CN115020054A - Magnetic alloy binder, composite rare earth permanent magnetic material and preparation method thereof - Google Patents

Magnetic alloy binder, composite rare earth permanent magnetic material and preparation method thereof Download PDF

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Publication number
CN115020054A
CN115020054A CN202110246844.4A CN202110246844A CN115020054A CN 115020054 A CN115020054 A CN 115020054A CN 202110246844 A CN202110246844 A CN 202110246844A CN 115020054 A CN115020054 A CN 115020054A
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magnetic
rare earth
binder
equal
earth permanent
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卢赐福
曾炜炜
周庆
唐仁衡
肖方明
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Institute of Rare Metals of Guangdong Academy of Sciences
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Institute of Rare Metals of Guangdong Academy of Sciences
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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
    • 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

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

Abstract

The invention discloses a magnetic alloy binder, a composite rare earth permanent magnetic material and a preparation method thereof. The magnetic alloy binder has a chemical formula of R in atomic percentage x Fe 100‑x‑y‑z‑ v M1 y M2 z B v Wherein R is at least one selected from La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y, 10.0<x<14.0; m1 is at least one of Al, Co, Si, Zr, Hf, Ta, Nb, Ti, V, Cr, Mn, Ni, W and Mo, and y is more than or equal to 0 and less than or equal to 15.0; m2 is at least one of Cu and Ga, z is 0-8.0, v is 3-10.0. The invention realizes the utilization of the magnetic binder with lower rare earth content, higher magnetic energy product, lower acquisition cost and wider component range to prepare Sm 2 Fe 17 N x 、Nd(Fe,M) 12 N x 、ThMn 12 Type Sm (Fe, M) 12 The magnetic powder is bonded into a high-performance composite permanent magnetic material.

Description

Magnetic alloy binder, composite rare earth permanent magnetic material and preparation method thereof
The technical field is as follows:
the invention relates to a rare earth permanent magnet material, in particular to a magnetic alloy binder, a composite rare earth permanent magnet material and a preparation method thereof.
The background art comprises the following steps:
the rare earth permanent magnetic material is an important basic functional material in modern society, and is widely applied to industries such as computers, automobiles, instruments, household appliances, petrochemical industry, medical care, aerospace, new energy and the like.
The Sm-Co permanent magnet invented in 1960 s was the first generation of high performance rare earth permanent magnet material. The Sm — Co is limited in its application field because it contains expensive and scarce strategic element Co having a high specific gravity.
The sintered Nd-Fe-B permanent magnet was invented by the Sumitomo special metal Kawawa (Masato Sagawa) in 1982, and is the most widely used rare earth permanent magnet material because of the highest magnetic energy product so far, because the sintered Nd-Fe-B permanent magnet does not contain strategic metal, has high cost performance and simple preparation method, and is widely applied. The bonded magnet prepared by using the rapidly quenched Nd-Fe-B magnetic powder invented by general electric company and organic resin is widely accepted by the market because of high dimensional precision and convenience in preparing special-shaped magnets.
After the Nd-Fe-B compound, Sm 2 Fe 17 N x (samarium-iron-nitrogen for short), Nd (Fe, M) 12 N x Neodymium iron nitrogen for short, and Sm (Fe, M) type ThMn12 12 Rare earth transition metal compounds such as (1: 12 samarium iron for short) were also found to have excellent intrinsic magnetic properties and are considered as candidates for the next generation of rare earth permanent magnetic materials. Wherein Sm 2 Fe 17 N x (samarium iron nitrogen for short), Nd (Fe, M) 12 N x The neodymium iron nitrogen is a metastable phase and can be decomposed at the temperature higher than 600 ℃, so that the neodymium iron nitrogen cannot be formed by the traditional high-temperature sintering process. Sm (Fe, M) 12 (1: 12 samarium iron for short) is stable at high temperature, but its bulk material is difficult to develop high coercive force. At present, the magnetic materials can only be prepared into superfine single crystal or polycrystalline powder to have higher coercive force so as to obtain high magnetic energy product, and are generally used for preparing resin or low-melting-point metal bonded magnets at present.
The use of organic resins for bonding makes it possible to manufacture anisotropic permanent magnetic materials by injection molding or compression molding processes, but injection molding or molding generally requires the addition of more than 30% v of organic resin. The use of resin bonding and injection molding has the following disadvantages in 3 respects: firstly, in order to ensure that the volume proportion of the flowable resin is higher than 30%, the remanence of the magnet is greatly reduced; secondly, the injection molding generally requires that magnetic powder is mixed and prepared into material particles, the process needs to be carried out at a temperature higher than the melting point of the binding resin, the superfine powder is easy to oxidize and causes the reduction of magnetic performance, in order to relieve the reduction of the magnetic performance, the magnetic powder needs to be coated with oxidation resistance and corrosion resistance, the technical requirement is very strict, and the cost is additionally increased; third, the organic resin itself has a low melting point, and the use temperature of the bonded composite magnet is limited by the strength of the resin. Similar problems exist with the use of compression molded bonded magnets.
