  • TM is a combination of Al, Co, Cu, Ga and Zr, or a combination of Al, Co, Cu, Ga and Nb, or a combination of Al, Co, Cu, Ga and Ti; preferably, TM is Al, Co , a combination of Cu, Ga and Zr; more preferably, TM is a combination of Al, Co, Cu, Ga and Zr, and the weight ratio of Al, Co, Cu, Ga and Zr is (0.2 ⁇ 3): (0.2 ⁇ 1.5): (0.1 ⁇ 0.5): (0.1 ⁇ 0.3): (0.1 ⁇ 0.16), more preferably (0.2 ⁇ 1.5): (0.2 ⁇ 1.0): (0.1 ⁇ 0.3): (0.1 ⁇ 0.3): ( 0.1 ⁇ 0.16); or,
  • TM is Al, Co, Cu, Ga, Nb and Zr, or a combination of Al, Co, Cu, Ga, Zr and Ti; preferably, TM is a combination of Al, Co, Cu, Ga, Zr and Ti; more Preferably, TM is a combination of Al, Co, Cu, Ga, Zr and Ti, and the weight ratio of Al, Co, Cu, Ga, Zr and Ti is (0.2 ⁇ 3):(0.2 ⁇ 1.5):(0.1 ⁇ 0.5): (0.1 ⁇ 0.3): (0.04 ⁇ 0.16): (0.05 ⁇ 0.2), more preferably (0.2 ⁇ 1.5): (0.2 ⁇ 1.0): (0.1 ⁇ 0.3): (0.1 ⁇ 0.3): ( 0.04 ⁇ 0.12): (0.05 ⁇ 0.15).
  • weight ratio of the first alloy and the second alloy is (80-90): (10-20).
  • another aspect of the present invention also provides a method for preparing the above-mentioned modified sintered NdFeB permanent magnet material provided by the present application.
  • the preparation method of the modified sintered NdFeB permanent magnet material includes: adding Pr -Nd alloy, LRE source, TM source are mixed with ferroboron and subjected to the first smelting process and the first flaking process to obtain the first alloy cast piece; the LRE source is selected from one of Gd-Fe alloy, Y element and Ce element One or more kinds; the TM source is selected from one or more of Al elemental substance, Cu elemental substance, Co elemental substance, Ga elemental substance, Nb-Fe alloy, Zr elemental substance and Ti elemental substance; The first alloy cast piece is crushed to obtain the first powder; subject the first powder to orientation molding and pressing treatment to obtain a green body; perform sintering treatment and tempering treatment on the green body to obtain a modified sintered NdFeB permanent magnet material.
  • the preparation method of the modified sintered NdFeB permanent magnet material also includes: mixing Pr-Nd alloy, TM' source and ferroboron and performing a second smelting process and a second slugging process to obtain a second alloy cast sheet.
  • the TM source is selected from one or more of Al element, Cu element, Co element, Ga element, Nb-Fe alloy, Zr element and Ti element;
  • a second alloy cast piece is added at the same time to Perform a crushing process together with the first alloy cast piece to obtain a second powder; mix the second powder with a lubricant before performing orientation molding; preferably, the crushing process includes hydrogen crushing treatment and airflow milling in sequence. Antioxidants are added to the mixture, and the second powder is obtained after airflow milling.
  • the weight ratio of the first powder, antioxidant and lubricant is 100:(0.05 ⁇ 0.2):(0.03 ⁇ 0.15); preferably, the average particle size of the first powder is selected from 3.0 ⁇ 3.8 ⁇ m.
  • the total weight of the first powder and the second powder and the weight ratio of the antioxidant and the lubricant are 100: (0.05 ⁇ 0.2): (0.03 ⁇ 0.15); preferably, the average particle size of the first powder and the second powder Each is independently selected from 3.0 to 3.8 ⁇ m.
  • rare earth elements such as Gd, Y and Ce elements
  • Pr and Nd elements in the traditional sintered NdFeB permanent magnet material ((PrNd)-Fe-B).
  • Modified sintered NdFe can be obtained with a maximum magnetic energy product (BH) max in the range of 5 to 30 MGOe and a magnetic property that meets the needs of low-end fields (remanence Br in the range of 6 to 11 kGs and intrinsic coercive force Hcj in the range of 5 to 11 kOe).
  • BH maximum magnetic energy product
  • the modified sintered NdFeB permanent magnet material includes a first alloy, and the first alloy has the chemical formula shown in Formula (I): ( Pr 0.25 Nd 0.75 ) a (LRE) b TM c Fe 100%-abcd B d (I), where LRE is a rare earth element, and LRE includes but is not limited to one or more of Gd, Y and Ce elements, And it contains at least Gd element, TM includes but is not limited to one or more of Al, Cu, Co, Ga, Nb, Zr and Ti elements, a is 5 to 20%, b is 13 to 28%, and c is 0.4 ⁇ 5.5%, d is 0.9 ⁇ 1%.
  • Formula (I) ( Pr 0.25 Nd 0.75 ) a (LRE) b TM c Fe 100%-abcd B d (I)
  • LRE is a rare earth element
  • LRE includes but is not limited to one or more of Gd, Y and Ce elements
  • TM includes but is not limited
  • a, b, c and d in the chemical formula shown in Formula (I) of the present application and x, y and z in the chemical formula of Formula (II) respectively refer to the weight percentage of the corresponding components.
  • the maximum magnetic energy product can be obtained ( BH) modified sintered NdFeB permanent magnet material with max in the range of 5 ⁇ 30MGOe and magnetic properties that meet the needs of low-end fields (remanence Br in the range of 6 ⁇ 11kGs, intrinsic coercive force Hcj in the range of 5 ⁇ 11kOe); the other In terms of specific types of rare earth elements and TM elements working together in a specific weight ratio of the present invention (strictly controlling the value ranges of a, b, c, and d), the temperature coefficient of the intrinsic coercive force can be improved, thereby improving its high temperature resistance. , making it suitable for applications under high temperature conditions. In addition, since the abundance of Gd, Y, Ce and other elements in natural resources is significantly higher than that of Pr and Nd
  • the modified sintered NdFeB permanent magnet material also includes a second alloy, and the second alloy has the chemical formula shown in Formula (II): (Pr 0.25 Nd 0.75 ) x TM' y Fe 100%- xyz B z (II), where TM' includes but is not limited to one or more of Al, Cu, Co, Ga, Nb, Zr and Ti elements, x is 35 ⁇ 45%, and y is 0.5 ⁇ 9% , z is 0.5 ⁇ 0.9%.
  • the modified sintered NdFeB permanent magnet material also contains the first alloy with specific components (strictly control the value ranges of a, b, c, and d) and
  • the second alloy with specific composition is conducive to exerting a synergistic effect between the two and is conducive to achieving magnetic coupling isolation, which is conducive to increasing the coercive force and further improving the magnetic properties;
  • it is conducive to further reducing the absolute value of the intrinsic coercive force temperature coefficient of the modified sintered NdFeB permanent magnet material, thereby further improving its comprehensive performance such as high temperature resistance and maximum magnetic energy product.
  • TM' Compared with other types of TM', the use of the above preferred types of TM' can, on the one hand, improve the microstructural grain structure and grain boundary phase distribution of the material, and better enhance the intrinsic properties of the material without reducing the residual magnetism of the material. Coercive force; on the other hand, it can improve the sintering characteristics of the material, and can obtain dense and uniform grain magnets within a certain temperature range, which is more conducive to the preparation of modified sintered NdFeB permanent magnet materials.
  • x is 38 to 42%
  • y is 1.6 ⁇ 4.5%
  • z is 0.6 ⁇ 0.8%.
  • the weight percentage of the second alloy does not exceed 30 wt% based on the total weight of the first alloy and the second alloy.
  • the weight percentage of the second alloy exceeds 30wt%, on the one hand, the effect of the second alloy on improving the grain boundary phase distribution of the modified sintered NdFeB material will be weakened, and the effect of improving the intrinsic coercive force will also be weakened;
  • too much rare earth elements and too little B content in the material composition will affect the sintering characteristics of the material, leading to a decrease in the residual magnetism and magnetic energy product of the modified sintered NdFeB permanent magnet material.
  • LRE is Gd and Ce, or Gd and Y, or Gd, Y and Ce.
  • LRE elements to replace Nd elements will, on the one hand, significantly reduce the cost of modified sintered NdFeB permanent magnet materials, and on the other hand, it will help improve its high temperature resistance while maintaining magnetic properties. higher level.
  • LRE is Gd and Ce; more preferably, LRE is Gd and Ce, and the weight ratio of Gd and Ce The ratio is (13-18):(8-10), more preferably (13-15):(8-10).
  • TM' is a combination of Co, Cu and Zr, or a combination of Al, Co, Cu and Zr, or a combination of Al, Co, Ga and Zr, or Al, Cu, A combination of Ga and Zr, or a combination of Al, Co, Cu, Ga and Zr.
  • doping with the above-mentioned specific types of TM’ elements is beneficial to reducing the cost of modified sintered NdFeB permanent magnet materials on the one hand, and on the other hand is beneficial to improving its magnetic properties and high temperature resistance.
  • TM is a combination of Al, Co, Cu, Ga and Zr, or a combination of Al, Co, Cu, Ga and Nb, or a combination of Al, Co, Cu, Ga and Ti .
  • doping with the above-mentioned specific types of TM elements will, on the one hand, help reduce the cost of modified sintered NdFeB permanent magnet materials, and on the other hand, it will help improve its magnetic properties and high temperature resistance.
  • TM is Al, Co, Cu, Ga, Nb and Zr, or a combination of Al, Co, Cu, Ga, Zr and Ti.
  • doping with the above-mentioned specific types of TM elements will, on the one hand, help reduce the cost of modified sintered NdFeB permanent magnet materials, and on the other hand, it will help improve its magnetic properties and high temperature resistance.
  • TM is a combination of Al, Co, Cu, Ga, Zr and Ti; more preferably, TM is a combination of Al, Co, Cu, Ga, Zr and Ti, and Al, Co, Cu, Ga, Zr and
  • the weight ratio of Ti is (0.2 ⁇ 3):(0.2 ⁇ 1.5):(0.1 ⁇ 0.5):(0.1 ⁇ 0.3):(0.04 ⁇ 0.16):(0.05 ⁇ 0.2), more preferably (0.2 ⁇ 1.5) ⁇ (0.2 ⁇ 1.0): (0.1 ⁇ 0.3): (0.1 ⁇ 0.3): (0.04 ⁇ 0.12): (0.05 ⁇ 0.15).
  • the weight ratio of the first alloy and the second alloy is (80-90): (10-20).
  • the weight ratio of the first alloy and the second alloy includes but is not limited to the above range. Limiting it within the above range is conducive to further exerting the synergistic effect of the two and is conducive to further improving the high temperature resistance of the modified sintered NdFeB permanent magnet material. performance while further reducing costs.
  • the second aspect of this application also provides a method for preparing the above-mentioned modified sintered NdFeB permanent magnet material provided by this application.
  • the preparation method of the modified sintered NdFeB permanent magnet material includes: combining Pr-Nd alloy, LRE
  • the source, TM source and ferroboron are mixed and subjected to the first smelting process and the first flake removal process to obtain the first alloy cast piece;
  • the LRE source includes but is not limited to one or more of Gd-Fe alloy, Y element and Ce element.
