WO2023046005A1 - 一种高剩磁钕铁硼磁体及其制备方法和应用 - Google Patents

一种高剩磁钕铁硼磁体及其制备方法和应用 Download PDF

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Publication number
WO2023046005A1
WO2023046005A1 PCT/CN2022/120487 CN2022120487W WO2023046005A1 WO 2023046005 A1 WO2023046005 A1 WO 2023046005A1 CN 2022120487 W CN2022120487 W CN 2022120487W WO 2023046005 A1 WO2023046005 A1 WO 2023046005A1
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Prior art keywords
magnet
cooling
temperature
sintering
aging treatment
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PCT/CN2022/120487
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English (en)
French (fr)
Inventor
于永江
刘磊
王有花
马丹
姜云瑛
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Jianghua Zhenghai Minmetals Advanced Materials Co Ltd
Yantai Zhenghai Magnetic Material Co Ltd
Original Assignee
Jianghua Zhenghai Minmetals Advanced Materials Co Ltd
Yantai Zhenghai Magnetic Material Co Ltd
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Application filed by Jianghua Zhenghai Minmetals Advanced Materials Co Ltd, Yantai Zhenghai Magnetic Material Co Ltd filed Critical Jianghua Zhenghai Minmetals Advanced Materials Co Ltd
Priority to EP22872050.4A priority Critical patent/EP4394809A4/en
Priority to US18/694,374 priority patent/US20250006411A1/en
Priority to JP2024518537A priority patent/JP7813354B2/ja
Priority to KR1020247009292A priority patent/KR102813774B1/ko
Publication of WO2023046005A1 publication Critical patent/WO2023046005A1/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
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    • B22F3/12—Both compacting and sintering
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    • B22F9/00—Making metallic powder or suspensions thereof
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • C—CHEMISTRY; METALLURGY
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    • C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
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    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/16—Ferrous alloys, e.g. steel alloys containing copper
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H01F41/0293—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets diffusion of rare earth elements, e.g. Tb, Dy or Ho, into permanent magnets
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02K—DYNAMO-ELECTRIC MACHINES
    • H02K1/00—Details of the magnetic circuit
    • H02K1/02—Details of the magnetic circuit characterised by the magnetic material
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    • B22—CASTING; POWDER METALLURGY
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    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/241—Chemical after-treatment on the surface
    • B22F2003/242—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/24—After-treatment of workpieces or articles
    • B22F2003/248—Thermal after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/044—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by jet milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2201/00—Treatment under specific atmosphere
    • B22F2201/10—Inert gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2201/00—Treatment under specific atmosphere
    • B22F2201/20—Use of vacuum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
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    • B22F2202/00—Treatment under specific physical conditions
    • B22F2202/05—Use of magnetic field
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    • B22F2301/00—Metallic composition of the powder or its coating
    • B22F2301/35—Iron
    • B22F2301/355—Rare Earth - Fe intermetallic alloys
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22C2202/02—Magnetic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/64—Electric machine technologies in electromobility

Definitions

  • the invention belongs to the field of neodymium-iron-boron magnets, and in particular relates to a sintered neodymium-iron-boron magnet and its preparation method and application.
  • Sintered NdFeB magnets as the fourth generation of permanent magnet materials, are known as the "Magnetic King” for their excellent magnetic properties, and are widely used in many fields such as automobiles, wind power, compressors, elevators, and industrial automation.
  • the limit remanence of pure NdFeB magnets is 1.61T.
  • the maximum remanence available under laboratory conditions is 1.56T, but due to the difficulty of the process and the accuracy of the equipment, it is far from enough to achieve mass production.
  • the mainstream residual magnetism range of magnets used in new energy vehicles and energy-saving home appliances is between 1.10-1.40T. If the residual magnetism can be further increased, it can effectively promote the miniaturization of motors and the requirements of high energy efficiency levels.
  • Patent CN11724985A uses low B component (0.80-0.93wt%) to smelt the alloy so that it has a certain amount of transition metal phase (R 6 T 13 M) to prepare sintered magnets (or diffused magnets), and sintered magnets (or Diffused magnet) at a temperature of 400°C to 600°C for 10 seconds to 30 minutes, so that it has both high remanence and high Hcj, and the remanence can reach 1.41T.
  • the use of low B components makes it possible to form a wider R 6 T 13 M phase at the grain boundary, but according to the requirements of the theoretical formula of NdFeB magnet remanence, the volume ratio of the main phase is reduced, so that Br is inevitably reduced.
  • the R 6 T 13 M phase in the grain boundary is beneficial to the improvement of Hcj, the stability of the grain boundary phase is poor, which requires high control of equipment process difficulty, and the squareness of the magnet is prone to fluctuations, which cannot be stabilized greater than 0.95, which directly affects The high temperature resistance demagnetization ability of the motor.
  • Patent CN10744699A uses low B component (0.94wt%) to smelt alloys to prepare thin alloy skins with a columnar crystal ratio of more than 95%. It uses a rotary hydrogen embrittlement furnace to prepare 3.75-3.9 ⁇ m airflow milling powder with high-pressure nitrogen, which can Prepare ultra-high-performance NdFeB magnets with Br at 1.44-1.48T and Hcj reaching 14-16kOe. The proportion of columnar crystals of alloy flakes is controlled, the HD production process is optimized, the particle size range of jet milling is controlled, and the sintering process is matched to obtain magnets with high Br and high Hcj.
  • the present invention proposes a high remanence NdFeB magnet and its preparation method and application.
  • the invention provides a neodymium-iron-boron magnet, the magnet has grains with R-T-B compound as the main structure, and a grain boundary phase; the neodymium-iron-boron magnet comprises:
  • R more than 28%wt and less than 30wt%;
  • R represents a rare earth element selected from Nd, or at least one of Nd and the following rare earth elements: Pr, La, Ce, Dy, Tb, Ho;
  • T more than 63wt% and less than 70wt%; T is selected from Fe and/or Co, wherein Fe accounts for more than 99wt% of the total amount of T;
  • M1 greater than 0wt%, less than 0.3wt%; M1 is selected from Cu and Ga, and Ga accounts for more than 75wt% of the total amount of M1.
  • M2 more than 0.04wt% and less than 0.15wt%; M2 is selected from at least one of Zr, Ti, and Nb.
  • M2 is selected from Ti.
  • the atomic number of the element in the raw materials for the preparation of the NdFeB magnet, also satisfies the following conditions:
  • [R] is the atomic percentage of R
  • [B] is the atomic percentage of B
  • [M2] is the atomic percentage of M2.
  • the atomic percentage refers to [the number of certain atoms]/[the total number of various atoms in the raw material].
  • [R]/([B]-2[M2]) is 2.15, 2.2, 2.24, 2.29, 2.3.
  • R when R is selected from at least one of Nd and the following rare earth elements: Pr, La, Ce, Dy, Tb, Ho, the total mass of Dy, Tb, Ho and other heavy rare earth elements accounts for 1 wt% or less of the mass, preferably 0.5 wt% or less.