In order to solve the problem of forming metastable magnetic powder such as samarium iron nitrogen, the invention patent CN111863369A discloses a method for using nanocrystalline R-Fe-B alloy as a magnetic binder, and improving the deformation capacity by reducing the melting point of a rare earth-rich grain boundary phase in the nanocrystalline neodymium iron boron magnetic powder and increasing the content of the rare earth-rich phase, so that the magnetic powder contains a considerable proportion of liquid phase at 400-550 ℃, thereby improving the filling performance of the binder and enabling the binder to become the magnetic binder with good binding capacity. However, the method proposed by CN111863369A for improving the filling performance of the binder requires that the rare earth content is greatly increased, and the melting point of the re-enriched rare earth grain boundary phase is lower than the temperature for hot pressing, i.e. the binder contains a certain proportion of liquid phase during the hot pressing process. Binders meeting these requirements are costly and have limited component ranges. Because the rare earth-rich phase belongs to the non-magnetic phase, the increase of the content of the rare earth-rich phase inevitably increases the content of rare earth elements in the magnetic powder, and the increase of the content of the rare earth elements can obviously increase the raw material cost of the binder on one hand and can also reduce the magnetic energy product of the binder on the other hand. In the patent CN111863369A, the method of reducing the melting point of the rare earth-rich phase and increasing the content of the rare earth-rich phase limits the range of the components of the magnetic binder, which inevitably increases the cost of the binder and limits the variety of the binder.
The invention content is as follows:
in order to solve the problems in the prior art, the invention provides a magnetic alloy binder, a composite rare earth permanent magnet material and a preparation method thereof, and the invention realizes the utilization of a magnetic binder with lower rare earth content, higher magnetic energy product, lower acquisition cost and wider component range, and Sm is added into the magnetic binder 2 Fe 17 N x 、Nd(Fe,M) 12 N x 、ThMn 12 Type Sm (Fe, M) 12 The magnetic powder is bonded into a high-performance composite permanent magnetic material. In addition, SmCo can be added into the magnetic alloy binder and the forming process provided by the invention 5 (1:5 type Sm-Co), Sm (Co, Fe, Zr, Cu) z (2:17 type Sm-Co, 5<z<8.5)、R 2 Fe 14 B, binding the rare earth transition metal compound magnetic powder into a compact magnet to prepare the high-performance composite permanent magnet material.
The first purpose of the invention is to provide a magnetic alloy adhesive, the chemical formula of which is expressed by atomic percentage is R x Fe 100-x-y-z-v M1 y M2 z B v The magnetic alloy binder according to (1), wherein R is at least one selected from lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), and yttrium (Y), 10.0<x<14.0; m1 is at least one of Al, Co, Si, Zr, Hf, Ta, Nb, Ti, V, Cr, Mn, Ni, W and Mo, and y is more than or equal to 0 and less than or equal to 15.0; m2 is at least one of Cu and Ga, z is 0-8.0, v is 3-10.0.
The magnetic alloy binder has the following microstructure and morphological characteristics: with a particle size of 10-500nm 2 Fe 14 B main phase and rare earth-rich phase distributed in the main phase grain boundary, wherein R 2 Fe 14 The atomic content occupied by the main phase B is 95-99%, and the atomic content occupied by the rare earth-rich phase is 0.1-5%; the magnetic alloy binder also contains C, O, N and its compound and other impurities, which are introduced in the preparation process, and the content of the impurities is less than 3 wt%. The magnetic alloy binder is in the form of powder particles having a size distribution of between 0.1 and 10 μm.
The preparation method of the magnetic alloy binder comprises the following steps:
the method comprises the following steps: the alloy adhesive with isotropic magnetic property is directly prepared by using a melt rapid quenching method, namely, the alloy adhesive has a chemical formula R expressed by atomic percentage x Fe 100-x-y-z-v M1 y M2 z B v Casting the melt onto a water-cooled copper roller, rapidly quenching the alloy melt at a roller speed of 10-50m/s to prepare an amorphous or nanocrystalline rapidly quenched thin strip, and preparing an isotropic magnetic binder, wherein the main phase R in the alloy 2 Fe 14 The size range of the B crystal grains is 10-120nm, and the rare earth-rich phase is uniformly distributed on the main phase grain boundary. Grinding the thin strip which is subjected to heat treatment and has permanent magnetic performance into a fine powder magnetic binder by using a ball mill or an air flow mill, wherein the diameter range of the powder is 0.1-10 mu m. The commercial quick-quenched neodymium-iron-boron magnetic powder with the specified microstructure characteristics can also be directly purchased through a quick quenching process. The commercial rapidly quenched neodymium-iron-boron magnetic powder is generally used as a magnetic material for manufacturing a resin or plastic bonded magnet or used as a raw material for preparing a high-performance permanent magnet material through hot pressing-hot deformation. Since the rapidly quenched neodymium-iron-boron magnetic powder generally has a nanocrystalline structure, and considering cost factors, commercial magnetic powder can be directly purchased, and the particles ground to 0.1-10 μm are used as the magnetic alloy binder in the invention. If the magnetic property and the filling capacity of the directly purchased quick-quenched magnetic powder are insufficient, the alloy binder with isotropic magnetic property can be prepared by performing grain boundary diffusion hypoeutectic alloy on the basis of the quick-quenched magnetic powder through the second method.