  • the TM source includes but is not limited to one or more of Al element, Cu element, Co element, Ga element, Nb-Fe alloy, Zr element and Ti element; the first alloy cast piece is crushed to obtain the third A powder; the first powder is oriented, molded and pressed to obtain a green body; the green body is sintered and tempered to obtain a modified sintered NdFeB permanent magnet material.
  • orientation molding treatment refers to the treatment in which the first powder overcomes the friction and agglomeration between powder particles under the action of an external magnetic field to form a degree of orientation
  • the pressing treatment refers to the use of pressure to make the first powder obtain compactness. and shape, thereby obtaining a green body; after the first powder is oriented, molded and pressed, a green body is obtained; the green body is sintering and tempered to obtain a modified sintered NdFeB permanent magnet material.
  • the weight ratio of the first powder, antioxidant and lubricant is 100: (0.05 ⁇ 0.2): (0.03 ⁇ 0.15) .
  • the average particle size of the first powder includes but is not limited to 3.0 ⁇ 3.8 ⁇ m.
  • the preparation method of the modified sintered NdFeB permanent magnet material also includes: mixing the Pr-Nd alloy, TM' source and FeB and performing a second smelting process and a second spinning process, Obtain the second alloy cast piece;
  • the TM source includes but is not limited to one or more of Al element, Cu element, Co element, Ga element, Nb-Fe alloy, Zr element and Ti element; during the crushing process, At the same time, a second alloy cast piece is added to be crushed together with the first alloy cast piece to obtain a second powder; the second powder is mixed with a lubricant before oriented molding.
  • a modified sintered NdFeB permanent magnet material with a more uniform distribution of grain boundary phases can be obtained, which can achieve magnetic coupling and isolation, thereby effectively improving the coercive force and high temperature resistance.
  • Mixing the second powder with the lubricant and then performing orientation molding processing can reduce the friction between the second powder particles, facilitate processing, and improve the orientation of the material.
  • Hydrogen destruction treatment can be divided into two stages: hydrogen absorption and dehydrogenation.
  • the principle is to use hydrogen to react with the Nd-rich phase and the main phase.
  • Crisp powder can be obtained after hydrogen cracking treatment, which is conducive to further fine crushing.
  • Airflow milling is a process that uses high-pressure gas flow to accelerate the hydrogen-broken powder particles to supersonic speeds, and causes the powder particles to collide with each other to break them.
  • the crushing treatment includes hydrogen crushing treatment and air-flow grinding in sequence.
  • Antioxidants are added during the air-flow grinding process, and the second powder is obtained after the air-flow grinding. Adding antioxidants during the airflow milling process is beneficial to inhibiting the first powder and the second powder from being oxidized by oxygen and other oxidizing substances in the environment, thereby preventing sudden performance degradation caused by oxidation.
  • the total weight of the first powder and the second powder the weight ratio of the antioxidant to the lubricant is 100:(0.05-0.2 ): (0.03 ⁇ 0.15).
  • the average particle sizes of the first powder and the second powder independently include but are not limited to 3.0 ⁇ 3.8 ⁇ m.
  • the antioxidants used in this application include but are not limited to one or more of Dongyang Antai YKJ-10, Tianjin Yuesheng YSH-01, and Ningbo Haotian HT-3.
  • the lubricants used in this application include but are not limited to one or more of Ningbo Haotian HT-3 and Tianjin Yuesheng YSH-06.
  • the temperatures of the first smelting process and the second smelting process independently include but are not limited to 1450°C to 1520°C.
  • the temperatures of the first smelting process and the second smelting process include but are not limited to the above range. Limiting it within the above range is beneficial to improving the crystal uniformity of the subsequently formed first alloy cast sheet and second alloy cast sheet, and further Improve the magnetic properties and high temperature resistance of the modified sintered NdFeB permanent magnet material subsequently produced, and further control the (BH) max of the modified sintered NdFeB permanent magnet material to be within the range of 5 to 30 MGOe.
  • the temperature of the first smelting treatment may be 1450°C, 1480°C, 1490°C, 1520°C, etc.; the temperature of the second smelting treatment may be 1450°C, 1470°C, 1520°C, etc.
  • the orientation forming process is carried out in an environment with an oxygen content of no more than 0.01%. Limiting the oxygen content in the oriented molding process to the above range is beneficial to inhibiting the oxidation of the raw materials by oxygen in the environment, thereby inhibiting the adverse effects on the magnetic properties and high temperature resistance of the modified sintered NdFeB permanent magnet material.
  • the pressing treatment is cold isostatic pressing
  • the pressure of cold isostatic pressing is 180-200MPa
  • the time is 60-120s.
  • the temperature of the sintering process is 1000-1060°C
  • the time is 2-10 hours
  • the vacuum degree does not exceed 5 ⁇ 10 -2 Pa.
  • the temperature and time of the sintering process include but are not limited to the above range. Limiting it within the above range is conducive to further reducing the absolute value of the intrinsic coercive force temperature coefficient of the modified sintered NdFeB permanent magnet material, thereby further improving its High temperature resistance.
  • the temperature of the sintering process is 1030-1050°C, the time is 4-8 hours, and the vacuum degree is less than 5 ⁇ 10 -2 Pa.
  • the tempering treatment process is a stage tempering treatment, including a first stage tempering treatment and a second stage tempering treatment; the temperature of the first stage tempering treatment is 850-950°C, and the time is 1 ⁇ 3h; the second stage tempering treatment is 480 ⁇ 600°C, and the time is 3 ⁇ 6h.
  • the temperature and time of the first-stage tempering treatment and the temperature and time of the second-stage tempering treatment respectively include but are not limited to the above ranges. Limiting them within the above ranges is conducive to further reducing the modified sintered neodymium.
  • the absolute value of the intrinsic coercive force temperature coefficient of the iron-boron permanent magnet material further improves its high temperature resistance.
  • a method for preparing modified sintered NdFeB permanent magnet material including:
  • Pr-Nd alloy, Gd-Fe alloy, Ce elemental substance, Al elemental substance, Co elemental substance, Cu elemental substance, Ga elemental substance, Zr elemental substance and boron iron are mixed and subjected to the first smelting treatment.
  • the temperature of the first smelting treatment is 1490°C.
  • the first alloy cast flake with a thickness of 0.2 ⁇ 0.4mm is obtained, of which the cast flakes with a thickness of 0.25 ⁇ 0.35mm account for more than 90%;
  • the first alloy cast piece prepared above was subjected to hydrogen breakage treatment, added with antioxidant (Dongyang Antai YKJ-10), mixed and stirred for 40 minutes, and then air-flow milled into powder, and then added lubricant (Tianjin Yuesheng YSH-06) and stirred In 60 minutes, the first powder with an average particle size of 3.4 ⁇ m was obtained; the weight ratio of the first powder, antioxidant and lubricant was 100:0.1:0.08;
  • the above-mentioned second powder is molded in a molding press with an oxygen content of less than 0.01% to obtain a compact with a density of 3.75g/ cm3 , and then is subjected to cold isostatic pressing to obtain a green compact with a density of 4.4g/ cm3 .
  • the pressure of cold isostatic pressing is 180MPa and the time is 120s;
  • the green body prepared above is transferred to a sintering furnace for sintering treatment, and the vacuum is evacuated to ⁇ 5 ⁇ 10 -2 Pa.
  • the temperature of the sintering treatment is 1030°C for 4.5 hours, and then the stage tempering treatment is performed: the first stage The temperature of the tempering treatment is 890°C and the time is 2 hours; the second stage tempering treatment is 540°C and the time is 5 hours, and finally the modified sintered NdFeB permanent magnet material is obtained.
  • the modified sintered NdFeB permanent magnet material prepared in this embodiment is composed of a first alloy, which is (Pr 0.25 Nd 0.75 ) 5 Gd 18 Ce 10 Fe 62.51 Al 3 Co 0.2 Cu 0.1 Ga 0.1 Zr 0.13 B 0.96 , where a is 5%, b is 28%, c is 3.53%, and d is 0.96%.
  • Example 1 The difference from Example 1 is that the dosage ratio of Pr-Nd alloy, Gd-Fe alloy, Ce elemental substance, Al elemental substance, Co elemental substance, Cu elemental substance, Ga elemental substance, Zr elemental substance and boron iron is changed; the temperature of the first smelting treatment is 1480°C, the average particle size of the first powder obtained was 3.3 ⁇ m.
  • Example 1 The difference from Example 1 is that the dosage ratio of Pr-Nd alloy, Gd-Fe alloy, Ce elemental substance, Al elemental substance, Co elemental substance, Cu elemental substance, Ga elemental substance, Zr elemental substance and boron iron is changed; the temperature of the first smelting treatment is 1480°C.
  • the modified sintered NdFeB permanent magnet material finally produced in this embodiment is composed of the first alloy, which is (Pr 0.25 Nd 0.75 ) 7.5 Gd 15 Ce 10 Fe 63.41 Al 1.5 Co 1 Cu 0.3 Ga 0.2 Zr 0.13 B 0.96 , where a is 7.5%, b is 25%, c is 3.13%, and d is 0.96%.
  • Pr-Nd alloy, Gd-Fe alloy, Ce elemental substance, Al elemental substance, Co elemental substance, Cu elemental substance, Ga elemental substance, Zr elemental substance and boron iron are mixed and subjected to the first smelting treatment.
  • the temperature of the first smelting treatment is 1480°C.
  • the first alloy cast flakes with a thickness of 0.2 ⁇ 0.4mm are obtained, of which the first alloy cast flakes with a thickness of 0.25 ⁇ 0.35mm account for more than 90%;
  • Pr-Nd alloy, Ce elemental substance, Al elemental substance, Co elemental substance, Cu elemental substance, Ga elemental substance, Zr elemental substance and boron iron are mixed and subjected to the second smelting treatment.
  • the temperature of the second smelting treatment is 1450°C.
  • After the second shaving treatment Obtain a second alloy cast piece with a thickness of 0.2-0.4mm, of which the second alloy cast piece with a thickness of 0.25-0.35mm accounts for more than 90%;
  • the above-mentioned second powder is molded in a molding press with an oxygen content of less than 0.01% to obtain a compact with a density of 3.8g/ cm3 , and then is subjected to cold isostatic pressing to obtain a green compact with a density of 4.45g/ cm3 .
  • the pressure of cold isostatic pressing is 180MPa and the time is 120s;
  • the modified sintered NdFeB permanent magnet material prepared in Example 4 has a different composition of the first alloy and a second alloy is introduced.
  • the modified sintered NdFeB permanent magnet material is composed of the first alloy. and a second alloy.
  • the first alloy is (Pr 0.25 Nd 0.75 ) 6.5 Gd 15 Ce 10 Fe 65.96 Al 1 Co 0.2 Cu 0.1 Ga 0.1 Zr 0.16 B 0.98 , where a is 6.5%, b is 25%, c is 1.56%, and d is 0.98%
  • the second alloy is (Pr 0.25 Nd 0.75 ) 40 Fe 55.7 Al 1.5 Co 0.2 Cu 0.5 Ga 0.5 Zr 0.1 B 0.7 , where x is 40%, y is 2.8%, and z is 0.7%.
  • the composition of the second alloy is the same as in Example 4.
