CN114220622A - Antioxidant composition, rare earth permanent magnet, sintered magnet material and preparation method - Google Patents

Antioxidant composition, rare earth permanent magnet, sintered magnet material and preparation method Download PDF

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Publication number
CN114220622A
CN114220622A CN202111414971.7A CN202111414971A CN114220622A CN 114220622 A CN114220622 A CN 114220622A CN 202111414971 A CN202111414971 A CN 202111414971A CN 114220622 A CN114220622 A CN 114220622A
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Prior art keywords
mas
mass
percentage
component
antioxidant composition
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CN202111414971.7A
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Chinese (zh)
Inventor
施尧
黄清芳
蓝琴
黄佳莹
欧阳福忠
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Fujian Changting Jinlong Rare Earth Co Ltd
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Xiamen Tungsten Co Ltd
Fujian Changting Jinlong Rare Earth Co Ltd
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Application filed by Xiamen Tungsten Co Ltd, Fujian Changting Jinlong Rare Earth Co Ltd filed Critical Xiamen Tungsten Co Ltd
Priority to CN202111414971.7A priority Critical patent/CN114220622A/en
Publication of CN114220622A publication Critical patent/CN114220622A/en
Priority to PCT/CN2022/129739 priority patent/WO2023093496A1/en
Priority to TW111144600A priority patent/TW202321364A/en
Pending legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/0555—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together
    • H01F1/0557—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 pressed, sintered or bonded together sintered
    • 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
    • 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
    • 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
    • B22F2009/042—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling using a particular milling fluid
    • 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

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

Abstract

The invention discloses an antioxidant composition, a rare earth permanent magnet, a sintered magnet material and a preparation method. The antioxidant composition comprises the following components: 30-60 mas% of poly-alpha-olefin; 10 to 30mas percent of butyl oleate; 1-20 mas% of fatty acid methyl ester; 10 to 40mas percent of solvent oil. The antioxidant composition can improve the dispersibility of powder and the milling efficiency in the process of preparing a permanent magnet, has excellent wetting property, can well wrap the magnetic powder, prevents oxygen and nitrogen from contacting the magnetic powder, plays a role in preventing oxidation and reduces the nitrogen content; meanwhile, on the premise of higher carbon content, higher remanence and coercive force of the sintered magnet and the rare earth permanent magnet can be ensured.