The second method comprises the following steps: the alloy binder with isotropic magnetic property is prepared by carrying out grain boundary diffusion low eutectic alloy on the basis of the rapidly quenched magnetic powder. Exemplified here with rare earth R, Cu and Al as starting materials with an impurity content of less than 1 wt.%, according to the formula R x Cu 100-x-y Al y (10<x<40，0≤y<10) Batching to form the alloy with the melting point lower than 600 ℃. Melting the alloy into uniform melt, and rapidly quenching at a roller speed of 10-50m/s to prepare amorphous or nanocrystalline rapidly quenched thin strips. Grinding the thin strip into low eutectic alloy by using a high-energy ball mill or a jet millPowder with a diameter in the range of 1-200 μm. Uniformly mixing the low eutectic alloy powder and commercial R-Fe-B rapid-quenching magnetic powder such as MQ magnetic powder to obtain a mixed alloy powder mixture with a chemical formula R expressed by atomic percentage x Fe 100-x-y-z-v M1 y M2 z B v The ingredients expressed. Mixing the materials in N 2 And uniformly mixing the materials in a mixer under the protection of gas or Ar gas, and then performing heat treatment under vacuum or Ar protection, wherein the heat treatment temperature is 520-750 ℃, and the heat treatment time is 30-360min, so that the low eutectic alloy is diffused into the crystal boundary of the R-Fe-B quick-quenched magnetic powder. The magnetic powder which is subjected to heat treatment and has permanent magnetic performance is ground into a magnetic alloy binder in a fine powder state by using a ball mill or an air flow mill, and the diameter range of the powder is 0.1-10 mu m. The method is used for preparing isotropic magnetic binder, R in alloy 2 Fe 14 The grain diameter of B is 10-200nm, preferably 10-100 nm.
The third method comprises the following steps: the alloy binder with anisotropic magnetic property is prepared by carrying out grain boundary diffusion low eutectic alloy on the basis of HDDR R-Fe-B magnetic powder. Using rare earth R, Cu with impurity content less than 1 wt% and Al as raw materials according to chemical formula R x Cu 100-x-y Al y (10<x<40，0≤y<10) Batching to form the alloy with the low melting point lower than 600 ℃. The metal raw materials are put into a crucible and are inductively smelted into a uniform melt. And pouring the melt onto a water-cooled copper roller, wherein the surface rotating speed of the copper roller is 10-40 m/s. Namely, the alloy melt is rapidly quenched to prepare an amorphous or nanocrystalline rapidly quenched thin strip. And grinding the thin strip into low eutectic alloy powder by using a high-energy ball mill or a jet mill, wherein the diameter range of the powder is 1-200 mu m. Uniformly mixing the low eutectic alloy powder and the commercial anisotropic HDDR R-Fe-B magnetic powder to obtain a mixed alloy powder mixture with a chemical formula R expressed by atomic percentage x Fe 100-x-y-z-v M1 y M2 z B v The stated components. Mixing the materials in N 2 Uniformly mixing the materials in a mixer under the protection of gas or Ar gas, and performing heat treatment under vacuum or Ar protection at 500-850 deg.C for 30-600min to diffuse the eutectic alloy into anisotropic HDGrain boundaries of DR R-Fe-B magnetic powder. Grinding the magnetic powder which is subjected to heat treatment and has permanent magnetic performance into a fine powder magnetic binder by using a ball mill or an air flow mill, wherein the diameter range of the powder is 0.5-10 mu m. The method can be used to prepare anisotropic magnetic binder, R in alloy 2 Fe 14 The grain diameter of B is in the range of 100-500nm, preferably in the range of 100-300 nm.
Preferably, the magnetic alloy binder has a chemical formula of R in atomic percentage x Fe 100-x-y-z- v M1 y M2 z B v Wherein R is selected from one of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y, 10.0<x<14.0; m1 is selected from one of Al, Co, Si, Zr, Hf, Ta, Nb, Ti, V, Cr, Mn, Ni, W and Mo, and y is more than or equal to 0 and less than or equal to 15.0; m2 is one of Cu and Ga, z is more than or equal to 0 and less than or equal to 8.0, and v is more than or equal to 3 and less than or equal to 10.0.