  • the magnet has the following magnetic properties:
  • Hcj ⁇ 1100kA/m such as 1100kA/m, 1110kA/m, 1120kA/m, 1130kA/m, 1140kA/m, 1150kA/m, 1160kA/m, 1170kA/m, 1180kA/m, 1190kA/m , 1200kA/m.
  • the present invention strictly limits the content of each element in the preparation raw material, specifically:
  • the magnetic polarization of R-T-B main phase grains composed of Pr, Dy, Tb, Ho and other rare earth elements is lower than that of Nd, it will significantly reduce the Br of the magnet. While ensuring the high Br of the magnet, it can be achieved by using a small amount of Dy and Tb , Ho and other heavy rare earth elements to increase the Hcj of the magnet.
  • R in the magnet is too high, the neodymium-rich phase of the magnet increases and Br decreases; when R is too low, a uniform and continuous Nd-rich phase cannot be formed in the magnet to magnetically isolate the main phase grains, and the Hcj and squareness of the magnet will deteriorate dramatically.
  • the existing technology uses low B ( ⁇ 0.95wt%) to prepare high-performance NdFeB magnets.
  • the grain boundary phases are thickened and the Hcj of the magnets is improved.
  • the increase of the grain boundary phases Thick inevitably reduces the volume ratio of the main phase grains, which will significantly reduce the Br performance of the magnet.
  • the present invention increases the volume ratio of the main phase grains by controlling the B content, and increases the Br of the magnet.
  • the proportion of the B-rich phase or Nd-rich phase formed is relatively high, and the volume ratio of the main phase grains is small, resulting in The Br of the magnet is low; when the B content is too high, the volume ratio of the B-rich phase increases significantly, which will greatly reduce the magnetic properties.
  • M1 is mainly enriched at the grain boundary, which can improve the grain boundary phase structure and greatly increase Hcj.
  • the main phase grains and B-rich phase of the magnet are relatively coarse, which will greatly reduce the magnetic properties of the magnet; when the Cu and Ga content in the magnet are too high, the growth of the grains will be inhibited, At the same time, the grain boundary phase becomes thicker, the grain volume ratio of the main phase decreases, and the Br of the magnet decreases.
  • the Ga content of the present invention is reached, the Hcj of the magnet can be significantly increased, and the temperature coefficient of the magnet can be significantly optimized, and the influence of low Co content on the temperature resistance of the magnet can be avoided.
  • M2 and B form A 2 B type compound, which exists in the grain boundary phase and plays a role in inhibiting the abnormal growth of magnet grains.
  • a 2 B type compound which exists in the grain boundary phase and plays a role in inhibiting the abnormal growth of magnet grains.
  • the content of M2 is too low, the existence of A 2 B type compound cannot be effectively formed, and the abnormal growth of the main phase grain of the magnet is suppressed; when the content of M2 is too high, the A 2 B type compound exists as a grain boundary phase, reducing If the volume ratio of the main phase grains is exceeded, the magnet cannot obtain high Br.
  • the present invention also provides a method for preparing the above-mentioned NdFeB magnet, including: (a) smelting process: melting the raw materials for the above-mentioned NdFeB magnet through high-temperature melting, casting, and secondary cooling to form an alloy sheet; (b) powder-making process : breaking the alloy flakes into alloy powder; (c) molding process: pressing the alloy powder under the action of a magnetic field to obtain a green body; (d) sintering process: sintering the green body at high temperature.
  • the (a) smelting process specifically includes: fully melting the raw materials for the above-mentioned NdFeB magnet into molten alloy steel in a vacuum or an inert gas atmosphere, then rapidly cooling to form an alloy sheet, and then After secondary cooling, and the interval between the secondary cooling and the rapid cooling does not exceed 10s, and the cooling rate of the secondary cooling is 5-20°C/s.
  • the melting is carried out by medium frequency induction heating in a vacuum induction melting furnace.
  • the rapid cooling method commonly used in the technical field can be selected as long as the desired alloy flakes can be obtained.
  • the rapid cooling is performed using a quench roll.
  • the secondary cooling can be carried out by using cooling methods and cooling devices commonly used in this technical field.
  • the secondary cooling is performed by any cooling device selected from the following: spraying of low-temperature inert gas, water-cooled disk or other cooling devices.
  • the cooling rate of the secondary cooling is preferably 5-20° C./s.
  • the alloy sheet has a thickness of 0.15-0.45 mm.
  • the (b) pulverizing process includes coarse crushing and fine crushing.
  • the coarse crushing is selected from hydrogen embrittlement and/or medium grinding.
  • the fine crushing is selected from jet mills.
  • the jet mill is performed under an inert gas atmosphere.
  • the inert gas is selected from nitrogen, helium and the like.
  • the hydrogen embrittlement, intermediate grinding or jet milling can be performed by known operations in the art.
  • the fine crushing After the fine crushing, it is obtained by screening, for example, screening by classifying wheels.
  • the particle size SMD of the alloy powder is between 2.0-3.4 ⁇ m, and X90/X10 ⁇ 4.5.
  • SMD is the area average particle size, the smaller the SMD, the smaller the particle size of the powder particles, the larger the SMD, the larger the particle size of the powder particles;
  • X90 represents the particle size value corresponding to the cumulative distribution percentage reaching 90% , that is, the particle size of all particles is not larger than this particle size, the number of particles larger than the secondary particle size value is 0, and X10 indicates the corresponding particle size value when the cumulative distribution percentage reaches 90%, that is, the particle size of all particles is not larger than For this particle size, the number of particles larger than the secondary particle size value is 0.
  • X90/X10 refers to the particle size distribution of the powder. The smaller the X90/X10, the more concentrated the particle size distribution of the powder.
  • a lubricant needs to be added during fine crushing, preferably before and after jet milling. Adding a lubricant before the jet mill can improve the fluidity of the powder, and improve the fluidity and uniformity of the powder during the jet mill; adding a lubricant after the jet mill can also improve the powder uniformity and fluidity, which is convenient for uniform powder filling and pressing .
  • the lubricant is selected from reagents known in the art, and used in an amount known in the art, so as to ensure that the powder is fully mixed and easy to shape.
  • the lubricant is selected from organic solvents such as volatile fats or alcohols, such as zinc stearate.
  • the lubricant is added in an amount of 0.1-1 wt% of the total mass of the raw materials for preparation.
  • mixing is also required.
  • the mixing time is 3-6h.
  • the mixing described in the present invention can be carried out by methods known in the art, such as placing in a mixing machine for mixing.
  • the (c) pressing process specifically includes: pressing the alloy powder under the action of a magnetic field to obtain a green body.
  • the compression forming takes place in a press mill cavity.
  • a reverse magnetic field is applied for demagnetization.
  • the formed body can also be processed in a cold isostatic press to further increase the density of the green body.
  • the (d) sintering process includes first sintering, first cooling, second sintering and second cooling.
  • the sintering process in the present invention can be carried out by methods known in the art.
  • the green body is sintered in a sintering furnace.
  • the sintering process is carried out under vacuum atmosphere.
  • the degree of vacuum is 10 -1 Pa or less.
  • the sintering temperature of the first sintering is 1000-1050° C.