  • the difference from Example 4 is that the dosage ratio of Pr-Nd alloy, Gd-Fe alloy, Ce elemental substance, Al elemental substance, Co elemental substance, Cu elemental substance, Ga elemental substance, Zr elemental substance and boron iron is changed, so that the final modified modified
  • the first alloy in the sintered NdFeB permanent magnet material is (Pr 0.25 Nd 0.75 ) 8 Gd 14 Ce 9 Fe 66.96 Al 0.5 Co 0.2 Cu 0.1 Ga 0.1 Zr 0.16 B 0.98 , where a is 8% and b is 23%, c is 1.06%, d is 0.98%; the temperature of the second smelting treatment is 1470°C, and the weight ratio of the first powder, the second powder, the antioxidant and the lubricant is 85:15:0.1:1.1.
  • the composition of the second alloy is the same as in Example 4.
  • the difference from Example 4 is that the dosage ratio of Pr-Nd alloy, Gd-Fe alloy, Ce elemental substance, Al elemental substance, Co elemental substance, Cu elemental substance, Ga elemental substance, Zr elemental substance and boron iron is changed, so that the final modified modified
  • the first alloy in the sintered NdFeB permanent magnet material is (Pr 0.25 Nd 0.75 ) 9 Gd 13 Ce 8 Fe 67.66 Al 0.2 Co 0.5 Cu 0.2 Ga 0.3 Zr 0.16 B 0.98 , where a is 9% and b is 21%.
  • c 1.36%
  • d 0.98%
  • the temperature of the second smelting treatment is 1490°C
  • the weight ratio of the first powder, the second powder, the antioxidant and the lubricant is 80:20:0.1:1.1
  • the temperature of the sintering treatment is 1050°C.
  • Example 2 The difference from Example 1 is that the object of the first smelting treatment is different, and the dosage ratio of Pr-Nd alloy, Gd-Fe alloy, Ce elemental substance, Co elemental substance, Cu elemental substance, Ti elemental substance and boron iron is changed, so that the final obtained
  • the first alloy in the modified sintered NdFeB permanent magnet material is (Pr 0.25 Nd 0.75 ) 20 Gd 10 Ce 3 Fe 65.7 Co 0.2 Cu 0.1 Ti 0.1 B 0.9 , where a is 20%, b is 13%, and c is 0.4%, d is 0.9%.
  • Example 1 The difference from Example 1 is that the object of the first smelting treatment is different, and the dosage ratio of Pr-Nd alloy, Gd-Fe alloy, Ce elemental substance, Al elemental substance, Co elemental substance, Cu elemental substance, Ga elemental substance, Ti elemental substance and boron iron is changed. , so that the first alloy in the finally prepared modified sintered NdFeB permanent magnet material is (Pr 0.25 Nd 0.75 ) 5 Gd 18 Ce 10 Fe 60.5 Al 3 Co 1.5 Cu 0.5 Ga 0.3 Ti 0.2 B 1 , where a is 5%, b is 28%, c is 5.5%, and d is 1%.
  • Example 1 The difference from Example 1 is that the object of the first smelting treatment is different, changing Pr-Nd alloy, Gd-Fe alloy, Ce element, Y element, Al element, Co element, Cu element, Ga element, Zr element and boron iron
  • the dosage ratio is such that the first alloy in the finally prepared modified sintered NdFeB permanent magnet material is (Pr 0.25 Nd 0.75 ) 5 Gd 13 Ce 10 Y 5 Fe 62.51 Al 3 Co 0.2 Cu 0.1 Ga 0.1 Zr 0.13 B 0.96 , where LRE is Gd, Ce and Y elements, and a, b, c and d are the same as in Example 1 respectively.
  • the composition of the first alloy is the same as in Example 4.
  • the difference from Example 4 is that the object of the second smelting treatment is different, and the dosage ratio of Pr-Nd alloy, Al element, Co element, Cu element, Ga element, Ti element and boron iron is changed, so that the final modified
  • the composition of the second alloy in the sintered NdFeB permanent magnet material is (Pr 0.25 Nd 0.75 ) 35 Fe 56.1 Al 2 Co 2 Cu 1.5 Ga 1.5 Ti 1 B 0.9 , where x is 35%, y is 8%, and z is 0.9%.
  • Embodiment 4 The difference from Embodiment 4 is:
  • the objects of the first smelting treatment are different. Only the proportions of Al element, Co element, Cu element, Zr element and Ti element are changed. The other raw materials remain unchanged, so that the third sintered NdFeB permanent magnet material is finally obtained.
  • the proportions of Al, Co, Cu, Zr and Ti elements in the first alloy are different.
  • the composition of the first alloy is (Pr 0.25 Nd 0.75 ) 6.5 Gd 15 Ce 10 Fe 65.96 Al 1 Co 0.2 Cu 0.2 Zr 0.06 Ti 0.1 B 0.98 , and a, b, c and d are the same as Example 1 respectively;
  • the objects of the second smelting treatment are different. Pr-Nd alloy, Cu elemental substance and Ti elemental substance are mixed with ferroboron and the second smelting treatment is performed.
  • TM' is a combination of Cu and Ti elements, so that the modified sintered neodymium iron is finally obtained.
  • the composition of the second alloy in the boron permanent magnet material is (Pr 0.25 Nd 0.75 ) 45 Fe 54 Cu 0.3 Ti 0.2 B 0.5
  • TM' is a combination of Cu and Ti elements, where x is 45%, y is 0.5%, z is 0.5%.
  • Embodiment 4 The difference from Embodiment 4 is:
  • the object of the first smelting treatment is different. Only the Zr element in the raw material is replaced by an equal amount of Ti element. The proportion of the raw material dosage remains unchanged, so that the composition of the first alloy in the finally obtained modified sintered NdFeB permanent magnet material is is (Pr 0.25 Nd 0.75 ) 6.5 Gd 15 Ce 10 Fe 65.96 Al 1 Co 0.2 Cu 0.1 Ga 0.1 Ti 0.16 B 0.98 , where TM is a combination of Al, Co, Cu, Ga and Ti elements, and a, b, c and d are the same as Example 4 respectively;
  • the object of the second smelting treatment is different.
  • the Pr-Nd alloy, Co element and ferroboron are mixed and the second smelting treatment is performed.
  • the dosage ratio of Pr_Nd alloy, Co element and boron iron is changed, so that the modified sintered neodymium iron is finally obtained.
  • the composition of the second alloy in the boron permanent magnet material is (Pr 0.25 Nd 0.75 ) 50 Fe 48.8 Co 0.2 B 1 , TM' is only Co element, in which x is 50%, y is 0.2%, and z is 1%.
  • Example 4 The difference from Example 4 is that the weight ratio of the first alloy cast piece and the second alloy cast piece during the crushing process is changed, so that the obtained modified sintered NdFeB permanent magnet material has a weight ratio of the first alloy to the second alloy.
  • the weight ratio is 70:30.
  • Example 4 The difference from Example 4 is that the weight ratio of the first alloy cast piece and the second alloy cast piece during the crushing process is changed, so that the obtained modified sintered NdFeB permanent magnet material has a weight ratio of the first alloy to the second alloy.
  • the weight ratio is 60:40.
  • Example 4 The difference from Example 4 is that the temperature of the first alloy smelting treatment is 1350°C, and the temperature of the second alloy smelting treatment is 1550°C.
  • Example 2 The difference from Example 1 is that the traditional sintered NdFeB permanent magnet material is used for magnetic performance testing.
  • the composition of this system is (PrNd) 32 Fe 66.49 Co 0.2 Cu 0.2 Zr 0.15 B 0.96 .
  • the preparation process is as follows:
  • Pr-Nd alloy, Co element, Cu element, Zr element and ferroboron are mixed and subjected to the first smelting treatment.
  • the temperature of the first smelting treatment is 1500°C.
  • an alloy with a thickness of 0.2 to 0.4mm is obtained.
  • the above powder is molded in a molding press with an oxygen content of less than 0.01% to obtain a compact with a density of 3.75g/ cm3 , and then is subjected to cold isostatic pressing to obtain a green compact with a density of 4.4g/ cm3 ; wherein The pressure of cold isostatic pressing is 180MPa and the time is 120s;
  • the green body prepared above is transferred to a sintering furnace for sintering treatment, and the vacuum is evacuated to ⁇ 5 ⁇ 10 -2 Pa.
  • the temperature of the sintering treatment is 1075°C for 4.5 hours, and then the stage tempering treatment is performed: the first stage The temperature of the tempering treatment is 920°C and the time is 2 hours; the second stage tempering treatment is 520°C and the time is 5 hours, and finally the sintered NdFeB permanent magnet material is obtained.
  • the difference from Comparative Example 1 is that the object of the first smelting treatment is different. Pr-Nd alloy, Dy-Fe alloy, Al element, Co element, Cu element, Ga element, Ti element and boron iron are mixed and the first smelting is performed. Process, change the proportion of the above raw materials, so that the final composition of the sintered NdFeB material is (Pr 0.25 Nd 0.75 ) 27 Dy 4 Fe 65.33 Al 0.8 Co 1 Cu 0.4 Ga 0.4 Ti 0.16 B 0.91 , in which LRE is only Dy element, TM is a combination of Al, Co, Cu, Ga and Ti elements.
  • Example 2 The difference from Example 1 is that the object of the first smelting treatment is different, and the raw material does not contain Gd-Fe alloy; the composition of the finally obtained sintered NdFeB material is (P r0.25 Nd 0.75 ) 5 Ce 28 Fe 62.59 Al 3 Co 0.2 Cu 0.1 Zr 0.15 B 0.96 , which does not contain the Gd element.
  • Example 1 The difference from Example 1 is that the objects of the first smelting treatment are different and the amounts of each raw material are different, so that the composition of the first alloy in the finally prepared modified sintered NdFeB permanent magnet material is (Pr 0.25 Nd 0.75 ) 3 Gd 30 Fe 62.35 Co 0.2 Zr 0.15 B 1.1 , where a is 3%, b is 30%, c is 0.35%, and d is 1.1%.
  • the permanent magnet material testing BH instrument NIM-2000 was used to conduct room temperature (20°C) and high temperature (120°C) magnetic properties tests on the modified sintered NdFeB permanent magnet materials prepared in all the examples and comparative examples of this application, and calculated Temperature remanence Br temperature coefficient and intrinsic coercive force Hcj temperature coefficient.
  • Hcj 0 is the intrinsic coercive force measured at 20°C.
  • Modified sintered NdFeB permanent magnet material has a negative temperature coefficient, and its magnetization intensity and intrinsic coercive force will decrease as the temperature increases, so the data in Table 1 are negative values.
  • Example 1 6.65 9.176 10.64 -0.1173 -0.6801
  • Example 2 7.58 10.452 13.46 -0.1083 -0.5742
  • Example 3 8.21 9.636 15.92 -0.1028 -0.4316
  • Example 4 9.02 9.400 19.28 -0.1056 -0.4675
  • Example 5 9.64 9.250 22.52 -0.1063 -0.4845
  • Example 6 10.26 9.890 25.64 -0.1058 -0.4781
  • Example 7 10.74 10.586 28.98 -0.1054 -0.4853
  • Example 8 6.32 9.522 9.84 -0.1158 -0.6741
  • Example 9 7.67 5.28 13.89 -0.1325 -0.7588
  • Example 10 9.14 9.650 19.65 -0.1061 -0.4686
  • Example 11 9.09 9.180 19.48 -0.1067 -0.4662
  • Example 12 8.83
  • Example 13 9.43 10.870 22.04 -0.1054 -0.4831
  • Example 14 8.42 9.670 15.44 -0.1087 -0.5335
  • Example 15 8.55 7.640 17.88 -0.1154 -0.5458
  • Comparative example 1 14.24 12.58 50.56 -0.1286 -0.7247
  • Comparative example 2 11.96 26.34 34.21 -0.1103 -0.5366
  • Comparative example 3 6.87 1.596 10.96 -0.1387 -0.8336
  • Comparative example 4 7.96 3.225 14.63 -0.0945 -0.3872
  • Nd element on the one hand, it can obtain the maximum magnetic energy product (BH) max in the range of 5 ⁇ 30MGOe and the magnetic properties meet the needs of low-end fields (remanence Br is 6 ⁇ 11kGs, intrinsic coercive force Hcj is 5 ⁇ 11kOe) Modified sintered NdFeB permanent magnet materials; on the other hand, specific types of rare earth elements and TM elements work together in a specific weight ratio of the present invention (strictly controlling the value ranges of a, b, c, and d) to improve the intrinsic correction. The temperature coefficient of force is improved, thereby improving its high temperature resistance and making it suitable for applications under high temperature conditions.