Description

Antioxidant composition, rare earth permanent magnet, sintered magnet material and preparation method
Technical Field
The invention relates to an antioxidant composition, a rare earth permanent magnet, a sintered magnet material and a preparation method thereof.
Background
The sintered neodymium-iron-boron magnet is a modern permanent magnet with the strongest magnetism, has excellent characteristics of high magnetic energy product, high cost performance and the like, is applied to the fields of aviation, aerospace, microwave communication technology, electronics, electroacoustic, electromechanics and the like, but the demand of people on the sintered neodymium-iron-boron magnet is increased along with the continuous expansion of the application range of the permanent magnet, and the higher demand is provided on the magnetic performance of the permanent magnet.
In the prior art, during the process of preparing the neodymium iron boron magnet material, a certain amount of lubricant or antioxidant is mixed in the air flow milling process or the forming process, namely a certain amount of carbon element is introduced, and the coercive force is reduced due to the high carbon content, so that the carbon content is generally controlled below 1050ppm by a person skilled in the art.
Therefore, there is a need for an appropriate antioxidant that can not only reduce the oxidation risk during the preparation of the ndfeb magnet material, but also maintain high magnetic performance on the premise that the introduced carbon content is high and the additional control of the carbon content is not required.
Disclosure of Invention
The invention aims to overcome the defects that carbon is introduced into a rare earth magnet by a traditional antioxidant in the prior art, so that the carbon content is high and the coercive force is reduced, and provides an antioxidant composition, a rare earth permanent magnet, a sintered magnet material and a preparation method thereof. The antioxidant composition can reduce the oxidation risk in the preparation process of the rare earth magnet material, and can still maintain higher magnetic performance on the premise of higher introduced carbon content and no need of additional control of the carbon content.
The invention solves the technical problems by the following scheme:
the invention provides an antioxidant composition, which comprises the following components in percentage by mass:
30-60 mas% of poly-alpha-olefin;
10 to 30mas percent of butyl oleate;
1-20 mas% of fatty acid methyl ester;
10 to 40mas percent of solvent oil;
mas% means the mass percentage of each component in the antioxidant composition.
In the antioxidant composition, the four components are respectively poly-alpha-olefin with good stability and wettability, and can cover and wrap the powder to isolate other gases from directly contacting the powder; the surfactant fatty acid methyl ester modified for the solution enables other solutions to have better affinity with the powder and enables the powder to have better dispersibility; the butyl oleate which has a lubricating effect on the powder is beneficial to the flow and rotation of the powder; the solvent oil is used as a solvent of the three organic matters and has the characteristics of easy volatilization and easy removal.
In the present invention, the content of the poly-alpha-olefin is preferably 30 to 45 mas%, for example 40 mas%, which means the mass percentage of each component in the antioxidant composition.
In the invention, the content of the butyl oleate is preferably 10-20 mas%, and mas% refers to the mass percentage of each component in the antioxidant composition.
In the present invention, the content of the fatty acid methyl ester is preferably 1 to 15 mas%, for example, 5 or 10 mas%, and mas% means the mass percentage of each component in the antioxidant composition.
In the invention, the solvent oil can be 90# solvent oil or 120# solvent oil.
In the present invention, the content of the solvent oil is preferably 10 to 30 mas%, for example, 20 or 25 mas%, and mas% means the mass percentage of each component in the antioxidant composition.
In a preferred embodiment of the invention, the antioxidant composition comprises the following components in percentage by mass: poly-alpha-olefin 40 mas%; 20 mas% of butyl oleate; fatty acid methyl ester 10 mas%; 30 mas% of solvent oil. In a preferred embodiment of the present invention, preferably, the antioxidant composition comprises the following components by mass percent: polyalphaolefin 60 mas%; 20 mas% of butyl oleate; fatty acid methyl ester 10 mas%; 10 mas% of solvent oil.
In a preferred embodiment of the present invention, preferably, the antioxidant composition comprises the following components by mass percent: poly-alpha-olefin 40 mas%; 10 mas% of butyl oleate; fatty acid methyl ester 10 mas%; solvent oil 40 mas%.
In a preferred embodiment of the present invention, preferably, the antioxidant composition comprises the following components by mass percent: poly-alpha-olefin 40 mas%; 20 mas% of butyl oleate; 15 mas% of fatty acid methyl ester; 25 mas% of solvent oil.
In a preferred embodiment of the present invention, preferably, the antioxidant composition comprises the following components by mass percent: 30 mas% of polyalphaolefin; butyl oleate 30 mas%; fatty acid methyl ester 20 mas%; 20 mas% of solvent oil.
In a preferred embodiment of the present invention, preferably, the antioxidant composition comprises the following components by mass percent: polyalphaolefin 45 mas%; 20 mas% of butyl oleate; fatty acid methyl ester 5 mas%; 30 mas% of solvent oil.
The invention also provides a preparation method of the antioxidant composition, which comprises the following steps: mixing the above components.
The invention also provides an application of the antioxidant composition as an antioxidant in preparation of a permanent magnet.
The invention provides a material for sintered magnets, which comprises the antioxidant composition.
In the present invention, the content of the antioxidant composition is preferably 0.15 to 0.45 mass%, for example, 0.2 or 0.4 mass%, and the mass% is the mass percentage of each component in the sintered magnet material.
In the present invention, the material for sintered magnets generally further includes a rare earth element R. The content of R is preferably 29 to 33 mas%, more preferably 29.5 to 32 mas%, for example 31 mas%, and mas% is the mass percentage of each component in the material for sintered magnet.