Preferably, the magnetic alloy binder has a chemical formula of R in atomic percentage x Fe 100-x-y-z- v M1 y M2 z B v Wherein R is Pr and/or Nd, 11.8 ≦ x ≦ 13.9, M1 is one of Zr and Nb, y is 0.5 to 1.0, z is 0.2 to 1.6, and v is 5.5 to 5.9.
The second purpose of the invention is to protect a preparation method of a composite rare earth permanent magnetic material, which comprises the following steps: the chemical formula represented by the above atomic percent is R x Fe 100-x-y-z-v M1 y M2 z B v The magnetic alloy binder is prepared by binding raw material magnetic powder into a magnet, and the raw material magnetic powder is selected from Sm 2 Fe 17 N x 、Nd(Fe,M) 12 N x 、ThMn 12 Type Sm (Fe, M) 12 、SmCo 5 (1:5 type Sm-Co), Sm (Co, Fe, Zr, Cu) z, R 2 Fe 14 B single crystal, oriented polycrystal HDDR-R 2 Fe 14 More than one rare earth transition metal compound magnetic powder in B, wherein Sm (Co, Fe, Zr, Cu) z is 2:17 type Sm-Co, 5<z<8.5. The average particle diameter of the raw material magnetic powder is 1-200 μm. Original sourceThe material magnetic powder has the function of providing magnetic performance for the composite magnet, the types and the proportion of the material magnetic powder can be adjusted according to the design target of cost and magnetic performance, and various magnetic powders can be mixed for use.
Preferably, the volume ratio of the raw material magnetic powder in the composite rare earth permanent magnet material is 60-95%, and the volume ratio of the magnetic alloy binder is 5-40%.
Preferably, the volume ratio of the raw material magnetic powder in the composite rare earth permanent magnet material is 80-90%, and the volume ratio of the magnetic alloy binder is 10-20%.
Preferably, the preparation method of the composite rare earth permanent magnetic material comprises the following specific steps: uniformly mixing raw material magnetic powder and a magnetic alloy binder under the protection of vacuum or inert gas, performing orientation compression in a magnetic field of more than 15kOe to form a pressed compact, transferring the pressed compact into a pressure sintering furnace, heating to 400-600 ℃ in vacuum or under the protection of inert gas, loading the pressure of 50-400MPa, keeping the pressure for 10-360min, and pressing the pressed compact into the composite rare earth permanent magnet material.
The density of the compact block magnetic alloy binder and the actual density of the composite rare earth permanent magnet material (composite magnet) are tested by an Archimedes method. The theoretical density of the composite magnet is the bulk magnetic alloy binder density plus the volume proportion of the magnetic alloy binder plus the theoretical density of the raw material magnetic powder plus the volume proportion of the raw material magnetic powder. The relative density of the composite magnet (actual density of the composite magnet/theoretical density of the composite magnet) is 100%. The low temperature filling performance of the magnetic alloy binder is measured by the relative density of the composite magnet.
In the invention, the filling of the binder and the molding of the composite magnet can be realized under the condition that the temperature is lower than the melting point of the rare earth-rich phase in the binder by prolonging the hot pressing or hot isostatic pressing time. In the process of hot pressing or hot isostatic pressing of the composite magnet, under the action of asymmetric stress, internal crystal grains of the binder particles with the nanocrystalline structures can slide through a crystal boundary, so that the binder particles are subjected to creep deformation and enter a magnetic powder gap, and the densification of the composite magnet is realized. The hot pressing may be performed in a vacuum, high purity argon atmosphere, using equipment such as a uniaxial hot pressing furnace, a hot isostatic pressing furnace, and a discharge plasma sintering furnace.
The invention also protects the composite rare earth permanent magnet material prepared by the preparation method of the composite rare earth permanent magnet material.
Compared with the prior art, the invention has the following advantages:
1. the invention utilizes the magnetic binder with lower rare earth content, higher magnetic energy product, lower cost and wider component range to prepare Sm 2 Fe 17 N x 、Nd(Fe,M) 12 N x 、ThMn 12 Type Sm (Fe, M) 12 、SmCo 5 (1:5 type Sm-Co), Sm (Co, Fe, Zr, Cu) z (2:17 type Sm-Co, 5)<z<8.5)、R 2 Fe 14 And B, binding the rare earth transition metal compound magnetic powder into a compact magnet. The invention utilizes the characteristic of fine grain size and the binder particles containing low-melting-point phase to deform through grain boundary sliding under the action of stress, so that the binder particles generate creep deformation under the condition that the temperature is higher than the melting point of the rare earth-rich phase and enter magnetic powder gaps, thereby realizing the densification of the composite magnet, ensuring that the relative density of the composite magnet reaches 90-99 percent, and preparing the high-performance composite permanent magnetic material. The invention can reduce the limitation of the rare earth-rich phase type, melting point and volume ratio in the magnetic binder, and broaden the component range and magnetic performance range of the magnetic binder. The invention solves the problems that the cost is overhigh due to overhigh content of the rare earth phase in the magnetic binder in the prior art, the composite permanent magnetic material is required to be pressed at the melting point of the rare earth-rich phase which is higher than the binder when being prepared, and the component selection range of the magnetic binder is limited due to too strict requirement, and avoids the reduction of the magnetic property of the binder caused by improving the content of the rare earth, thereby being beneficial to improving the magnetic energy product of the composite magnet.