  • BH maximum magnetic energy product
  • Proportional Examples 2 to 7 and 10 to 14 and Comparative Examples 1 and 2 show that specific types of rare earth elements Gd and Ce are used to replace Pr and Nd elements in the sintered NdFeB permanent magnet material, and a specific proportion of TM elements is used.
  • the Hcj (6 ⁇ 11kOe) of the obtained material is much lower than that of conventional sintered NdFeB materials, its remanence and intrinsic coercive force temperature coefficient are significantly better than those of N grade (Hcj between 12 ⁇ 14kOe) sintered Nd
  • the iron-boron permanent magnet material is close to or even better than the UH grade (Hcj at 25-30kOe) sintered neodymium-iron-boron permanent magnet material, which enables the modified sintered neodymium-iron-boron permanent magnet material in this application to meet the needs of high-temperature applications within 150°C.
  • Comparing Examples 1, 7 and 8 and Comparative Example 4 it can be seen that the Gd element content in the first alloy of the modified sintered NdFeB permanent magnet material prepared in Comparative Example 4 is very high (up to 30%), while the content of Gd in Example 4 is very high (up to 30%).
  • the Gd element content in 1, 7 and 8 is within the preferred range of this application.
  • Comparing Examples 1 and 9 and Comparative Examples 2 and 3 it can be seen that compared with other types of elements, the use of the preferred type of LRE element in the present application can improve the high temperature resistance of the modified sintered NdFeB permanent magnet material. It can be seen from the performance results measured in Comparative Example 2 in Table 1 that although Comparative Example 2 meets the high-performance sintered NdFeB material grade N35UH, its performance is excellent. However, comparing Example 1 and Comparative Example 2, it can be seen that the preparation cost of the modified sintered NdFeB permanent magnet material in Comparative Example 2 is significantly higher than that in Example 1. This shows that using the specific type and amount of rare earth elements in this application to replace the Pr and Nd elements in the traditional sintered NdFeB permanent magnet material can not only improve the high temperature resistance, but also reduce the preparation cost.
  • the modified sintered NdFeB permanent magnet material containing both the first alloy and the second alloy is beneficial to the performance of the two components.
  • the synergistic effect of the two is conducive to further improving the magnetic properties; at the same time, it is conducive to further reducing the absolute value of the intrinsic coercive force temperature coefficient of the modified sintered NdFeB permanent magnet material, thereby further improving its high temperature resistance.
  • the temperatures of the first smelting process and the second smelting process include but are not limited to the preferred range of the present application. Limiting it to the preferred range of the present application is beneficial to improving the subsequent formation of the first alloy cast sheet and The crystal uniformity of the second alloy cast piece can thereby improve the magnetic properties and high temperature resistance of the subsequently prepared modified sintered NdFeB permanent magnet material, and at the same time further control the properties of the prepared modified sintered NdFeB permanent magnet material.
  • (BH) max is in the range of 5 ⁇ 30MGOe.

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Abstract

本发明提供了一种改性烧结钕铁硼永磁材料及其制备方法。该改性烧结钕铁硼永磁材料包括第一合金，第一合金具有式(I)所示化学式：(Pr 0.25Nd 0.75) a(LRE) bTM cFe 100％-a-b-c-dB d(I)，其中，LRE为稀土元素，且LRE选自Gd、Y和Ce元素中的一种或多种，且至少含有Gd元素，TM选自Al、Cu、Co、Ga、Nb、Zr和Ti元素中的一种或多种，a为5～20％，b为13～28％，c为0.4～5.5％，d为0.9～1％。本申请提供的改性烧结钕铁硼永磁材料的最大磁能积在5～30MGOe且剩磁在6～11kGs、内禀矫顽力在5～11kOe范围内，同时具有优异的耐高温性能且成本低。

Description

改性烧结钕铁硼永磁材料及其制备方法
本申请是以CN申请号为202210761631.X，申请日为2022年6月30日的中国申请为基础，并主张其优先权，该CN申请的公开内容再次作为整体引入本申请中。
技术领域
本发明涉及稀土永磁材料技术领域，具体而言，涉及一种改性烧结钕铁硼永磁材料及其制备方法。
背景技术
永磁材料具有被磁化后不易退磁的特性，被广泛应用于工业和生活的各类领域中。根据永磁材料的磁能积大小、耐温特性以及成本，可以根据不同应用领域的要求和特点选择相对合适的高性价比永磁材料。
目前常用的永磁材料中，永磁铁氧体磁性能低(其最大磁能积(BH)max低于5MGOe)但价格低廉，在低端应用市场中占据主导地位。烧结钕铁硼作为第三代稀土永磁材料，具有高磁能积((BH)max为30～55MGOe)和高矫顽力的特点，在高性能应用领域中具有较优异的性能和成本优势。因此，烧结钕铁硼永磁材料自发现后便迅速替代第二代SmCo系稀土永磁材料成为计算机、信息、通讯、家电、交通运输、办公自动化等高端应用的主要选择。然而，在永磁铁氧体和烧结钕铁硼之间的中低端应用领域还存在一部分性能空白，尤其是(BH)max在5～30MGOe之间的永磁材料尚未报道。虽然粘结钕铁硼和SmCo系永磁体性能在上述范围之间，但粘结钕铁硼的(BH)max仅为13MGOe，相对较低，而且SmCo系磁体成本又太高，使得企业压力大，导致粘结钕铁硼和SmCo系永磁体也无法满足这部分低端应用领域的需求。
在此基础上，开发一种性能介于永磁铁氧体和烧结钕铁硼之间的低成本永磁体对于应对永磁体中低端应用需求和缓解企业压力具有重要意义。
近年来研究人员和企业针对降低烧结钕铁硼磁体的成本和推广低端应用方面开展了大量工作，主要通过采用储量丰富且价格低廉的高丰度稀土La、Ce、Y等部分替代 金属钕来降低产品成本，且发明了很多不同性能的永磁体，并实现了产业化，这部分磁体主要集中在(BH)max高于28MGOe的永磁体，且大部分应用于对使用温度要求较低的低端应用领域。对于更低磁能积、低成本及高耐温性烧结钕铁硼磁体方面的研究相对较少。因此，开发这一类磁体具有重大的实用价值。