  • the holding time of the first sintering is 240-360 minutes.
  • the second sintering temperature is 30-70°C higher than the first sintering temperature, preferably 1030-1100°C.
  • the holding time for the second sintering is 270-360 minutes.
  • both the first cooling and the second cooling are below 200°C.
  • the sintering process further includes aging treatment, and the aging treatment is performed after the second cooling.
  • the aging treatment is selected from primary aging treatment or secondary aging treatment.
  • the conditions of the primary aging treatment are as follows: the aging treatment temperature is between 500-700° C., and the holding time is 240-420 minutes.
  • the secondary aging treatment includes: raising the temperature for the first aging treatment, the temperature of the first aging treatment is 800-950°C, and the holding time is 180-300min; cooling to below 150°C, and then raising the temperature for the second aging treatment Secondary aging treatment, the temperature of the second aging treatment is between 450-600°C, and the holding time is 240-360min.
  • a diffusion treatment may also be performed.
  • the diffusion treatment includes applying a diffusion material on the surface of the magnet, performing vacuum high-temperature diffusion treatment, diffusion cooling and diffusion aging treatment.
  • the diffusion material is selected from pure metals of Dy and/or Tb, or alloys such as hydrides, oxides, hydroxides, fluorides, etc. of Dy and/or Tb.
  • the diffusion treatment can be carried out by means of vacuum evaporation, magnetron sputtering, coating or burying.
  • the temperature of high-temperature diffusion is 850-950°C, and the time of high-temperature diffusion is 10-30h.
  • the diffusion cooling temperature is below 100°C.
  • the temperature of the diffusion aging treatment is 450-600°C, and the time of the diffusion aging treatment is 4-8h.
  • the green body after the sintering process and before the diffusion treatment, can also be processed into the target size.
  • the present invention needs to strictly limit the conditions of each process in the magnet preparation method, specifically:
  • the alloy flakes on the surface of the quenching roller form nucleation points, and the nucleation point is the starting point to form crystal grains and grow up.
  • the alloy sheet falls off on the quenching roll, and its temperature drops from the melting temperature to about 800°C. At this time, the crystal grains are still growing slowly, so it is necessary to carry out secondary cooling in time to reduce the temperature of the alloy sheet.
  • the secondary cooling time When the interval is too long, the main phase grains on the alloy sheet will continue to grow, and even the secondary crystals will be derived due to the uneven divergence of the alloy sheet temperature.
  • the magnet grain size difference is relatively small Large and fine powders are easy to agglomerate and melt to form triangular grain boundary phases, and adjacent coarse powders fuse to form large grains, which will seriously affect the squareness of the magnet.
  • the present invention can greatly improve the performance of the magnet by adopting the secondary sintering process, and effectively suppress the abnormal growth of the crystal grains of the magnet.
  • the second sintering temperature is higher than the first sintering temperature, and the lower temperature is used for the first sintering, which can improve the compactness of the magnet, but there are still some gaps. Avoid the abnormal growth of the main phase grains; and the second sintering temperature has a large increase compared with the first sintering temperature, which can promote the sufficient growth of the main phase grains, but it will not form abnormally long main phase grains. large, resulting in a sharp deterioration of the magnetic properties.
  • the first sintering temperature is higher, and the grain arrangement is already relatively tight, and the lower second sintering temperature cannot fully reset the magnet grain structure Optimization, resulting in the inability to obtain higher magnetic performance.
  • the temperature difference between the two sinterings is too large, the first sintering temperature is low, the gap is larger, and the second sintering temperature is too high, the crystal grains in some areas will grow abnormally, resulting in the deterioration of the magnet performance.
  • the present invention also provides the application of the above-mentioned magnet in the field of motors.
  • the present invention also provides a motor, which includes the above-mentioned magnet.
  • the present invention also provides the application of the above-mentioned motor.
  • the motor can be used in new energy vehicles and energy-saving home appliances.
  • the NdFeB magnet of the present invention can obtain a higher grain volume ratio of the main phase by adjusting the proportion relationship of B, Cu, Ga, RE, Ti and other elements, and effectively suppress the proportion of the B-rich phase in the grain boundary phase.
  • Metal elements M1 (such as Ga) and M2 (such as Ti) optimize and adjust the structure of the grain boundary phase, so that the magnet has a high Br, and has excellent Hcj and squareness performance.
  • the B content is higher than that of common sintered NdFeB magnets.
  • NdFeB magnets take into account the performance of Br and Hcj of the magnet, [R]/([B]-2[M2]) will be slightly greater than 2.35, greater than 2.5, so that it has less B-rich phase, or not The presence of a B-rich phase is formed.
  • the present invention makes the ratio between 2.15-2.35, theoretically more B-rich phases can be formed than ordinary NdFeB magnets, but within the ratio range of this relational formula, combined with the secondary cooling in the preparation method of the present invention , can increase the grain volume ratio of the main phase of the magnet, suppress the excessive formation of B-rich phase, and have excellent Hcj and squareness indicators while ensuring the Br of the magnet.
  • the magnet of the present invention uses a very small amount of heavy rare earth elements such as Dy/Tb, or even does not use them to obtain high remanence and coercive force, and the squareness of the magnet is ⁇ 0.95, the production process is simple, and the mass production stability is high.
  • the magnet prepared by the preparation method of the present invention has high residual magnetism, Br ⁇ 1.44T, and has a very high energy density. It can effectively increase the power output per unit volume when applied to a motor, effectively reduce the volume of the motor, and save the cost of other components of the motor. Material loss plays an important role in the miniaturization and cost reduction of motors.
  • the atomic percentage refers to [the number of a certain atom]/[the total number of various atoms in the raw material].
  • M1 is selected from Cu and Ga;
  • M2 is selected from at least one of Zr, Ti, and Nb;
  • R is selected from at least one of Nd and the following rare earth elements: Pr, La, Ce, Dy, Tb, Ho.
  • Embodiment 1-4
  • Example 1 - 29 0.5 0.99 - 0.05 0.25 - 0.12 margin
  • Example 2 - 29 0.5 1.03 - 0.05 0.25 - 0.12 margin
  • Example 3 6 23.8 - 1.02 0.05 - 0.2 0.05 0.08 margin
  • Example 4 - 29 - 1.04 - 0.05 0.25 - 0.12 margin
  • the holding time of the two sinterings is 270min.
  • the time is 240min, and the second aging is carried out after cooling.
  • the optimal aging temperature is adjusted according to the difference of each component.
  • the aging holding time is 280min.
  • the specific sintering aging system is shown in Table 2.
  • Table 2 The average thickness of the alloy flakes, the particle size of the jet mill and the sintering process in Examples 1-4
  • the magnet after sintering and aging treatment was processed into a standard sample column with a diameter of 10mm and a height of 10mm, and the performance of the magnet was tested with a BH instrument.
  • the specific magnetic performance test results are shown in Table 3.