2. The magnetic alloy binder provided by the invention is mainly deformed through creep deformation, so that high deformation can be obtained through prolonging time at a temperature lower than the melting point of a rare earth-rich phase in the magnetic binder and a pressure lower than 400MPa, high filling rate is realized, and simultaneously, the reaction of the binder and magnetic powder is reduced, thereby reducing the loss of magnetic performance caused by the reaction of the binder and raw material magnetic powder. In addition, lower processing temperatures and lower pressures facilitate selection of molds, reducing mold wear, and thus may reduce mold cost while achieving the same densification.
3. The magnetic alloy binder provided by the invention can bind Sm 2 Fe 17 N x 、Nd(Fe,M) 12 N x The magnetic powder is bonded into a compact magnet at the temperature lower than the decomposition temperature (600 ℃); ThMn can also be blended using low temperature binding ability 12 Type Sm (Fe, M) 12 、SmCo 5 (1:5 type Sm-Co), Sm (Co, Fe, Zr, Cu) z (2:17 type Sm-Co, 5)<z<8.5)、R 2 Fe 14 B, and the like, and the magnetic powder of the rare earth transition metal compound is bonded into a compact permanent magnet material. Therefore, according to the magnetic performance and the cost requirement of the composite magnet, the corresponding magnetic powder can be selected to prepare a composite permanent magnet material with high performance and low cost, or a magnet with specific magnetic performance. And the binder with better corrosion resistance can be selected according to the service environment requirement of the composite magnet. Meanwhile, the method for preparing the compact magnet by using the magnetic binder is also an efficient method for recycling waste magnets and fragments formed in the magnet processing process.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
Example 1
Using MQ-UF quick-quenched magnetic powder (component Nd) from Magen 13.6 Fe 73.6 Ga 0.6 Co 6.6 B 5.6 Magnetic performance parameters: br ═ 0.77T, (BH) max 12.4 Hcj 19.8kOe) is a magnetic alloy binder. And (3) grinding the MQ-UF quick-quenched magnetic powder into fine powder with the average particle diameter of 3 mu m by using an airflow grinding powder device. Sm in an average particle diameter of 3 mu m 2 Fe 17 N 3 The anisotropic magnetic powder is used as raw material magnetic powder, the coercive force of the magnetic powder is 9.2kOe, and the maximum magnetic energy product of the magnetic powder is 33.2 MGOe. Using MQ-UF quick-quenched magnetic powder as a magnetic alloy binder, wherein the mass ratio of the magnetic alloy binder to the magnetic powder is 20:80, and mixing the raw material magnetic powder and the magnetic alloy binderLoading into a three-dimensional mixer, and mixing uniformly under the protection of high-purity argon. And (3) performing orientation compression on the mixture in a magnetic field with the temperature of more than 20kOe to form a pressed blank, wherein the pressure loading direction is vertical to the magnetic field direction, and the pressure is 100 MPa. The compact was transferred to a pressure sintering furnace with the pressure loading direction perpendicular to the orientation direction at 3 x 10 -3 Heating to 480 ℃ in vacuum of Pa, loading 240Mpa of pressure, keeping the pressure for 10-360min, and pressing the pressed blank into a compact composite magnet. Table 1 shows magnetic alloy binder and Sm 2 Fe 17 N 3 When the mass ratio of the magnetic powder is 20:80, the hot pressing process influences the density and the magnetic performance of the composite magnet.
TABLE 1
Composite magnet numbering Hot pressing process Relative density/%) Coercive force/kOe Maximum magnetic energy product/MGOe
SUF-1 240Mpa*10min 85 10.3 22.2
SUF-2 240Mpa*20min 88 10.4 25.3
SUF-3 240Mpa*30min 93 10.5 26.7
SUF-4 240Mpa*40min 95 10.4 27.3
SUF-5 240Mpa*60min 96 10.3 27.6
Example 2
The same as example 1, except that: the mass ratio of the magnetic alloy binder to the magnetic powder is 5-40:60-95, and the hot pressing process is 240Mpa for 60 min. The effect of the magnetic alloy binder ratio on the magnetic properties of the composite magnet at 240 Mpa-60 min of hot pressing is shown in table 2.