采用高丰度稀土La、Ce、Y元素替代Pr和Nd元素是常用的进一步降低无重稀土烧结钕铁硼磁体成本的方法，但大部分方法都关注制备高磁能积材料和高丰度稀土的替代量，对材料的高温使用特性关注较少。
因此，研究并开发出一种最大磁能积(BH)max在5～30MGOe之间、同时具有耐高温性能优异以及成本低的烧结钕铁硼磁性材料具有重要意义。
发明内容
本发明的主要目的在于提供一种改性烧结钕铁硼永磁材料及其制备方法，以解决现有技术中烧结钕铁硼永磁材料的耐高温性能差和成本高的问题，同时能够弥补现有的粘结钕铁硼和烧结钕铁硼之间的性能空白，以解决现有的永磁材料产品难以满足最大磁能积在5～30MGOe之间的市场需求的问题。
为了实现上述目的，本发明一方面提供了一种改性烧结钕铁硼永磁材料，该改性烧结钕铁硼永磁材料包括第一合金，第一合金具有式(I)所示化学式：(Pr 0.25Nd 0.75) a(LRE) bTM cFe 100％-a-b-c-dB d(I)，其中，LRE为稀土元素，且LRE选自Gd、Y和Ce元素中的一种或多种，且至少含有Gd元素，TM选自Al、Cu、Co、Ga、Nb、Zr和Ti元素中的一种或多种，a为5～20％，b为13～28％，c为0.4～5.5％，d为0.9～1％。
进一步地，a为7～16％，b为16～26％，c为0.7～3.3％，d为0.92～0.98％。
进一步地，改性烧结钕铁硼永磁材料还包括第二合金，第二合金具有式(II)所示化学式：(Pr 0.25Nd 0.75) xTM’ yFe 100％-x-y-zB z(II)，其中，TM’选自Al、Cu、Co、Ga、Nb、Zr和Ti元素中的一种或多种，x为35～45％，y为0.5～9％，z为0.5～0.9％；优选地，x为38～42％，y为1.6～4.5％，z为0.6～0.8％。
进一步地，以第一合金和第二合金的总重量计，第二合金的重量百分含量不超过30wt％。
进一步地，LRE为Gd和Ce，或者为Gd和Y，或者为Gd、Y和Ce；优选地，LRE为Gd和Ce；更优选地，LRE为Gd和Ce，且Gd和Ce的重量比为(13～18)∶(8～10)，更进一步优选为(13～15)∶(8～10)；TM’为Co、Cu和Zr的组合，或者为Al、Co、Cu和Zr的组合，或者为Al、Co、Ga和Zr的组合，或者为Al、Cu、Ga和Zr的组合，或者为Al、Co、Cu、Ga和Zr的组合；优选地，TM’为Al、Co、Cu、Ga和Zr的组合；更优选地，TM’为Al、Co、Cu、Ga和Zr的组合，且Al、Co、Cu、Ga和Zr的重量比为(0～3)∶(0.2～1.5)∶(0.1～0.5)∶(0～0.3)∶(0.1～0.16)，更进一步优选为(0.2～1.5)∶(0.2～1.0)∶(0.1～0.3)∶(0.1～0.3)∶(0.1～0.16)；
TM为Al、Co、Cu、Ga和Zr的组合，或者为Al、Co、Cu、Ga和Nb的组合，或者为Al、Co、Cu、Ga和Ti的组合；优选地，TM为Al、Co、Cu、Ga和Zr的组合；更优选地，TM为Al、Co、Cu、Ga和Zr的组合，且Al、Co、Cu、Ga和Zr的重量比为(0.2～3)∶(0.2～1.5)∶(0.1～0.5)∶(0.1～0.3)∶(0.1～0.16)，更进一步优选为(0.2～1.5)∶(0.2～1.0)∶(0.1～0.3)∶(0.1～0.3)∶(0.1～0.16)；或，
TM为Al、Co、Cu、Ga、Nb和Zr，或者为Al、Co、Cu、Ga、Zr和Ti的组合；优选地，TM为Al、Co、Cu、Ga、Zr和Ti的组合；更优选地，TM为Al、Co、Cu、Ga、Zr和Ti的组合，且Al、Co、Cu、Ga、Zr和Ti的重量比为(0.2～3)∶(0.2～1.5)∶(0.1～0.5)∶(0.1～0.3)∶(0.04～0.16)∶(0.05～0.2)，更进一步优选为(0.2～1.5)∶(0.2～1.0)∶(0.1～0.3)∶(0.1～0.3)∶(0.04～0.12)∶(0.05～0.15)。
进一步地，第一合金和第二合金的重量比为(80～90)∶(10～20)。
为了实现上述目的，本发明另一个方面还提供了一种本申请提供的上述改性烧结钕铁硼永磁材料的制备方法，该改性烧结钕铁硼永磁材料的制备方法包括：将Pr-Nd合金、LRE源、TM源与硼铁混合并进行第一熔炼处理和第一甩片处理，得到第一合金铸片；LRE源选自Gd-Fe合金、Y单质和Ce单质中的一种或多种；TM源选自Al单质、Cu单质、Co单质、Ga单质、Nb-Fe合金、Zr单质和Ti单质中的一种或多种； 对第一合金铸片进行破碎处理，得到第一粉末；将第一粉末进行取向成型和压制处理，得到生坯；对生坯进行烧结处理和回火处理，得到改性烧结钕铁硼永磁材料。
进一步地，改性烧结钕铁硼永磁材料的制备方法还包括：将Pr-Nd合金、TM’源与硼铁混合并进行第二熔炼处理和第二甩片处理，得到第二合金铸片；TM源选自Al单质、Cu单质、Co单质、Ga单质、Nb-Fe合金、Zr单质和Ti单质中的一种或多种；在破碎处理的过程中，同时加入第二合金铸片以与第一合金铸片一起进行破碎处理，得到第二粉末；在进行取向成型之前将第二粉末与润滑剂混合；优选地，破碎处理依次包括氢破处理和气流磨制粉，在气流磨过程中加入抗氧化剂，在气流磨制粉结束后得到第二粉末。
进一步地，第一粉末、抗氧化剂与润滑剂的重量比为100∶(0.05～0.2)∶(0.03～0.15)；优选地，第一粉末的平均粒度选自3.0～3.8μm。
进一步地，第一粉末和第二粉末的总重量、抗氧化剂与润滑剂的重量比为100∶(0.05～0.2)∶(0.03～0.15)；优选地，第一粉末和第二粉末的平均粒度分别独立地选自3.0～3.8μm。
应用本发明的技术方案，使特定种类和用量的稀土元素(如Gd、Y和Ce元素)替代传统烧结钕铁硼永磁材料((PrNd)-Fe-B)中的Pr、Nd元素，一方面能够得到最大磁能积(BH) max在5～30MGOe范围内且磁性能满足低端领域需求(剩磁Br在6～11kGs、内禀矫顽力Hcj在5～11kOe)的改性烧结钕铁硼永磁材料；另一方面特定种类的稀土元素与TM元素以本发明特定的重量比(严格控制a、b、c、d的取值范围)共同作用能够改善内禀矫顽力的温度系数，从而提高其耐高温性能，使其满足高温条件下的应用。此外，由于Gd、Y、Ce等元素在天然资源中的丰度明显高于Pr、Nd元素，能够在实现上述效果的同时降低材料本身的成本。
具体实施方式
需要说明的是，在不冲突的情况下，本申请中的实施例及实施例中的特征可以相互组合。下面将结合实施例来详细说明本发明。
正如背景技术所描述的，现有的烧结钕铁硼永磁材料存在无法兼具耐高温性能优异和成本低的问题，以及现有的粘结钕铁硼产品和烧结钕铁硼产品之间存在性能空白，难以满足最大磁能积在5～30MGOe之间的市场需求。为了解决上述技术问题，本申请提供了一种改性烧结钕铁硼永磁材料，该改性烧结钕铁硼永磁材料包括第一合金，第一合金具有式(I)所示化学式：(Pr 0.25Nd 0.75) a(LRE) bTM cFe 100％-a-b-c-dB d(I)，其中，LRE为稀土元素，且LRE包括但不限于Gd、Y和Ce元素中的一种或多种，且至少含有Gd元素，TM包括但不限于Al、Cu、Co、Ga、Nb、Zr和Ti元素中的一种或多种，a为5～20％，b为13～28％，c为0.4～5.5％，d为0.9～1％。
需要说明的是，本申请式(I)所示化学式中的a、b、c和d以及式(II)化学式中的x、y和z分别指对应成分的重量百分含量。
使特定种类和用量的稀土元素(如Gd、Y和Ce元素)替代传统烧结钕铁硼永磁材料((PrNd)-Fe-B)中的Pr、Nd元素，一方面能够得到最大磁能积(BH) max在5～30MGOe范围内且磁性能满足低端领域需求(剩磁Br在6～11kGs、内禀矫顽力Hcj在5～11kOe)的改性烧结钕铁硼永磁材料；另一方面特定种类的稀土元素与TM元素以本发明特定的重量比(严格控制a、b、c、d的取值范围)共同作用能够改善内禀矫顽力的温度系数，从而提高其耐高温性能，使其满足高温条件下的应用。此外，由于Gd、Y、Ce等元素在天然资源中的丰度明显高于Pr、Nd元素，能够在实现上述效果的同时降低材料本身的成本。
在一种优选的实施方式中，a为7～16％，b为16～26％，c为0.7～3.3％，d为0.92～0.98％。a、b、c、d的取值范围分别包括但不限于上述范围，将其进一步限定在上述范围内有利于提高改性烧结钕铁硼永磁材料的磁性能，并使其(BH) max在5～30MGOe范围内；同时有利于降低其内禀矫顽力温度系数的绝对值，进而有利于提高其耐高温性能。
在一种优选的实施方式中，改性烧结钕铁硼永磁材料还包括第二合金，第二合金具有式(II)所示化学式：(Pr 0.25Nd 0.75) xTM’ yFe 100％-x-y-zB z(II)，其中，TM’包括但不限于Al、Cu、Co、Ga、Nb、Zr和Ti元素中的一种或多种，x为35～45％，y为0.5～9％，z为0.5～0.9％。相比于单一合金成分的改性烧结钕铁硼永磁材料，使改性烧结 钕铁硼永磁材料同时含有特定成分第一合金(严格控制a、b、c、d的取值范围)与特定成分的第二合金(严格控制x、y和z的取值范围)有利于发挥二者的协同作用，有利于实现磁耦合隔离，从而有利于提升矫顽力，有利于进一步提高磁性能；同时有利于进一步降低改性烧结钕铁硼永磁材料的内禀矫顽力温度系数的绝对值，进而进一步提高其耐高温性能和最大磁能积等综合性能。相比于其它种类的TM’，采用上述优选种类的TM’一方面能够改善材料的微观结构晶粒结构和晶界相分布，在不降低材料剩磁的情况下更好地提升材料的内禀矫顽力；另一方面可改善材料的烧结特性，能够在一定的温度范围内获得致密和晶粒均匀的磁体，更有利于改性烧结钕铁硼永磁材料的制备。
为了更进一步发挥第一合金和第二合金的协同作用，进而更进一步提高改性烧结钕铁硼永磁材料的磁性能和耐高温性能等综合性能，优选地，x为38～42％，y为1.6～4.5％，z为0.6～0.8％。
在一种优选的实施方式中，以第一合金和第二合金的总重量计，第二合金的重量百分含量不超过30wt％。当第二合金的重量百分含量超过30wt％时，一方面第二合金对改性烧结钕铁硼材料晶界相分布的改善作用会减弱，对内禀矫顽力的提升效果也会减弱；另一方面材料成分中稀土元素含量过多和B含量过少，会影响材料的烧结特性，导致改性烧结钕铁硼永磁材料的剩磁和磁能积的下降。将第二晶相的重量百分含量限定在上述范围内有利于发挥二者的协同作用，有利于进一步提高改性烧结钕铁硼永磁材料的耐高温性能，同时进一步降低成本并使磁性能维持较高水平。
在一种优选的实施方式中，LRE为Gd和Ce，或者为Gd和Y，或者为Gd、Y和Ce。相比于其它种类，采用上述特定种类的LRE元素替代Nd元素一方面有利于大幅度降低改性烧结钕铁硼永磁材料的成本，另一方面有利于提高其耐高温性能同时使磁性能维持较高水平。
为了进一步在降低改性烧结钕铁硼永磁材料的成本同时提高磁性能和耐高温性能，优选地，LRE为Gd和Ce；更优选地，LRE为Gd和Ce，且Gd和Ce的重量比为(13～18)∶(8～10)，更进一步优选为(13～15)∶(8～10)。