  • the raw materials are prepared according to the target composition of the magnet in Table 4, and the NdFeB alloy sheet is prepared by the strip casting process. After the alloy sheet is cooled and fallen off by the quenching roll, it is sprayed with low-temperature argon for secondary cooling. By adjusting the low-temperature argon The flow rate and temperature of the alloy flakes are secondary cooled at a cooling rate of 10°C/s to obtain alloy flakes, and the alloy flakes are dropped on a water-cooled disk for recovery to obtain alloy flakes.
  • Raw materials were prepared according to the target composition of the magnet in Table 4, and NdFeB alloy flakes were prepared by strip casting process. After the alloy flakes were quenched on the quenching roller, they were directly dropped on the water-cooled disc for cooling and recovery.
  • Raw materials were prepared according to the target composition of the magnet in Table 4, and NdFeB alloy flakes were prepared by strip casting process. After the alloy flakes were quenched on the quenching roller, they were directly dropped on the water-cooled disc for cooling and recovery.
  • the specific process parameters are shown in Table 5.
  • the magnet prepared in comparative example 1-4 is processed into a standard sample column with a diameter of 10mm and a height of 10mm, and the BH instrument is used to test the magnet performance, and the magnet performance is tested.
  • the specific magnetic performance test results are shown in Table 6.
  • the ratio of [Cu] to [Ga] in Comparative Example 2 is far less than 0.75, so that the Br and Hcj of the magnet are significantly lower than those in the examples, and cannot have both high remanence and high coercive force.
  • the target magnet composition of Comparative Example 3 is the same as that of Example 1, but in the smelting process, the alloy sheet is not subjected to secondary cooling in the manner required by this patent. According to Table 3, it can be seen that when the secondary cooling of the alloy sheet is canceled At the same time, the thickness of the alloy sheet increases due to the significant growth of the crystal grains.
  • the jet mill powder of the target SMD is also obtained, the particle size distribution (X90/X10) is significantly deteriorated, and the coarse powder and fine powder The powder ratio increases, and the powder uniformity is poor; and only one sintering process is carried out in the sintering process, and the secondary sintering process is not used, and the remanence and coercive force of the magnet are also significantly reduced.
  • Example 1 Take the magnet after sintering and aging in Example 1, process it into a sheet product with a length of 20mm, a width of 20mm, and a thickness of 5mm, apply a layer of metal Dy film on the surface of the magnet by dipping process, and then keep it warm at 900°C for 15 hours Diffusion treatment is carried out, and after the diffusion temperature is cooled below 100°C, the temperature is raised to 500°C for 5 hours of aging treatment. The final magnet is subjected to magnetic performance test and composition test. The results of its final composition and magnetic properties are shown in Table 9 and Table 10.