TABLE 2
Composite magnet numbering Magnetic alloy binder wt% Relative density/%) Coercive force/kOe Maximum magnetic energy/MGOe
SUF-7 5 88 9.1 26.4
SUF-8 10 94 9.5 28.2
SUF-9 15 95 10.3 27.6
SUF-10 20 96 10.4 27.6
SUF-11 25 97 10.5 26.3
SUF-12 40 98 12.3 23.5
Example 3
MQ-16-9HD quick-quenching magnetic powder (component Nd) from Megaku magnet 10.6 Fe 82.1 Zr 0.9 B 6.4 Magnetic performance parameters: br ═ 0.87T, (BH) max 15.5 Hcj 9.4kOe) is a magnetic alloy binder. And (3) grinding the rapidly quenched magnetic powder into fine powder with the average particle diameter of 3 mu m by using an airflow milling powder preparation device. Sm in an average particle diameter of 3 mu m 2 Fe 17 N 3 The anisotropic magnetic powder is used as raw material magnetic powder, the coercive force of the magnetic powder is 9.2kOe, and the maximum magnetic energy product of the magnetic powder is 33.2 MGOe. The method comprises the steps of taking rapidly quenched magnetic powder as a magnetic alloy binder, wherein the mass ratio of the magnetic alloy binder to the magnetic powder is 20:80, loading the raw material magnetic powder and the magnetic alloy binder into a three-dimensional mixer, and uniformly mixing under the protection of high-purity argon. And (3) performing orientation compression on the mixture in a magnetic field with the temperature of more than 20kOe to form a pressed blank, wherein the pressure loading direction is vertical to the magnetic field direction, and the pressure is 100 MPa. The compact was transferred to a pressure sintering furnace with the pressure loading direction perpendicular to the orientation direction at 3 x 10 -3 Pa to 500 deg.C, loading 300MPa pressure for 10-360min, and pressing into compact. Table 3 shows the effect of the hot pressing process on the density and magnetic properties of the composite magnet at a mass ratio of 20:80 of magnetic alloy binder to magnetic powder.
TABLE 3
Composite magnet numbering Hot pressing process Relative density/%) Coercive force/kOe Maximum magnetic energy product/MGOe
SHD-1 300Mpa*10min 83 9.1 24.0
SHD-2 300Mpa*20min 85 9.2 24.6
SHD-3 300Mpa*30min 90 9.2 26.1
SHD-4 300Mpa*40min 92 9.1 26.6
SHD-5 300Mpa*60min 93 9.2 27.0
Example 4
The same as in example 3, except that: the mass ratio of the magnetic alloy binder to the magnetic powder is 5-40:60-95, and the hot pressing process is 300Mpa 60 min. The effect of the magnetic alloy binder ratio on the magnetic properties of the composite magnet at 300 Mpa-60 min hot pressing is shown in table 4.
TABLE 4
Composite magnet numbering Magnetic alloy binder wt% Relative density/%) Coercive force/kOe Maximum magnetic energy product/MGOe
SHD-7 5 84 9.1 26.5
SHD-8 10 90 9.2 27.6
SHD-9 15 92 9.1 27.4
SHD-10 20 93 9.2 27.0
SHD-11 25 95 9.1 26.7
SHD-12 40 97 9.2 24.8
Example 5
With the impurity content of less than 1 wt% of metal PrNd (Pr) 20 Nd 80 ) Cu as a raw material in an atomic ratio (PrNd) 70 Cu 30 And (4) preparing materials for preparing low-melting-point diffusion source alloy powder. The metal raw materials are put into a crucible and are inductively smelted into a uniform melt. And pouring the melt onto a water-cooled copper roller, wherein the surface rotating speed of the copper roller is 30m/s, and preparing the quick-quenched thin belt. And grinding the rapidly quenched thin strip into powder with the particle diameter of 10-30 mu m by using an air flow mill. MQ-16-9HD quick-quenched magnetic powder (ingredient Nd10.6Fe82.1Zr0.9B6.4, magnetic property parameter: Br ═ 0.87T, (BH) from Magnus max 15.5 Hcj 9.4kOe) with a PdNdCu alloy powder in a ratio of 1 to 4 at% (as shown in table 5), uniformly mixed, and subjected to diffusion heat treatment in vacuum at a heat treatment temperature of 620 ℃ for 30 min. The rapidly quenched ribbon after diffusion heat treatment was tested for magnetic properties using PPMS. Table 5 shows the PrNdCu alloy content, the melting point of the rare earth-rich phase and the bonding in the mixed magnetic powderAnd (5) testing the coercive force and the maximum energy product of the agent magnetic powder.