在一种优选的实施方式中，TM’为Co、Cu和Zr的组合，或者为Al、Co、Cu和Zr的组合，或者为Al、Co、Ga和Zr的组合，或者为Al、Cu、Ga和Zr的组合，或者为Al、Co、Cu、Ga和Zr的组合。相比于其它种类，采用上述特定种类的TM’元素进行掺杂一方面有利于降低改性烧结钕铁硼永磁材料的成本，另一方面有利于提高其磁性能和耐高温性能。
为了进一步在降低改性烧结钕铁硼永磁材料的成本同时提高磁性能和耐高温性能，优选地，TM’为Al、Co、Cu、Ga和Zr的组合；更优选地，TM’为Al、Co、Cu、Ga和Zr的组合，且Al、Co、Cu、Ga和Zr的重量比为(0～3)∶(0.2～1.5)∶(0.1～0.5)∶(0～0.3)∶(0.1～0.16)，更进一步优选为(0.2～1.5)∶(0.2～1.0)∶(0.1～0.3)∶(0.1～0.3)∶(0.1～0.16)。
在一种优选的实施方式中，TM为Al、Co、Cu、Ga和Zr的组合，或者为Al、Co、Cu、Ga和Nb的组合，或者为Al、Co、Cu、Ga和Ti的组合。相比于其它种类，采用上述特定种类的TM元素进行掺杂，一方面有利于降低改性烧结钕铁硼永磁材料的成本，另一方面有利于提高其磁性能和耐高温性能。
为了进一步在降低改性烧结钕铁硼永磁材料的成本同时提高磁性能和耐高温性能，优选地，TM为Al、Co、Cu、Ga和Zr的组合；更优选地，TM为Al、Co、Cu、Ga和Zr的组合，且Al、Co、Cu、Ga和Zr的重量比为(0.2～3)∶(0.2～1.5)∶(0.1～0.5)∶(0.1～0.3)∶(0.1～0.16)，更进一步优选为(0.2～1.5)∶(0.2～1.0)∶(0.1～0.3)∶(0.1～0.3)∶(0.1～0.16)。
在另一种优选的实施方式中，TM为Al、Co、Cu、Ga、Nb和Zr，或者为Al、Co、Cu、Ga、Zr和Ti的组合。相比于其它种类，采用上述特定种类的TM元素进行掺杂，一方面有利于降低改性烧结钕铁硼永磁材料的成本，另一方面有利于提高其磁性能和耐高温性能。
优选地，TM为Al、Co、Cu、Ga、Zr和Ti的组合；更优选地，TM为Al、Co、Cu、Ga、Zr和Ti的组合，且Al、Co、Cu、Ga、Zr和Ti的重量比为(0.2～3)∶(0.2～ 1.5)∶(0.1～0.5)∶(0.1～0.3)∶(0.04～0.16)∶(0.05～0.2)，更进一步优选为(0.2～1.5)∶(0.2～1.0)∶(0.1～0.3)∶(0.1～0.3)∶(0.04～0.12)∶(0.05～0.15)。
在一种优选的实施方式中，第一合金和第二合金的重量比为(80～90)∶(10～20)。第一合金和第二合金的重量比包括但不限于上述范围，将其限定在上述范围内有利于进一步发挥二者的协同作用，有利于进一步提高改性烧结钕铁硼永磁材料的耐高温性能，同时进一步降低成本。
本申请第二方面还提供了一种本申请提供的上述改性烧结钕铁硼永磁材料的制备方法，该改性烧结钕铁硼永磁材料的制备方法包括：将Pr-Nd合金、LRE源、TM源与硼铁混合并进行第一熔炼处理和第一甩片处理，得到第一合金铸片；LRE源包括但不限于Gd-Fe合金、Y单质和Ce单质中的一种或多种；TM源包括但不限于Al单质、Cu单质、Co单质、Ga单质、Nb-Fe合金、Zr单质和Ti单质中的一种或多种；对第一合金铸片进行破碎处理，得到第一粉末；将第一粉末进行取向成型和压制处理，得到生坯；对生坯进行烧结处理和回火处理，得到改性烧结钕铁硼永磁材料。
对上述原料进行第一熔炼处理以便于进行后续的第一甩片处理，得到第一合金铸片；对第一合金铸片进行破碎处理能够将其破碎细化成粒度较小的第一粉末，便于后续进行取向成型处理；取向成型处理是指在外磁场作用下使第一粉末克服粉末颗粒之间的摩擦力和团聚从而形成具有取向度的处理；压制处理是指采用压力使第一粉末获得密实度和形状，从而得到生坯；将第一粉末进行取向成型和压制处理之后，得到生坯；对生坯进行烧结处理和回火处理，得到改性烧结钕铁硼永磁材料。
为了进一步提高破碎处理的效果和粒径更加均一的粉末，在一种优选的实施方式中，第一粉末、抗氧化剂与润滑剂的重量比为100∶(0.05～0.2)∶(0.03～0.15)。优选地，第一粉末的平均粒度包括但不限于3.0～3.8μm。
在一种优选的实施方式中，改性烧结钕铁硼永磁材料的制备方法还包括：将Pr-Nd合金、TM’源与硼铁混合并进行第二熔炼处理和第二甩片处理，得到第二合金铸片；TM源包括但不限于Al单质、Cu单质、Co单质、Ga单质、Nb-Fe合金、Zr单质和Ti单质中的一种或多种；在破碎处理的过程中，同时加入第二合金铸片以与第一合金 铸片一起进行破碎处理，得到第二粉末；在进行取向成型之前将第二粉末与润滑剂混合。采用上述处理方法能够得到晶界相分布更均匀的改性烧结钕铁硼永磁材料，能够实现磁耦合隔离，从而能够有效地提升矫顽力和耐高温性能。将第二粉末与润滑剂混合后再进行取向成型处理能够减小第二粉末颗粒之间的摩擦力，便于加工和提升材料的取向度。
氢破处理可分为吸氢和脱氢两个阶段，其原理是利用氢与富Nd相和主相发生氢化反应。氢破处理后能够得到酥脆的粉末，进而有利于进一步细破碎。气流磨制粉是利用高压气体流将氢破处理的粉末颗粒加速到超音速，并使粉末颗粒间相互对撞而发生破碎的工艺。在一种优选的实施方式中，破碎处理依次包括氢破处理和气流磨制粉，在气流磨制粉过程中加入抗氧化剂，在气流磨制粉结束后得到第二粉末。在气流磨制粉过程中加入抗氧化剂有利于抑制第一粉末以及第二粉末被环境中的氧气等氧化性物质氧化，进而防止因氧化导致的性能骤降。
为了进一步提高破碎处理的效果和粒径更加均一的粉末，在一种优选的实施方式中，第一粉末和第二粉末的总重量、抗氧化剂与润滑剂的重量比为100∶(0.05～0.2)∶(0.03～0.15)。优选地，第一粉末和第二粉末的平均粒度分别独立地包括但不限于3.0～3.8μm。
本申请采用的抗氧化剂包括但不限于东阳安泰YKJ-10、天津悦晟YSH-01、宁波昊天HT-3中的一种或多种。本申请采用的润滑剂包括但不限于宁波昊天HT-3、天津悦晟YSH-06中的一种或多种。
在一种优选的实施方式中，第一熔炼处理和第二熔炼处理过程的温度分别独立地包括但不限于1450～1520℃。第一熔炼处理和第二熔炼处理过程的温度包括但不限于上述范围，将其限定在上述范围内有利于提高后续形成的第一合金铸片和第二合金铸片的晶型均一性，进而提高后续制得的改性烧结钕铁硼永磁材料的磁性能和耐高温性能，同时进一步控制制得的改性烧结钕铁硼永磁材料的(BH) max在5～30MGOe范围内。第一熔炼处理的温度可以为1450℃、1480℃、1490℃、1520℃等；第二熔炼处理的温度可以为1450℃、1470℃、1520℃等。
在一种优选的实施方式中，取向成型的过程在含氧量不超过0.01％的环境中进行。将取向成型的过程在含氧量限定在上述范围内有利于抑制原料被环境中的氧气氧化，进而抑制对改性烧结钕铁硼永磁材料磁性能和耐高温性能的不利影响。
在一种优选的实施方式中，压制处理为冷等静压处理，冷等静压处理的压强为180～200MPa，时间为60～120s。
在一种优选的实施方式中，烧结处理过程的温度为1000～1060℃，时间为2～10h，真空度不超过5×10 -2Pa。烧结处理过程的温度和时间包括但不限于上述范围，将其限定在上述范围内有利于进一步降低改性烧结钕铁硼永磁材料的内禀矫顽力温度系数的绝对值，进而进一步提高其耐高温性能。
为了更进一步降低内禀矫顽力温度系数的绝对值，进而更进一步提高其耐高温性能，优选地，烧结处理过程的温度为1030～1050℃，时间为4～8h，真空度低于5×10 -2Pa。
在一种优选的实施方式中，回火处理过程为阶段回火处理，包括第一段回火处理和第二段回火处理；第一段回火处理的温度为850～950℃，时间为1～3h；第二段回火处理为480～600℃，时间为3～6h。回火处理过程中，第一段回火处理的温度和时间以及第二段回火处理的温度和时间分别包括但不限于上述范围，将其限定在上述范围内有利于进一步降低改性烧结钕铁硼永磁材料的内禀矫顽力温度系数的绝对值，进而进一步提高其耐高温性能。
以下结合具体实施例对本申请作进一步详细描述，这些实施例不能理解为限制本申请所要求保护的范围。
实施例1
一种改性烧结钕铁硼永磁材料的制备方法，包括：
将Pr-Nd合金、Gd-Fe合金、Ce单质、Al单质、Co单质、Cu单质、Ga单质、Zr单质与硼铁混合并进行第一熔炼处理，第一熔炼处理的温度为1490℃，第一甩片处 理后得到厚度为0.2～0.4mm的第一合金铸片，其中厚度为0.25～0.35mm的铸片占90％以上；
将上述制得的第一合金铸片进行氢破处理，加入抗氧化剂(东阳安泰YKJ-10)混合并搅拌40min，进行气流磨制粉，之后加入润滑剂(天津悦晟YSH-06)并搅拌60min，得到平均粒度为3.4μm的第一粉末；第一粉末、抗氧化剂与润滑剂的重量比为100∶0.1∶0.08；
将上述第二粉末在氧含量小于0.01％的成型压机中进行成型，得到密度为3.75g/cm 3的压坯，然后经冷等静压处理后得到密度为4.4g/cm 3的生坯；冷等静压处理的压强为180MPa，时间为120s；
对上述制得的生坯转移至烧结炉中进行烧结处理，抽真空至＜5×10 -2Pa，烧结处理的温度为1030℃，时间为4.5h，再进行阶段回火处理：第一段回火处理的温度为890℃，时间为2h；第二段回火处理为540℃，时间为5h，最终得到改性烧结钕铁硼永磁材料。
本实施例中制得的改性烧结钕铁硼永磁材料由第一合金构成，该第一合金为(Pr 0.25Nd 0.75) 5Gd 18Ce 10Fe 62.51Al 3Co 0.2Cu 0.1Ga 0.1Zr 0.13B 0.96，其中a为5％，b为28％，c为3.53％，d为0.96％。
实施例2
与实施例1的区别在于：改变Pr-Nd合金、Gd-Fe合金、Ce单质、Al单质、Co单质、Cu单质、Ga单质、Zr单质与硼铁的用量比例；第一熔炼处理的温度为1480℃，得到的第一粉末的平均粒度为3.3μm。
本实施例中最终制得的改性烧结钕铁硼永磁材料由第一合金构成，该第一合金为(Pr 0.25Nd 0.75) 6.5Gd 16Ce 10Fe 63.31Al 2Co 0.5Cu 0.3Ga 0.3Zr 0.13B 0.96，其中a为6.5％，b为26％，c为3.23％，d为0.96％；
实施例3
与实施例1的区别在于：改变Pr-Nd合金、Gd-Fe合金、Ce单质、Al单质、Co单质、Cu单质、Ga单质、Zr单质与硼铁的用量比例；第一熔炼处理的温度为1480℃。
本实施例中最终制得的改性烧结钕铁硼永磁材料由第一合金构成，该第一合金为(Pr 0.25Nd 0.75) 7.5Gd 15Ce 10Fe 63.41Al 1.5Co 1Cu 0.3Ga 0.2Zr 0.13B 0.96，其中a为7.5％，b为25％，c为3.13％，d为0.96％。
实施例4
一种改性烧结钕铁硼永磁材料的制备方法不同，包括：
将Pr-Nd合金、Gd-Fe合金、Ce单质、Al单质、Co单质、Cu单质、Ga单质、Zr单质与硼铁混合并进行第一熔炼处理，第一熔炼处理的温度为1480℃，第一甩片处理后得到厚度为0.2～0.4mm的第一合金铸片，其中厚度为0.25～0.35mm的第一合金铸片占90％以上；