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Abstract

本发明提供一种高剩磁钕铁硼磁体及其制备方法和应用。本发明的钕铁硼磁体具有以R-T-B型化合物为主要结构的晶粒，以及晶界相。本发明的钕铁硼磁体通过调整B、Cu、Ga、RE、Ti等元素的比例关系，可以获得较高的主相晶粒体积比，有效抑制晶界相中富B相的比例，使得磁体具备较高的Br，兼具优良的Hcj和方形度性能。

Description

一种高剩磁钕铁硼磁体及其制备方法和应用
优先权和相关申请
本申请要求享有2021年9月22日向中国国家知识产权局提交的，专利申请号为202111107088.3，发明名称为“一种高剩磁钕铁硼磁体及其制备方法和应用”的在先申请的优先权。所述在先申请的全文通过引用的方式结合于本申请中。
技术领域
本发明属于钕铁硼磁体领域，具体涉及一种烧结钕铁硼磁体及其制备方法和应用。
背景技术
烧结钕铁硼磁体作为第四代永磁材料，以其优良的磁性能被称为“磁王”，被广泛应用于汽车、风电、压缩机、电梯，以及工业自动化等众多领域。
进入21世纪以来，磁钢更多的关注于矫顽力性能的提升，尤其是在储量较为稀少的重稀土资源的供给出现失衡，导致原材料价格急速上涨而带来的成本压力下，众多学者及企业纷纷开始研究在降低重稀土使用量的前提下，保持甚至提高矫顽力性能，以保证磁钢在工作温度下的耐减磁能力，如细晶技术或晶界扩散技术。
随着新能源汽车市场的崛起以及高能效节能家电的新政策推出，电机的小型化、高能效指标成为新的关注点，为了保证尽可能的降低电机尺寸，保持甚至提高电机的输出功率，作为动力核心的磁钢必须具备高的能量密度，即高剩磁。
理论上纯钕铁硼磁体的极限剩磁为1.61T，目前，在实验室条件下可获得的剩磁最高为1.56T，但由于工艺难度及设备精度等原因，远远不足以实现量产。 同时，新能源汽车以及节能家电等领域使用的磁钢，其主流剩磁范围为1.10-1.40T之间，若可进一步提高剩磁，则可有效促进电机小型化以及高能效等级的要求。
专利CN11724985A，采用低B组分(0.80-0.93wt％)熔炼合金，使其具有一定量的过渡金属相(R 6T 13M)制备烧结磁体(或扩散后磁体)，并将烧结磁体(或扩散后磁体)在400℃以上600℃以下的温度进行10秒以上30分钟以下的保温处理，使其兼具高剩磁和高Hcj，剩磁可达到1.41T。采用低B组分使其在晶界生成了宽度较大的R 6T 13M相，但依照钕铁硼磁体剩磁理论公式要求，降低了主相体积比例，使其Br不可避免的降低，而且虽然晶界中的R 6T 13M相有利于Hcj的提升，但该晶界相稳定性较差，对设备工艺难度控制要求高，磁体方形度易出现波动，不能稳定大于0.95，直接影响电机的高温耐减磁能力。
专利CN10744699A，采用低B组分(0.94wt％)熔炼合金，制备柱状晶比例为95％以上的合金薄皮，采用旋转氢脆炉处理，用高压氮气制备3.75-3.9μm大小的气流磨粉，可制备Br在1.44-1.48T，Hcj达到14-16kOe的超高性能的钕铁硼磁体。控制了合金鳞片的柱状晶比例，优化了HD生产工艺，控制气流磨粉的粒度范围，以及匹配了烧结工艺，获得高Br及高Hcj的磁体。但其RE含量极低，在烧结时没有足够的富Nd相均匀包裹主相晶粒，进行助烧结，同时没有Zr或Ti的硼化物等晶界相的存在，容易形成异常晶粒长大，由于磁体晶粒大小的均匀性差引起方形度恶化，虽然具备高的Br和Hcj，但是异常晶粒长大区域极易产生反向磁化，使得磁体的耐减磁能力劣化。
发明内容
为解决上述技术问题，本发明提出了一种高剩磁钕铁硼磁体及其制备方法和应用。
本发明提供一种钕铁硼磁体，所述磁体具有以R-T-B型化合物为主要结构的晶粒，以及晶界相；所述钕铁硼磁体包括：
R：28％wt以上，30wt％以下；R代表稀土元素，选自Nd，或者Nd与下述稀土元素中的至少一种：Pr，La，Ce，Dy，Tb，Ho；
T：63wt％以上，70wt％以下；T选自Fe和/或Co，其中，Fe占T总量的99wt％以上；
B：0.98wt％以上，1.05wt％以下；
M1：大于0wt％，0.3wt％以下；M1选自Cu和Ga，且Ga占M1总量的75wt％以上。
M2：0.04wt％以上，0.15wt％以下；M2选自Zr、Ti、Nb中的至少一种。
优选地，M2选自Ti。
根据本发明的实施方案，所述钕铁硼磁体的制备原料中，元素的原子数还满足如下以下条件：
2.15≤[R]/([B]-2[M2])≤2.35
其中，[R]为R的原子百分比，[B]为B的原子百分比，[M2]为M2的原子百分比。本发明中，原子百分比是指[某原子的数目]/[原料中各种原子的总数]。
示例性地，[R]/([B]-2[M2])为2.15、2.2、2.24、2.29、2.3。
根据本发明的实施方案，当R选自Nd与下述稀土元素中的至少一种：Pr，La，Ce，Dy，Tb，Ho时，Dy，Tb，Ho等重稀土元素的总质量占磁体的质量的1wt％以下，优选为0.5wt％以下。
根据本发明的实施方案，所述磁体具有以下磁性能：
(1)方形度≥0.95，例如为0.95、0.96、0.97、0.98、0.99；
(2)Br≥1.44T，例如为1.45T、1.46T、1.47T、1.48T、1.49T、1.5T；
(3)Hcj≥1100kA/m，例如为1100kA/m、1110kA/m、1120kA/m、1130kA/m、1140kA/m、1150kA/m、1160kA/m、1170kA/m、1180kA/m、1190kA/m、1200kA/m。
本发明严格限定制备原料中各元素的含量，具体来讲：
因为Pr、Dy、Tb、Ho等稀土元素构成的R-T-B系主相晶粒的磁极化强度低 于Nd，会显著降低磁体的Br，在保证磁体的高Br的同时，可通过少量使用Dy、Tb、Ho等重稀土元素来提高磁体的Hcj。当磁体中的R过高时，磁体的富钕相增多，Br降低；当R过低时，磁体中不能形成均匀连续的富Nd相进行主相晶粒的磁隔绝，磁体的Hcj及方形度会急剧恶化。
因为Co会占据主相晶粒中Fe的位置，而Co的原子磁矩要小于Fe，添加Co会降低磁体的Br，因此控制Fe占T总量的99％以上，同时，通过控制其他成分以及优化工艺弥补改善Co对磁体的耐腐蚀及耐温性。
现有技术采用低B(≤0.95wt％)来制备高性能钕铁硼磁体，通过形成R-T-Ga型晶界相来起到晶界相增厚，改善磁体的Hcj，但是晶界相的增厚，不可避免的降低了主相晶粒的体积比，进而会显著降低磁体的Br性能。本发明通过控制B含量来提高主相晶粒的体积比，提高磁体的Br，当B含量过低时，形成的富B相或富Nd相比例较高，主相晶粒体积比小，导致磁体Br偏低；当B含量过高时，富B相体积比例显著提高，会大幅降低磁性能。
M1主要在晶界相处富集，能够改善晶界相结构，大幅提高Hcj。当磁体中不含Cu、Ga时，磁体的主相晶粒和富B相相对粗大，会大幅降低磁体磁性能；当磁体中的Cu、Ga含量过高时，会抑制晶粒的长大，同时晶界相增厚，主相晶粒体积比降低，降低磁体的Br。当达到本发明的Ga含量时，可以显著提升磁体的Hcj，且对磁体温度系数的具有显著的优化作用，避免低Co含量对磁体耐温性的影响。