TABLE 5
Binder numbering PrNdCu alloy content/at% Melting point/deg.C of rare earth-rich phase Coercive force/kOe Maximum magnetic energy product/MGOe
MQ-B 0 - 8.9 15.0
PN-2 1 516 9.6 14.9
PN-3 2 516 10.3 14.6
PN-4 3 516 12.4 14.3
PN-5 4 516 13.7 14.1
The rapidly quenched ribbon subjected to the diffusion heat treatment was ground into a fine powder having an average particle diameter of 3 μm using a jet mill powder-making apparatus. Sm in an average particle diameter of 3 mu m 2 Fe 17 N 3 Anisotropic magnetic powder is used as raw material magnetic powder, the coercive force of the magnetic powder is 10.2kOe, and the maximum magnetic energy product of the magnetic powder is 33.2 MGOe. Using the neodymium-iron-boron-based alloy powder (shown in table 5) obtained by the above preparation as a magnetic alloy binder, the volume ratio of the magnetic alloy binder to the magnetic powder is 20:80, and the raw material magnetic powder and the binder are loaded into a three-dimensional mixer and mixed uniformly under the protection of high-purity argon. And (3) performing orientation compression on the mixture in a magnetic field with the temperature of more than 20kOe to form a pressed blank, wherein the pressure loading direction is vertical to the magnetic field direction, and the pressure is 100 MPa. Transferring the compact to a pressure sintering furnace with a pressure loading direction perpendicular to the orientation direction at 3 x 10 -3 Heating to 480 ℃ in vacuum of Pa, loading 300Mpa of pressure, keeping the pressure for 60min, and pressing the pressed compact into a compact composite magnet. Table 6 shows the magnetic alloy binder and Sm 2 Fe 17 N 3 The relative density, coercive force and maximum magnetic energy product of the composite magnet prepared from the magnetic powder.
TABLE 6
Composite magnet numbering Magnetic alloy binder Relative density/%) Coercive force/kOe Maximum magnetic energy product/MGOe
SMQ-B MQ-B 88 9.1 26.5
SPN-2 PN-2 91 10.2 28.3
SPN-3 PN-3 92 10.4 28.8
SPN-4 PN-4 94 10.4 30.0
SPN-5 PN-5 95 10.5 30.6
Example 6
Metal Nd, Fe, M1, Cu and ferroboron with impurity content less than 1 wt% are used as raw materials, and are mixed according to a chemical formula shown in a table 7 and expressed by element proportion, and 1% of burning loss compensation is required to be added to rare earth Nd. The metal raw material is put into a crucible and is melted into a uniform melt by induction. Table 7 shows the components of the neodymium-iron-boron-based alloy binder, the melting point of the rare earth-rich phase, the coercive force of the magnetic powder of the binder, and the maximum magnetic energy product test table. And pouring the melt onto a water-cooled copper roller, wherein the surface rotating speed of the copper roller is 25 m/s. Namely, the alloy melt is rapidly quenched to prepare an amorphous or nanocrystalline rapidly quenched thin strip. And carrying out heat treatment on the thin strip in vacuum, wherein the heat treatment temperature is 630 ℃, and the heat treatment time is 15 min. The quenched ribbon was milled into a fine powder having an average particle diameter of 3 μm using an air jet mill. Sm in an average particle diameter of 3 mu m 2 The anisotropic magnetic powder of Fe17N3 was used as a raw material magnetic powder, the coercive force of the magnetic powder was 10.2kOe, and the maximum magnetic energy product of the magnetic powder was 36.9 MGOe. Neodymium-iron-boron-based alloy powder in table 7 is used as a magnetic alloy binder, the volume ratio of the magnetic alloy binder to the magnetic powder is 20:80, the raw material magnetic powder and the magnetic alloy binder are loaded into a three-dimensional mixer, and the raw material magnetic powder and the magnetic alloy binder are uniformly mixed under the protection of high-purity argon. And (3) performing orientation compression on the mixture in a magnetic field with the temperature of more than 20kOe to form a pressed blank, wherein the pressure loading direction is vertical to the magnetic field direction, and the pressure is 100 MPa. The compact was transferred to a pressure sintering furnace with the pressure loading direction perpendicular to the orientation direction at 3 x 10 -3 Heating to 480 ℃ in vacuum of Pa, loading 300Mpa of pressure, keeping the pressure for 60min, and pressing the pressed compact into a compact composite magnet. Table 8 shows the rapid quenching neodymium iron boron binder and Sm 2 Fe 17 N 3 And (3) a test data table of the relative density, the coercive force and the maximum magnetic energy product of the composite magnet prepared from the magnetic powder.
TABLE 7
Binder numbering Binder component Melting point of rare earth-rich phase Coercive force/kOe Maximum magnetic energy product/MGOe
N-1 Nd11.8FebalB5.9Cu0.2 /678 9.4 139
N-2 Nd12.5FebalB5.9Cu0.2 534 12.3 13.6
N-3 Nd13.2FebalB5.9Cu0.2 534 13.6 13.42
N-4 Nd13.9FebalB5.9Cu0.2 534 14.2 13.1
N-5 Nd12.5FebalB5.9Cu0.2Zr0.5 534 14.4 12.8
TABLE 8
Figure BDA0002964390960000131
Figure BDA0002964390960000141
As can be seen from Table 8.