将Pr-Nd合金、Ce单质、Al单质、Co单质、Cu单质、Ga单质、Zr单质与硼铁混合并进行第二熔炼处理，第二熔炼处理的温度为1450℃，第二甩片处理后得到厚度为0.2～0.4mm的第二合金铸片，其中厚度为0.25～0.35mm的第二合金铸片占90％以上；
将上述制得的第一合金铸片与第二合金铸片混合，依次进行氢破处理和气流磨制粉；在气流磨过程中加入抗氧化剂(东阳安泰YKJ-10)混合并搅拌40min，加入润滑剂(天津悦晟YSH-01和YSH-06)并搅拌60min，得到平均粒度为3.3μm的第二粉末；第一粉末、第二粉末、抗氧化剂与润滑剂的重量比为90∶10∶0.1∶0.11，其中润滑剂YSH-01与YSH-06的重量比为0.03∶0.08；
将上述第二粉末在氧含量小于0.01％的成型压机中进行成型，得到密度为3.8g/cm 3的压坯，然后经冷等静压处理后得到密度为4.45g/cm 3的生坯；冷等静压处理的压强为180MPa，时间为120s；
对上述制得的生坯转移至烧结炉中进行烧结处理，抽真空至＜5×10 -2Pa，烧结处理的温度为1045℃，时间为4.5h，再进行阶段回火处理，其中第一段回火处理的温度 为890℃，时间为2h；第二段回火处理为550℃，时间为5h，最终得到改性烧结钕铁硼永磁材料。
与实施例1相比，实施例4制得的改性烧结钕铁硼永磁材料中第一合金的成分不同中还引入了第二合金，改性烧结钕铁硼永磁材料由第一合金和第二合金构成。具体地，第一合金为(Pr 0.25Nd 0.75) 6.5Gd 15Ce 10Fe 65.96Al 1Co 0.2Cu 0.1Ga 0.1Zr 0.16B 0.98，其中a为6.5％，b为25％，c为1.56％，d为0.98％，第二合金为(Pr 0.25Nd 0.75) 40Fe 55.7Al 1.5Co 0.2Cu 0.5Ga 0.5Zr 0.1B 0.7，其中x为40％，y为2.8％，z为0.7％。
实施例5
第二合金的成分与实施例4相同。与实施例4的区别在于：改变Pr-Nd合金、Gd-Fe合金、Ce单质、Al单质、Co单质、Cu单质、Ga单质、Zr单质与硼铁的用量比例，使得最终制得的改性烧结钕铁硼永磁材料中的第一合金为(Pr 0.25Nd 0.75) 8Gd 14Ce 9Fe 66.96Al 0.5Co 0.2Cu 0.1Ga 0.1Zr 0.16B 0.98，其中a为8％，b为23％，c为1.06％，d为0.98％；第二熔炼处理的温度为1470℃，第一粉末、第二粉末、抗氧化剂与润滑剂的重量比为85∶15∶0.1∶1.1。
实施例6
第二合金的成分与实施例4相同。与实施例4的区别在于：改变Pr-Nd合金、Gd-Fe合金、Ce单质、Al单质、Co单质、Cu单质、Ga单质、Zr单质与硼铁的用量比例，使得最终制得的改性烧结钕铁硼永磁材料中的第一合金为(Pr 0.25Nd 0.75) 9Gd 13Ce 8Fe 67.66Al 0.2Co 0.5Cu 0.2Ga 0.3Zr 0.16B 0.98，其中a为9％，b为21％，c为1.36％，d为0.98％；第二熔炼处理的温度为1490℃，第一粉末、第二粉末、抗氧化剂与润滑剂的重量比为80∶20∶0.1∶1.1，烧结处理的温度为1050℃。
实施例7
与实施例1的区别在于：第一熔炼处理的对象不同，改变Pr-Nd合金、Gd-Fe合金、Ce单质、Co单质、Cu单质、Ti单质与硼铁的用量比例，使得最终制得的改性烧结钕铁硼永磁材料中的第一合金为(Pr 0.25Nd 0.75) 20Gd 10Ce 3Fe 65.7Co 0.2Cu 0.1Ti 0.1B 0.9，其中a为20％，b为13％，c为0.4％，d为0.9％。
实施例8
与实施例1的区别在于：第一熔炼处理的对象不同，改变Pr-Nd合金、Gd-Fe合金、Ce单质、Al单质、Co单质、Cu单质、Ga单质、Ti单质与硼铁的用量比例，使得最终制得的改性烧结钕铁硼永磁材料中的第一合金为(Pr 0.25Nd 0.75) 5Gd 18Ce 10Fe 60.5Al 3Co 1.5Cu 0.5Ga 0.3Ti 0.2B 1，其中a为5％，b为28％，c为5.5％，d为1％。
实施例9
与实施例1的区别在于：第一熔炼处理的对象不同，改变Pr-Nd合金、Gd-Fe合金、Ce单质、Y单质、Al单质、Co单质、Cu单质、Ga单质、Zr单质与硼铁的用量比例，使得最终制得的改性烧结钕铁硼永磁材料中的第一合金为(Pr 0.25Nd 0.75) 5Gd 13Ce 10Y 5Fe 62.51Al 3Co 0.2Cu 0.1Ga 0.1Zr 0.13B 0.96，其中LRE为Gd、Ce和Y元素，且a、b、c和d分别与实施例1相同。
实施例10
第一合金的成分与实施例4相同。与实施例4的区别在于：第二熔炼处理的对象不同，改变Pr-Nd合金、Al单质、Co单质、Cu单质、Ga单质、Ti单质与硼铁的用量比例，使得最终制得的改性烧结钕铁硼永磁材料中的第二合金的成分为(Pr 0.25Nd 0.75) 35Fe 56.1Al 2Co 2Cu 1.5Ga 1.5Ti 1B 0.9，其中x为35％，y为8％，z为0.9％。
实施例11
与实施例4的区别在于：
第一熔炼处理的对象不同，仅改变Al单质、Co单质、Cu单质、Zr单质以及Ti单质的用量比例，其余原料不变，使得最终制得的改性烧结钕铁硼永磁材料中的第一合金中的Al、Co、Cu、Zr和Ti元素用量比例不同，其第一合金的成分为(Pr 0.25Nd 0.75) 6.5Gd 15Ce 10Fe 65.96Al 1Co 0.2Cu 0.2Zr 0.06Ti 0.1B 0.98，且a、b、c和d分别与实施例1相同；
第二熔炼处理的对象不同，将Pr-Nd合金、Cu单质以及Ti单质与硼铁混合并进行第二熔炼处理，TM’为Cu和Ti元素的组合，使得最终制得的改性烧结钕铁硼永磁材料中的第二合金的成分为(Pr 0.25Nd 0.75) 45Fe 54Cu 0.3Ti 0.2B 0.5，TM’为Cu和Ti元素的组合，其中x为45％，y为0.5％，z为0.5％。
实施例12
与实施例4的区别在于：
第一熔炼处理的对象不同，仅将原料中的Zr单质替换为等量的Ti单质，原料用量比例不变，使得最终制得的改性烧结钕铁硼永磁材料中的第一合金的成分为(Pr 0.25Nd 0.75) 6.5Gd 15Ce 10Fe 65.96Al 1Co 0.2Cu 0.1Ga 0.1Ti 0.16B 0.98，其中TM为Al、Co、Cu、Ga和Ti元素的组合，且a、b、c和d分别与实施例4相同；
第二熔炼处理的对象不同，将Pr-Nd合金、Co单质与硼铁混合并进行第二熔炼处理，改变Pr_Nd合金、Co单质与硼铁的用量比例，使得最终制得的改性烧结钕铁硼永磁材料中的第二合金的成分为(Pr 0.25Nd 0.75) 50Fe 48.8Co 0.2B 1，TM’仅为Co元素，其中x为50％，y为0.2％，z为1％。
实施例13
与实施例4的区别在于：改变破碎处理过程中第一合金铸片与第二合金铸片的重量比，使得制得的改性烧结钕铁硼永磁材料中第一合金与第二合金的重量比为70∶30。
实施例14
与实施例4的区别在于：改变破碎处理过程中第一合金铸片与第二合金铸片的重量比，使得制得的改性烧结钕铁硼永磁材料中第一合金与第二合金的重量比为60∶40。
实施例15
与实施例4的区别在于：第一合金熔炼处理的温度为1350℃，第二合金熔炼处理的温度为1550℃。
对比例1
与实施例1的区别在于：采用传统烧结钕铁硼永磁材料进行磁性能测试，该统烧结钕铁硼永磁材料的成分为(PrNd) 32Fe 66.49Co 0.2Cu 0.2Zr 0.15B 0.96，其制备过程如下：
将Pr-Nd合金、Co单质、Cu单质、Zr单质与硼铁混合并进行第一熔炼处理，第一熔炼处理的温度为1500℃，第一甩片处理后得到厚度为0.2～0.4mm的合金铸片，其中厚度为0.25～0.35mm的铸片占90％以上；
将上述制得的第一合金铸片进行依次进行氢破处理和气流磨制粉，其中气流磨制粉前加入抗氧化剂(东阳安泰YKJ-10)混合并搅拌40min，气流磨后加入润滑剂(天津悦晟YSH-06)混合并搅拌60min，得到平均粒度为3.2μm的第一粉末；第一粉末、抗氧化剂与润滑剂的重量比为100∶0.1∶0.08；
将上述粉末在氧含量小于0.01％的成型压机中进行成型，得到密度为3.75g/cm 3的压坯，然后经冷等静压处理后得到密度为4.4g/cm 3的生坯；其中冷等静压处理的压强为180MPa，时间为120s；
对上述制得的生坯转移至烧结炉中进行烧结处理，抽真空至＜5×10 -2Pa，烧结处理的温度为1075℃，时间为4.5h，再进行阶段回火处理：第一段回火处理的温度为920℃，时间为2h；第二段回火处理为520℃，时间为5h，最终得到烧结钕铁硼永磁材料。
对比例2
与对比例1的区别在于：第一熔炼处理的对象不同，将Pr-Nd合金、Dy-Fe合金、Al单质、Co单质、Cu单质、Ga单质、Ti单质与硼铁混合并进行第一熔炼处理，改变上述原料的用量比例，使最终制得的烧结钕铁硼材料的成分为(Pr 0.25Nd 0.75) 27Dy 4Fe 65.33Al 0.8Co 1Cu 0.4Ga 0.4Ti 0.16B 0.91，其中LRE仅为Dy元素，TM为Al、Co、Cu、Ga和Ti元素的组合。
对比例3
与实施例1的区别在于：第一熔炼处理的对象不同，原料中未包含Gd-Fe合金；最终制得的烧结钕铁硼材料的成分为(P r0.25Nd 0.75) 5Ce 28Fe 62.59Al 3Co 0.2Cu 0.1Zr 0.15B 0.96，其中未包含Gd元素。
对比例4
与实施例1的区别在于：第一熔炼处理的对象不同，且各原料用量不同，使得最终制得的改性烧结钕铁硼永磁材料中第一合金的成分为(Pr 0.25Nd 0.75) 3Gd 30Fe 62.35Co 0.2Zr 0.15B 1.1，且a为3％，b为30％，c为0.35％，d为1.1％。
采用永磁材料测试B-H仪NIM-2000对本申请全部实施例和对比例中制得的改性烧结钕铁硼永磁材料分别进行室温(20℃)和高温(120℃)磁性能测试，并计算温度剩磁Br温度系数和内禀矫顽力Hcj温度系数。剩磁Br温度系数的计算公式为：α＝(Br 1-Br 0)/(100Br 0)×100％，其中Br 1为120℃条件下测得的改性烧结钕铁硼永磁材料的剩磁，Br 0为20℃条件下测得的剩磁。内禀矫顽力Hcj温度系数的计算公式为：β＝(Hcj 1-Hcj 0)/(100Hcj 0)×100％，其中Hcj 1为120℃条件下测得的改性烧结钕铁硼永磁材料的内禀矫顽力，Hcj 0为20℃条件下测得的内禀矫顽力。
测试结果见表1。改性烧结钕铁硼永磁材料具有负温度系数，其磁化强度和内禀矫顽力会随着温度的升高而降低，因此表1中的数据为负值。
表1
  Br/kGs Hcj/kOe (BH)max/MGOe α(Br)/(％/℃) β(Hcj)/(％/℃)
实施例1 6.65 9.176 10.64 -0.1173 -0.6801
实施例2 7.58 10.452 13.46 -0.1083 -0.5742
实施例3 8.21 9.636 15.92 -0.1028 -0.4316
实施例4 9.02 9.400 19.28 -0.1056 -0.4675
实施例5 9.64 9.250 22.52 -0.1063 -0.4845