M2与B形成A 2B型化合物，在晶界相中存在，起到抑制磁体晶粒异常长大。当M2的含量过低时，不能有效形成A 2B型化合物的存在，抑制磁体主相晶粒的异常长大；当M2的含量过高时，A 2B型化合物作为晶界相存在，降低了主相晶粒的体积比，磁体无法获得高Br。
本发明还提供上述钕铁硼磁体的制备方法，包括：(a)熔炼工序：将上述钕铁硼磁体的制备原料经高温熔融、浇铸、二次冷却后形成合金片；(b)制粉 工序：将合金片破碎成合金粉末；(c)压型工序：将合金粉末在磁场作用下压制成型，得到坯体；(d)烧结工序：将坯体经高温烧结处理。
根据本发明的实施方案，所述(a)熔炼工序具体包括：将上述钕铁硼磁体的制备原料在真空或惰性气体氛围下，充分熔融为合金钢液，然后经急速冷却形成合金片，再经过二次冷却，且所述二次冷却与急速冷却间隔不超过10s，且所述二次冷却的冷却速度为5-20℃/s。优选地，所述熔融在真空感应熔炼炉中通过中频感应加热进行。本发明中，急速冷却可选用本技术领域常用的急速冷却方法，只要能得到所需合金片即可。示例性地，所述急速冷却采用急冷辊进行。
本发明中，所述二次冷却可选用本技术领域常用的冷却方式和冷却装置进行。示例性地，所述二次冷却采用选自以下任一种冷却装置进行：低温惰性气体的喷淋、水冷圆盘或其他形式的冷却装置。
优选地，所述二次冷却的冷却速度优选为5-20℃/s。
优选地，所述合金片的厚度为0.15-0.45mm。
根据本发明的实施方案，所述(b)制粉工序包括粗破碎和细破碎。
优选地，所述粗破碎选自氢脆和/或中磨。
优选地，所述细破碎选自气流磨。优选地，所述气流磨在惰性气体气氛下进行。优选地，所述惰性气体选自氮气、氦气等。
本发明中，所述氢脆、中磨或气流磨可以采用本领域已知操作。
优选地，在所述细破碎后，还要通过筛选得到，例如经过分级轮筛选。
优选地，所述合金粉末的粒度SMD在2.0-3.4μm之间，且X90/X10≤4.5。其中，SMD为面积平均粒径，SMD越小，指代粉末颗粒的粒度越小，SMD越大，指代粉末颗粒的粒度越大；X90表示累计分布百分数达到90％时所对应的粒径值，即全部颗粒的粒径均不大于此粒径，大于次粒径值的颗粒数量为0，X10表示累计分布百分数达到90％时所对应的粒径值，即全部颗粒的粒径均不大于此粒径，大于次粒径值的颗粒数量为0，在此以X90/X10指代粉末的粒度分布，X90/X10越小，表征粉末的粒度分布更为集中。
优选地，在细破碎时还需要加入润滑剂，优选在气流磨前后均加入润滑剂。在气流磨前添加润滑剂，可以提高粉末流动性，在气流磨时改善粉末的流动性和均匀性；在气流磨后添加润滑剂，也可以改善粉末均匀性及流动性，便于均匀填粉压制。
优选地，所述润滑剂选自本领域已知试剂，以及本领域已知用量，以达到粉末充分混匀、易于成型为准。示例性地，所述润滑剂选自易挥发的脂类或醇类等有机溶剂，例如为硬脂酸锌。示例性地，所述润滑剂的添加量为制备原料总质量的0.1-1wt％。
优选地，加入润滑剂后，还需进行混料。优选地，混料时间为3-6h。
本发明中所述混料可采用本技术领域已知的方法进行，例如放置于混料机中进行混料。
根据本发明的实施方案，所述(c)压型工序具体包括：在磁场作用下将合金粉末压制成型，得到坯体。
优选地，压制成型在压机磨具腔体中进行。
优选地，压制成型前，需在2T的磁场强度下进行取向充磁、成型。
优选地，在压制成型后，施加反向磁场进行退磁。
优选地，成型坯体还可以在冷等静压机中处理，进一步提高坯体密度。
根据本发明的实施方案，所述(d)烧结工序包括第一次烧结、第一次冷却、第二次烧结和第二次冷却。本发明中的烧结工序可采用本技术领域已知的方法进行。示例性地，所述坯体在烧结炉中进行烧结。
优选地，所述烧结工序在真空气氛下进行。优选地，加热时，真空度为10 -1Pa以下。
优选地，所述第一次烧结的烧结温度为1000-1050℃，所述第一次烧结的保温时间为240-360min。
优选地，第二次烧结温度较第一次烧结温度高30-70℃，优选为1030-1100℃。
优选地，第二烧结的保温时间为270-360min。
优选地，第一次冷却和第二次冷却均低于200℃。
根据本发明的实施方案，所述烧结工序还包括时效处理，所述时效处理在第二次冷却之后进行。
优选地，所述时效处理选自一次时效处理，或者二次时效处理。
优选地，所述一次时效处理的条件为：时效处理温度为500-700℃之间，保温时间为240-420min。
优选地，所述二次时效处理包括：升温进行第一次时效处理，第一次时效处理温度为800-950℃，保温时间为180-300min；冷却至150℃以下，然后进行升温进行第二次时效处理，第二次时效处理温度为450-600℃之间，保温时间为240-360min。
根据本发明的实施方案，在烧结工序后，还可以进行扩散处理。
优选地，所述扩散处理包括将扩散材料施加在磁体表面，进行真空高温扩散处理、扩散冷却和扩散时效处理。
优选地，扩散材料选自Dy和/或Tb的纯金属、或Dy和/或Tb的氢化物、氧化物、氢氧化物、氟化物等合金。
优选地，扩散处理可选用真空蒸镀、磁控溅射、涂覆或掩埋等方式进行。
优选地，高温扩散的温度为850-950℃，高温扩散的时间为10-30h。
优选地，扩散冷却温度为低于100℃。
优选地，所述扩散时效处理的温度为450-600℃，所述扩散时效处理的时间为4-8h。
根据本发明的实施方案，在烧结工序后、扩散处理前，还可以将坯体加工成目标尺寸。
本发明需要严格限定磁体制备方法中各工序的条件，具体来讲：
合金钢液在急速冷却时，以在急冷辊上急速冷却为例，在急冷辊辊面上的合金片形成形核点，以形核点为起点，形成晶粒并长大。合金片在急冷辊上脱 落，其温度自熔融温度降低至800℃左右，此时，晶粒还在缓慢长大，因此需要及时进行二次冷却，降低合金片的温度，当二次冷却的时间间隔过长时，合金片上的主相晶粒会继续长大，甚至由于合金片温度的不均匀发散衍生二次晶，这些二次晶的存在会导致主相晶粒粒径的均匀性变差，从而导致磁体的方形度的恶化。当冷却速度过慢时，富B相会在主相晶粒周围的晶界相中大量生产，此时生产的富B相在制粉、烧结等工序无法有效的消除或减少，必然导致磁性能的急剧恶化；当冷却速度过高时，合金薄片会迅速冷却，主相晶粒停止生长，无法熔融吸收周围的晶界相和富B相进一步长大，体积比较小，从而导致磁体Br的降低。
由上文可知，由于磁体的制备原料中R含量较少，合金片上的主相晶粒和主相晶粒之间除了有二元晶界相和三元晶界相的存在外，还会存在部分主相晶粒直接接触，这种直接接触的主相晶粒之间具有极高的结合强度。当合金粉末粒度过小时，合金粉末颗粒以晶界相为主要断裂区域发生断裂的同时，为了达到目标粉末粒度，还会发生主相晶粒的内部断裂，这种断裂的粉末尺寸、表面状态不规则，经烧结后，与相邻晶粒以及晶界相的接触区域易形成反磁化点，表现为磁体方形度低，在高温或其他外部磁场的作用下容易导致磁体退磁。当粉末粒度过大时，晶界相不能与主相晶粒充分脱离，导致烧结时，主相晶粒熔融附着的富Nd相长大，没有足够的富Nd相包裹主相晶粒，导致磁体的Hcj大幅降低。当粉末粒度分布X90/X10在本发明的范围内时，可以获得粒径均匀一致的磁体，此时具备较高的Br和Hcj，当粒度分布X90/X10过大时，磁体晶粒大小差异较大，细粉末易团聚熔融形成三角晶界相，相邻粗粉末熔融形成大晶粒，这些都会严重影响磁体的方形度。