Example 7
Reference example 1, the green compact was transferred into a pressure sintering furnace with the pressure loading direction perpendicular to the orientation direction at 3 x 10 -3 Heating to 400 ℃ in vacuum of Pa, loading pressure of 400Mpa, keeping the pressure for 10min, and pressing the pressed compact into a compact composite magnet.
Example 8
Reference example 1, the green compact was transferred into a pressure sintering furnace with the pressure loading direction perpendicular to the orientation direction at 3 x 10 -3 Heating to 600 ℃ in vacuum of Pa, loading pressure of 50Mpa, keeping the pressure for 360min, and pressing the pressed compact into a compact composite magnet.
The above embodiments are only for the purpose of helping understanding the technical solution of the present invention and the core idea thereof, and it should be noted that those skilled in the art can make several improvements and modifications to the present invention without departing from the principle of the present invention, and these improvements and modifications also fall within the protection scope of the claims of the present invention.

Claims (8)

1. A magnetic alloy binder is characterized in that the chemical formula expressed by atomic percentage is R x Fe 100-x-y-z- v M1 y M2 z B v The magnetic alloy binder according to (1), wherein,r is at least one of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y, 10.0<x<14.0; m1 is selected from at least one of Al, Co, Si, Zr, Hf, Ta, Nb, Ti, V, Cr, Mn, Ni, W and Mo, and y is more than or equal to 0 and less than or equal to 15.0; m2 is at least one of Cu and Ga, z is more than or equal to 0 and less than or equal to 8.0, and v is more than or equal to 3 and less than or equal to 10.0.
2. The magnetic alloy binder of claim 1 wherein the chemical formula expressed in atomic percent is R x Fe 100-x-y-z-v M1 y M2 z B v Wherein R is selected from one of La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y, 10.0<x<14.0; m1 is selected from one of Al, Co, Si, Zr, Hf, Ta, Nb, Ti, V, Cr, Mn, Ni, W and Mo, and y is more than or equal to 0 and less than or equal to 15.0; m2 is one of Cu and Ga, z is more than or equal to 0 and less than or equal to 8.0, and v is more than or equal to 3 and less than or equal to 10.0.
3. The magnetic alloy binder of claim 1 wherein the chemical formula expressed in atomic percent is R x Fe 100-x-y-z-v M1 y Cu z B v Wherein R is Pr and/or Nd, 11.8 ≦ x ≦ 13.9, M1 is one of Zr and Nb, y is 0.5 to 1.0, z is 0.2 to 1.6, and v is 5.5 to 5.9.
4. The preparation method of the composite rare earth permanent magnetic material is characterized by comprising the following steps: the chemical formula represented by atomic percent of claim 1 is R x Fe 100-x-y-z-v M1 y M2 z B v The magnetic alloy binder is prepared by binding raw material magnetic powder into a magnet, and the raw material magnetic powder is selected from Sm 2 Fe 17 N x 、Nd(Fe,M) 12 N x 、ThMn 12 Type Sm (Fe, M) 12 、SmCo 5 、Sm(Co,Fe,Zr,Cu)z、R 2 Fe 14 B single crystal, oriented polycrystalline HDDR-R 2 Fe 14 B, one or more rare earth transition metal compound magnetic powders, theSm (Co, Fe, Zr, Cu) z of (1) is 2:17 type Sm-Co, 5<z<8.5。
5. The method for preparing a composite rare earth permanent magnetic material according to claim 4, wherein the volume ratio of the raw material magnetic powder in the composite rare earth permanent magnetic material is 60-95%, and the volume ratio of the magnetic alloy binder is 5-40%.
6. The method for preparing a composite rare earth permanent magnetic material according to claim 5, wherein the volume ratio of the raw material magnetic powder in the composite rare earth permanent magnetic material is 80-90%, and the volume ratio of the magnetic alloy binder is 10-20%.
7. The preparation method of the composite rare earth permanent magnetic material according to claim 4, characterized by comprising the following steps: uniformly mixing raw material magnetic powder and a magnetic alloy binder under the protection of vacuum or inert gas, performing orientation compression in a magnetic field of more than 15kOe to form a pressed compact, transferring the pressed compact into a pressure sintering furnace, heating to 400-600 ℃ in vacuum or under the protection of inert gas, loading the pressure of 50-400MPa, keeping the pressure for 10-360min, and pressing the pressed compact into the composite rare earth permanent magnet material.
8. The composite rare earth permanent magnetic material prepared by the method for preparing a composite rare earth permanent magnetic material according to claim 4.
CN202110246844.4A 2021-03-05 2021-03-05 Magnetic alloy binder, composite rare earth permanent magnetic material and preparation method thereof Pending CN115020054A (en)

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