实施例6 10.26 9.890 25.64 -0.1058 -0.4781
实施例7 10.74 10.586 28.98 -0.1054 -0.4853
实施例8 6.32 9.522 9.84 -0.1158 -0.6741
实施例9 7.67 5.28 13.89 -0.1325 -0.7588
实施例10 9.14 9.650 19.65 -0.1061 -0.4686
实施例11 9.09 9.180 19.48 -0.1067 -0.4662
实施例12 8.83 8.75 18.89 -0.1112 -0.4922
实施例13 9.43 10.870 22.04 -0.1054 -0.4831
实施例14 8.42 9.670 15.44 -0.1087 -0.5335
实施例15 8.55 7.640 17.88 -0.1154 -0.5458
对比例1 14.24 12.58 50.56 -0.1286 -0.7247
对比例2 11.96 26.34 34.21 -0.1103 -0.5366
对比例3 6.87 1.596 10.96 -0.1387 -0.8336
对比例4 7.96 3.225 14.63 -0.0945 -0.3872
从以上的描述中，可以看出，本发明上述的实施例实现了如下技术效果：
比较实施例1以及对比例1至4可知，使特定种类和用量的稀土元素(如Gd、Y和Ce元素)替代传统烧结钕铁硼永磁材料((PrNd)-Fe-B)中的Pr、Nd元素，一方面能够得到最大磁能积(BH) max在5～30MGOe范围内且磁性能满足低端领域需求(剩磁Br在6～11kGs、内禀矫顽力Hcj在5～11kOe)的改性烧结钕铁硼永磁材料；另一方面特定种类的稀土元素与TM元素以本发明特定的重量比(严格控制a、b、c、d的取值范围)共同作用能够改善内禀矫顽力的温度系数，从而提高其耐高温性能，使其满足高温条件下的应用。
比例实施例2至7以及10至14和对比例1、2可知，使特定种类的稀土元素Gd和Ce替代烧结钕铁硼永磁材料中的Pr、Nd元素，以及采用特定配比的TM元素，虽然所得材料的Hcj(6～11kOe)比常规烧结钕铁硼材料的低很多，但其剩磁和内禀矫顽力温度系数显著优于N牌号(Hcj在12～14kOe之间)烧结钕铁硼永磁材料，接近甚至优于UH牌号(Hcj在25～30kOe)烧结钕铁硼永磁材料，这使得本申请中的改性烧结钕铁硼材料可以满足150℃以内的高温应用需求。
比较实施例1、7和8以及对比例4可知，对比例4中制得的改性烧结钕铁硼永磁材料的第一合金中的Gd元素含量很高(高达30％)，而实施例1、7和8中的Gd元素含量在本申请优选范围内。结合表1中对比例4测得的性能结果可知，虽然对比例4耐高温性能相较于实施例1、7和8略有提升，但是其内禀矫顽力Hcj仅为3.225kOe(明显低于实施例1、7和8)，综合性能较差，不利于实际应用。这表明，将第一合金中a、b、c和d的取值分别限定在本申请优选范围内并采用本申请优选种类的LRE和TM元素能够提高制得的改性烧结钕铁硼永磁材料的耐高温性能。
比较实施例1、9以及对比例2和3可知，相比于其它种类的元素，采用本申请优选种类的LRE元素能够提高制得的改性烧结钕铁硼永磁材料的耐高温性能。由表1中对比例2测得的性能结果可知，虽然对比例2满足高性能的烧结钕铁硼材料牌号N35UH，其性能较优异。但是比较实施例1和对比例2可知，对比例2中改性烧结钕铁硼永磁材料的制备成本显著高于实施例1。这表明采用本申请特定种类和用量的稀土元素替代传统烧结钕铁硼永磁材料中的Pr、Nd元素不仅能够提高耐高温性能，还能够降低制备成本。
比较实施例1、10至12可知，相比于具有单一合金成分改性烧结钕铁硼永磁材料，使改性烧结钕铁硼永磁材料同时含有第一合金与第二合金有利于发挥二者的协同作用，有利于进一步提高磁性能；同时有利于进一步降低改性烧结钕铁硼永磁材料的内禀矫顽力温度系数的绝对值，进而进一步提高其耐高温性能。
比较实施例4、13和14可知，相比于其它范围，将第一合金与第二合金的重量比限定在本申请优选范围范围内有利于高效发挥二者的协同作用，有利于进一步提高改性烧结钕铁硼永磁材料的耐高温性能，同时进一步降低成本并使磁性能维持较高水平。
比较实施例4和15可知，第一熔炼处理和第二熔炼处理过程的温度包括但不限于本申请优选范围，将其限定在本申请优选范围内有利于提高后续形成的第一合金铸片和第二合金铸片的晶型均一性，进而提高后续制得的改性烧结钕铁硼永磁材料的磁性能和耐高温性能，同时进一步控制制得的改性烧结钕铁硼永磁材料的(BH) max在5～30MGOe范围内。
需要说明的是，本申请的说明书和权利要求书中的术语“第一”、“第二”等是用于区别类似的对象，而不必用于描述特定的顺序或先后次序。应该理解这样使用的术语在适当情况下可以互换，以便这里描述的本申请的实施方式例如能够以除了在这里描述的那些以外的顺序实施。
以上所述仅为本发明的优选实施例而已，并不用于限制本发明，对于本领域的技术人员来说，本发明可以有各种更改和变化。凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种改性烧结钕铁硼永磁材料，其特征在于，所述改性烧结钕铁硼永磁材料包括第一合金，所述第一合金具有式(I)所示化学式：(P r0.25Nd 0.75) a(LRE) bTM cFe 100％-a-b-c-dB d(I)，其中，LRE为稀土元素，且所述LRE选自Gd、Y和Ce元素中的一种或多种，且至少含有Gd元素，TM选自Al、Cu、Co、Ga、Nb、Zr和Ti元素中的一种或多种，a为5～20％，b为13～28％，c为0.4～5.5％，d为0.9～1％。
  2. 根据权利要求1所述的改性烧结钕铁硼永磁材料，其特征在于，所述a为7～16％，所述b为16～26％，所述c为0.7～3.3％，所述d为0.92～0.98％。
  3. 根据权利要求1或2所述的改性烧结钕铁硼永磁材料，其特征在于，所述改性烧结钕铁硼永磁材料还包括第二合金，所述第二合金具有式(II)所示化学式：(Pr 0.25Nd 0.75) xTM’ yFe 100％-x-y-zB z(II)，其中，TM’选自Al、Cu、Co、Ga、Nb、Zr和Ti元素中的一种或多种，x为35～45％，y为0.5～9％，z为0.5～0.9％；
    优选地，所述x为38～42％，所述y为1.6～4.5％，所述z为0.6～0.8％。
  4. 根据权利要求3所述的改性烧结钕铁硼永磁材料，其特征在于，以所述第一合金和第二合金的总重量计，所述第二合金的重量百分含量不超过30wt％。
  5. 根据权利要求4所述的改性烧结钕铁硼永磁材料，其特征在于，所述LRE为Gd和Ce，或者为Gd和Y，或者为Gd、Y和Ce；优选地，所述LRE为Gd和Ce；更优选地，所述LRE为Gd和Ce，且所述Gd和所述Ce的重量比为(13～18)∶(8～10)，更进一步优选为(13～15)∶(8～10)；
    所述TM’为Co、Cu和Zr的组合，或者为Al、Co、Cu和Zr的组合，或者为Al、Co、Ga和Zr的组合，或者为Al、Cu、Ga和Zr的组合，或者为Al、Co、Cu、Ga和Zr的组合；优选地，所述TM’为Al、Co、Cu、Ga和Zr的组合；更优选地，所述TM’为Al、Co、Cu、Ga和Zr的组合，且所述Al、所述Co、所述Cu、所述Ga和所述Zr的重量比为(0～3)∶(0.2～1.5)∶(0.1～0.5)∶(0～0.3)∶(0.1～0.16)，更进一步优选为(0.2～1.5)∶(0.2～1.0)∶(0.1～0.3)∶(0.1～0.3)∶(0.1～0.16)；
    所述TM为Al、Co、Cu、Ga和Zr的组合，或者为Al、Co、Cu、Ga和Nb的组合，或者为Al、Co、Cu、Ga和Ti的组合；优选地，所述TM为Al、Co、Cu、Ga和Zr的组合；更优选地，所述TM为Al、Co、Cu、Ga和Zr的组合，且所述Al、所述Co、所述Cu、所述Ga和所述Zr的重量比为(0.2～3)∶(0.2～1.5)∶(0.1～0.5)∶(0.1～0.3)∶(0.1～0.16)，更进一步优选为(0.2～1.5)∶(0.2～1.0)∶(0.1～0.3)∶(0.1～0.3)∶(0.1～0.16)；或，
    所述TM为Al、Co、Cu、Ga、Nb和Zr，或者为Al、Co、Cu、Ga、Zr和Ti的组合；优选地，所述TM为Al、Co、Cu、Ga、Zr和Ti的组合；更优选地，所述TM为Al、Co、Cu、Ga、Zr和Ti的组合，且所述Al、所述Co、所述Cu、所述Ga、所述Zr和所述Ti的重量比为(0.2～3)∶(0.2～1.5)∶(0.1～0.5)∶(0.1～0.3)∶(0.04～0.16)∶(0.05～0.2)，更进一步优选为(0.2～1.5)∶(0.2～1.0)∶(0.1～0.3)∶(0.1～0.3)∶(0.04～0.12)∶(0.05～0.15)。
  6. 根据权利要求5所述的改性烧结钕铁硼永磁材料的制备方法，其特征在于，所述第一合金和所述第二合金的重量比为(80～90)∶(10～20)。
  7. 一种权利要求1或2所述的改性烧结钕铁硼永磁材料的制备方法，其特征在于，所述改性烧结钕铁硼永磁材料的制备方法包括：
    将Pr-Nd合金、LRE源、TM源与硼铁混合并进行第一熔炼处理和第一甩片处理，得到第一合金铸片；所述LRE源选自Gd-Fe合金、Y单质和Ce单质中的一种或多种；所述TM源选自Al单质、Cu单质、Co单质、Ga单质、Nb-Fe合金、Zr单质和Ti单质中的一种或多种；
    对所述第一合金铸片进行破碎处理，得到第一粉末；
    将所述第一粉末进行取向成型和压制处理，得到生坯；
    对所述生坯进行烧结处理和回火处理，得到所述改性烧结钕铁硼永磁材料。
  8. 根据权利要求7所述的改性烧结钕铁硼永磁材料的制备方法，其特征在于，所述改性烧结钕铁硼永磁材料的制备方法还包括：
    将Pr-Nd合金、TM’源与硼铁混合并进行第二熔炼处理和第二甩片处理，得到第二合金铸片；所述TM源选自Al单质、Cu单质、Co单质、Ga单质、Nb-Fe合金、Zr单质和Ti单质中的一种或多种；
    在所述破碎处理的过程中，同时加入所述第二合金铸片以与所述第一合金铸片一起进行所述破碎处理，得到第二粉末；
    在进行所述取向成型之前将所述第二粉末与润滑剂混合；
    优选地，所述破碎处理依次包括氢破处理和气流磨制粉，在所述气流磨过程中加入抗氧化剂，在所述气流磨制粉结束后得到所述第二粉末。
  9. 根据权利要求7所述的改性烧结钕铁硼永磁材料的制备方法，其特征在于，所述第一粉末、所述抗氧化剂与所述润滑剂的重量比为100∶(0.05～0.2)∶(0.03～0.15)；
    优选地，所述第一粉末的平均粒度选自3.0～3.8μm。
  10. 根据权利要求8所述的改性烧结钕铁硼永磁材料的制备方法，其特征在于，所述第一粉末和所述第二粉末的总重量、所述抗氧化剂与所述润滑剂的重量比为100∶(0.05～0.2)∶(0.03～0.15)；
    优选地，所述第一粉末和所述第二粉末的平均粒度分别独立地选自3.0～3.8μm。
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