同时，本发明通过采用二次烧结工艺可大幅提高磁体性能，且有效抑制磁体晶粒的异常长大。本发明涉及的钕铁硼磁体制备方法，第二次烧结温度较第一次烧结温度高，采用较低的温度进行第一次烧结，可以将磁体的致密性提高，但仍存在部分的空隙，避免的主相晶粒的异常长大；而第二次烧结温度较一次 烧结温度有较大幅度的提升，可促进主相晶粒的充分长大，但不至于形成主相晶粒的异常长大，从而导致磁性能的急剧恶化。当两次烧结温度的温差过低时，为保证磁体烧结的致密性，一次烧结温度较高，晶粒排列已较为紧密，较低的二次烧结温度无法将磁体晶粒结构进行充分的重置优化，导致无法获得较高的磁性能。当两次烧结的温差过大时，一次烧结温度偏低，空隙较大，二次烧结温度过高，部分区域出现晶粒就异常长大，导致磁体性能恶化。
本发明还提供上述磁体在电机领域的应用。
本发明还提供一种电机，所述电机包括上述磁体。
本发明还提供上述电机的应用，优选地，所述电机可用于新能源汽车、节能家电。
有益效果：
本发明的钕铁硼磁体通过调整B、Cu、Ga、RE、Ti等元素的比例关系，可以获得较高的主相晶粒体积比，有效抑制晶界相中富B相的比例，通过添加过渡金属元素M1(如Ga)、M2(如Ti)对晶界相的结构优化调整，使得磁体具备较高的Br，兼具优良的Hcj和方形度性能。
本发明中，B含量较一般的烧结钕铁硼磁体的要高。一般钕铁硼磁体在兼顾磁体的Br和Hcj的性能时，[R]/([B]-2[M2])会略大于2.35，大于2.5，使其具有较少的富B相，或者不形成富B相的存在。本发明使得该比例在2.15-2.35之间，理论上会比一般的钕铁硼磁体形成更多的富B相，但在本关系式的比例范围内，结合本发明制备方法中的二次冷却，可提高磁体主相晶粒体积比，抑制富B相的过度形成，在保证磁体Br的同时，具有优良的Hcj及方形度指标。
本发明的磁体采用极少量的Dy/Tb等重稀土元素，甚至不使用，即可获得高剩磁及矫顽力，且磁体的方形度≥0.95，生产工艺简单，量产稳定性高。
采用本发明的制备方法制备磁体，剩磁高，Br≥1.44T，具有非常高的能量 密度，应用在电机上可有效提高单位体积的功率输出，可有效减少电机体积，节省电机的其他组件的材料损耗，对电机的小型化，低沉本发展具有重要作用。
具体实施方式
下文将结合具体实施例对本发明的技术方案做更进一步的详细说明。应当理解，下列实施例仅为示例性地说明和解释本发明，而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。
除非另有说明，以下实施例中使用的原料和试剂均为市售商品，或者可以通过已知方法制备。
以下实施例中，原子百分比是指[某原子的数目]/[原料中各种原子的总数]。其中，M1选自Cu和Ga；M2选自Zr、Ti、Nb中的至少一种；R选自Nd与下述稀土元素中的至少一种：Pr，La，Ce，Dy，Tb，Ho。
实施例1-4：
(1)按照表1磁体的目标组分配制原料，并采用甩带浇铸工艺制备得到钕铁硼合金片，合金片在急冷辊冷却脱落后，由低温氩气进行喷射进行二次冷却，通过调控低温氩气的流量及温度，从而使合金片以10℃/s的冷却速率进行二次冷却得到合金片，合金片掉落在水冷圆盘上进行回收，从而制得0.15-0.45mm厚度的合金片。
表1实施例磁体的目标组分(质量百分比)
编号 Pr Nd Dy B Co Cu Ga Al Zr Fe和杂质元素
实施例1 - 29 0.5 0.99 - 0.05 0.25 - 0.12 余量
实施例2 - 29 0.5 1.03 - 0.05 0.25 - 0.12 余量
实施例3 6 23.8 - 1.02 0.05 - 0.2 0.05 0.08 余量
实施例4 - 29 - 1.04 - 0.05 0.25 - 0.12 余量
(2)采用氢脆工艺对上述合金薄片进行粗破碎处理得到粉末，在粉末中添加质量为原材料的0.1wt％的硬脂酸锌作为润滑剂，混料60min。混料后的物料在流化床式气流磨进行细破碎处理，以氮气为研磨气体，通过调整分级轮转速、 研磨压力等设备参数来获得目标粒度SMD＝2.5μm的气流磨粉。
(3)将制得的目标粒度的气流磨粉再添加质量为原材料的0.2wt％的硬脂酸锌作为润滑剂，充分混料后，在2T的充磁场强下压制成坯体，再通过油冷等静压处理提高坯体密实度。
(4)将坯体放置于烧结炉中，在真空氛围下，进行二次烧结处理，两次烧结保温时间均为270min，烧结冷却低于80℃时后，加热升温至890℃进行保温，保温时间240min，冷却后进行二次时效，根据各组分不同调整为最佳时效温度，时效保温时间为280min，具体烧结时效制度见表2。
表2实施例1-4中合金片平均厚度、气流磨粉粒度及烧结工艺
Figure PCTCN2022120487-appb-000001
将烧结时效处理后的磁体，加工成直径10mm、高度10mm的标准样柱，采用BH仪测试磁体性能，测试磁体性能，具体磁性能测试结果见表3。
表3实施例磁性能测试结果
Figure PCTCN2022120487-appb-000002
根据表3结果可以得出，当各元素组分在控制范围内时，磁体可以具备较高的剩磁和矫顽力，同时确保方形度可以≥0.95。这保证了磁体在电机运转时可 以提供稳定功率输出。
对比例1-2
按照表4磁体的目标组分配制原材料，并采用甩带浇铸工艺制备得到钕铁硼合金片，合金片在急冷辊冷却脱落后，由低温氩气进行喷射进行二次冷却，通过调控低温氩气的流量及温度，合金片以10℃/s的冷却速率进行二次冷却得到合金片，合金片掉落在水冷圆盘上进行回收，获得合金片。
对比例3
按照表4磁体的目标组分配制原材料，并采用甩带浇铸工艺制备得到钕铁硼合金片，合金片在急冷辊上急冷后，直接掉落在水冷圆盘上进行冷却回收。
对比例4
按照表4磁体的目标组分配制原材料，并采用甩带浇铸工艺制备得到钕铁硼合金片，合金片在急冷辊上急冷后，直接掉落在水冷圆盘上进行冷却回收。
表4对比例1-4磁体的目标组分(质量百分比)
编号 Pr Nd Dy B Co Cu Ga Ti Zr Fe和杂质元素
对比例1 - 29 0.5 0.93 - 0.05 0.25 - 0.12 余量
对比例2 - 29 0.5 1.03 - 0.05 0.25 - 0.12 余量
对比例3 - 29 0.5 0.99 - 0.05 0.25 - 0.12 余量
对比例4 - 28.6 0.1 1.01 - 0.07 0.15 0.15 - 余量
将对比例1-4所获得的合金片按照实施例相同工艺制备成目标SMD＝2.5μm的气流磨粉，并压制，烧结时效处理。具体过程参数见表5。
表5对比例中合金片平均厚度、气流磨粉粒度及烧结工艺
Figure PCTCN2022120487-appb-000003
将对比例1-4制备的磁体，加工成直径10mm、高度10mm的标准样柱，采 用BH仪测试磁体性能，测试磁体性能，具体磁性能测试结果见表6。
表6对比例1-4磁性能测试结果
Figure PCTCN2022120487-appb-000004
根据对比例1可以看出，当[R]、[B]、[M2]的比值关系超出2.35时，虽然Hcj略有提高，但Br降低明显，且方形度低于0.95，导致其耐减磁能力波动，不能在电机高速运转时稳定输出磁场；
对比例2的[Cu]、[Ga]比例关系远小于0.75，使得磁体的Br及Hcj较实施例均出现明显的降低，不能兼具高剩磁及高矫顽力。
对比例3的目标磁体组分与实施例1的相同，但在熔炼工序并未采用本专利要求的方式对合金片进行二次冷却，根据表3可以看出，当取消对合金片二次冷却时，合金片因晶粒的显著长大导致厚度增大，在进行气流磨研磨时，虽然也获得了目标SMD的气流磨粉，但是，粒度分布(X90/X10)显著恶化，粗粉及细粉比例增加，粉末均匀性差；且在烧结工序仅进行一次烧结，并未采用二次烧结工艺，磁体的剩磁及矫顽力也均明显降低。
根据对比例4可以看出，当[Cu]、[Ga]的比值关系小于0.75时，且没有采用本发明述的二次冷却和二次烧结工艺，其Hcj明显偏低，且方形度远低于0.95，导致其耐减磁能力波动，不能在电机高速运转时稳定输出磁场；
实施例5
取实施例1的烧结时效后的磁体，加工为长20mm、宽20mm、厚5mm的薄片产品，采用浸蘸工艺，在磁体表面施加一层金属Dy的薄膜，然后在900℃下，保温15小时进行扩散处理，扩散温度冷却低于100℃后，再升温至500℃进行5小时的时效处理。将最终磁体进行磁性能测试和成分测试。其最终成分及磁性能结果见表9及表10。
表9实施例5的成分测试结果
编号 Pr Nd Dy B Co Cu Ga Al Zr Fe及杂质元素
实施例5 - 28.6 0.8 0.99 - 0.05 0.25 - 0.12 余量
表10实施例5的磁性能测试结果
Figure PCTCN2022120487-appb-000005
由上述结果可知，扩散后的磁体矫顽力获得了显著提升，且Br未明显降低，本发明的磁体也可作为扩散基材。
以上，对本发明的示例性实施方式进行了说明。但是，本发明不拘囿于上述实施方式。本领域技术人员在本发明的精神和原则之内，所做的任何修改、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. 一种钕铁硼磁体，其特征在于，所述钕铁硼磁体具有以R-T-B型化合物为主要结构的晶粒，以及晶界相；所述钕铁硼磁体的包括：
    R：28％wt以上，30wt％以下；R代表稀土元素，选自Nd，或者Nd与下述稀土元素中的至少一种：Pr，La，Ce，Dy，Tb，Ho；
    T：63wt％以上，70wt％以下；T选自Fe和/或Co，其中，Fe占T总量的99wt％以上；
    B：0.98wt％以上，1.05wt％以下；
    M1：大于0wt％，0.3wt％以下；M1选自Cu和Ga，且Ga占M1总量的75wt％以上；
    M2：0.04wt％以上，0.15wt％以下；M2选自Zr、Ti、Nb中的至少一种；
    所述钕铁硼磁体的制备原料中，元素的原子数还满足如下以下条件：
    2.15≤[R]/([B]-2[M2])≤2.35，
    其中，[R]为R的原子百分比，[B]为B的原子百分比，[M2]为M2的原子百分比；
    当R选自Nd与下述稀土元素中的至少一种：Pr，La，Ce，Dy，Tb，Ho时，Dy，Tb，Ho等重稀土元素的总质量占磁体的质量的1wt％以下；
    所述磁体具有以下磁性能：
    (4)方形度≥0.95；
    (5)Br≥1.44T；
    (6)Hcj≥1100kA/m。
  2. 根据权利要求1所述的钕铁硼磁体，其特征在于，Dy，Tb，Ho等重稀土元素的总质量占磁体的质量的0.5wt％以下；
    优选地，M2选自Ti。
  3. 权利要求1或2所述的钕铁硼磁体的制备方法，其特征在于，包括：(a) 熔炼工序：将上述钕铁硼磁体的制备原料经高温熔融、浇铸、二次冷却后形成合金片；(b)制粉工序：将合金片破碎成合金粉末；(c)压型工序：将合金粉末在磁场作用下压制成型，得到坯体；(d)烧结工序：将坯体经高温烧结处理。
  4. 根据权利要求3所述的制备方法，其特征在于，所述(a)熔炼工序具体包括：将上述钕铁硼磁体的制备原料在真空或惰性气体氛围下，充分熔融为合金钢液，然后经急速冷却形成合金片，再经过二次冷却，且所述二次冷却与急速冷却间隔不超过10s，且所述二次冷却的冷却速度为5-20℃/s。
  5. 根据权利要求3或4所述的制备方法，其特征在于，所述急速冷却采用急冷辊进行。
    优选地，所述二次冷却采用选自以下任一种冷却装置进行：低温惰性气体的喷淋、水冷圆盘或其他形式的冷却装置。
    优选地，所述二次冷却的冷却速度优选为5-20℃/s。
    优选地，所述合金片的厚度为0.15-0.45mm。
  6. 根据权利要求3-5任一项所述的制备方法，其特征在于，所述(b)制粉工序包括粗破碎和细破碎。
    优选地，所述粗破碎选自氢脆和/或中磨。
    优选地，所述细破碎选自气流磨。优选地，所述气流磨在惰性气体气氛下进行。优选地，所述惰性气体选自氮气、氦气等。
    优选地，在所述细破碎后，还要通过筛选得到，例如经过分级轮筛选。
    优选地，所述合金粉末的粒度SMD在2.0-3.4μm之间，且X90/X10≤4.5。
    优选地，在细破碎时还需要加入润滑剂，优选在气流磨前后均加入润滑剂。优选地，所述润滑剂选自易挥发的脂类或醇类等有机溶剂。示例性地，所述润滑剂的添加量为制备原料总质量的0.1-1wt％。
    优选地，加入润滑剂后，还需进行混料。优选地，混料时间为3-6h。
    优选地，所述(c)压型工序具体包括：在磁场作用下将合金粉末压制成型， 得到坯体。
    优选地，压制成型前，需在2T的磁场强度下进行取向充磁、成型。
    优选地，在压制成型后，施加反向磁场进行退磁。
    优选地，成型坯体还可以在冷等静压机中处理，进一步提高坯体密度。
  7. 根据权利要求3-6任一项所述的制备方法，其特征在于，所述(d)烧结工序包括第一次烧结、第一次冷却、第二次烧结和第二次冷却。
    优选地，所述烧结工序在真空气氛下进行。优选地，加热时，真空度为10 -1Pa以下。
    优选地，所述第一次烧结的烧结温度为1000-1050℃，所述第一次烧结的保温时间为240-360min。
    优选地，第二次烧结温度较第一次烧结温度高30-70℃，优选为1030-1100℃。
    优选地，第二烧结的保温时间为270-360min。
    优选地，第一次冷却和第二次冷却均低于200℃。
    优选地，所述烧结工序还包括时效处理，所述时效处理在第二次冷却之后进行。
    优选地，所述时效处理选自一次时效处理，或者二次时效处理。
    优选地，所述一次时效处理的条件为：时效处理温度为500-700℃之间，保温时间为240-420min。
    优选地，所述二次时效处理包括：升温进行第一次时效处理，第一次时效处理温度为800-950℃，保温时间为180-300min；冷却至150℃以下，然后进行升温进行第二次时效处理，第二次时效处理温度为450-600℃之间，保温时间为240-360min。
    优选地，在烧结工序后，还可以进行扩散处理。
    优选地，所述扩散处理包括将扩散材料施加在磁体表面，进行真空高温扩散处理、扩散冷却和扩散时效处理。
    优选地，扩散材料选自Dy和/或Tb的纯金属、或Dy和/或Tb的氢化物、氧化 物、氢氧化物、氟化物等合金。
    优选地，扩散处理可选用真空蒸镀、磁控溅射、涂覆或掩埋等方式进行。
    优选地，高温扩散的温度为850-950℃，高温扩散的时间为10-30h。
    优选地，扩散冷却温度为低于100℃。
    优选地，所述扩散时效处理的温度为450-600℃，所述扩散时效处理的时间为4-8h。
  8. 权利要求1-2所述的磁体在电机领域的应用。
  9. 一种电机，所述电机包括权利要求1-2所述的磁体。
  10. 权利要求9所述的电机的应用，优选地，所述电机可用于新能源汽车、节能家电。
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