Wherein, preferably, the R comprises PrNd and/or Nd. Preferably, the R also comprises a heavy rare earth element RH. The RH preferably includes one or more of Tb, Dy, Ho and Gd. Preferably, the RH content is 0 to 2.5 mas% and is not 0, for example, 1.5 mas%, and mas% is a mass percentage of each component in the material for sintered magnet.
In the present invention, the material for sintered magnets preferably further includes B (boron). The content of B is preferably 0.86 to 1 mas%, for example, 0.99, 0.88 or 0.95 mas%, and mas% is the mass percentage of each component in the sintered magnet material.
In the present invention, the material for a sintered magnet preferably further includes Ga (gallium). The content of Ga is preferably 0 to 0.7 mas% and is not 0, for example, 0.05, 0.5 or 0.25 mas%, and mas% is the mass percentage of each component in the sintered magnet material.
In the present invention, the material for a sintered magnet preferably further includes Cu (copper). The content of Cu is preferably 0 to 0.5 mas% and is not 0, for example, 0.36, 0.4 or 0.16 mas%, and mas% is the mass percentage of each component in the sintered magnet material.
In the present invention, the material for sintered magnets preferably further includes M containing at least one of Ti, Zr, and Nb. The content of M is preferably 0 to 0.4 mas% and is not 0, for example, 0.2, 0.28 or 0.3 mas%, and mas% is the mass percentage of each component in the sintered magnet material.
When the M includes Nb, the content of Nb is preferably 0 to 0.1 mas% and is not 0, and mas% is a mass percentage of each component in the material for sintered magnets.
When M includes Ti, the content of Ti is preferably 0 to 0.2 mass% and is not 0, for example, 0.18 mass%, and mass% is a mass percentage of each component in the material for a sintered magnet.
When the M includes Zr, the Zr content is preferably 0 to 0.3 mas% and is not 0, and mas% is the mass percentage of each component in the material for sintered magnet.
In the present invention, the material for a sintered magnet preferably further includes Co (cobalt). The content of Co is preferably 0 to 2 mas%, more preferably 0 to 1.5 mas%, for example 0.5 or 1 mas%, and mas% is the mass percentage of each component in the sintered magnet material.
In the present invention, the material for sintered magnets preferably further includes Al (aluminum). The content of Al is preferably 0 to 0.5 mas%, for example, 0.3 mas%, and mas% is the mass percentage of each component in the material for sintered magnets.
In the present invention, the material for sintered magnets generally further contains Fe (iron). The content of Fe is preferably 64-70 mas%.
In a preferred embodiment of the present invention, the material for sintered magnets comprises, by mass: nd29.5 mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, antioxidant composition 0.2 mas%, and the balance of iron; wherein the antioxidant composition consists of the following components: poly-alpha-olefin 40 mas%; 20 mas% of butyl oleate; fatty acid methyl ester 10 mas%; 30 mas% of solvent oil, wherein the mass% of each component accounts for the mass percent of the antioxidant composition.
In a preferred embodiment of the present invention, the material for sintered magnets comprises, by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, antioxidant composition 0.2 mas%, and the balance of iron; wherein the antioxidant composition consists of the following components: polyalphaolefin 60 mas%; 20 mas% of butyl oleate; fatty acid methyl ester 10 mas%; 10 mas% of solvent oil, wherein the mass% of each component accounts for the mass percent of the antioxidant composition.
In a preferred embodiment of the present invention, the material for sintered magnets comprises, by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, antioxidant composition 0.2 mas%, and the balance of iron; wherein the antioxidant composition consists of the following components: poly-alpha-olefin 40 mas%; 10 mas% of butyl oleate; fatty acid methyl ester 10 mas%; 40 mas% of solvent oil, wherein the mass% of each component accounts for the mass percent of the antioxidant composition.
In a preferred embodiment of the present invention, the material for sintered magnets comprises, by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, antioxidant composition 0.2 mas%, and the balance of iron; wherein the antioxidant composition consists of the following components: poly-alpha-olefin 40 mas%; 20 mas% of butyl oleate; 15 mas% of fatty acid methyl ester; 25 mas% of solvent oil, wherein the mass% of each component accounts for the mass percent of the antioxidant composition.
In a preferred embodiment of the present invention, the material for sintered magnets comprises, by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, antioxidant composition 0.2 mas%, and the balance of iron; wherein the antioxidant composition consists of the following components: 30 mas% of polyalphaolefin; butyl oleate 30 mas%; fatty acid methyl ester 20 mas%; 20 mas% of solvent oil, wherein the mass% of each component accounts for the mass percent of the antioxidant composition.
In a preferred embodiment of the present invention, the material for sintered magnets comprises, by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, antioxidant composition 0.2 mas%, and the balance of iron; wherein the antioxidant composition consists of the following components: polyalphaolefin 45 mas%; 20 mas% of butyl oleate; fatty acid methyl ester 5 mas%; 30 mas% of solvent oil, wherein the mass% of each component accounts for the mass percent of the antioxidant composition.
In a preferred embodiment of the present invention, the material for sintered magnets comprises, by mass: PrNd31 mas%, Co0.5mas%, Cu0.4mas%, Ga0.5mas%, Ti0.2mas%, B0.88mas%, antioxidant composition 0.2 mas%, and the balance of iron; wherein the antioxidant composition consists of the following components: poly-alpha-olefin 40 mas%; 20 mas% of butyl oleate; fatty acid methyl ester 10 mas%; 30 mas% of solvent oil, wherein the mass% of each component accounts for the mass percent of the antioxidant composition.
In a preferred embodiment of the present invention, the material for sintered magnets comprises, by mass: PrNd29.5mas%, Dy2.5mas%, Co1.5mas%, Cu0.16mas%, Ga0.25mas%, Al0.3mas%, Zr0.3mas%, B0.95mas%, antioxidant composition 0.2 mas%, and the balance of iron; wherein the antioxidant composition consists of the following components: poly-alpha-olefin 40 mas%; 20 mas% of butyl oleate; fatty acid methyl ester 10 mas%; 30 mas% of solvent oil, wherein the mass% of each component accounts for the mass percent of the antioxidant composition.
In a preferred embodiment of the present invention, the material for sintered magnets comprises, by mass: PrNd31 mas%, Co0.5mas%, Cu0.4mas%, Ga0.5mas%, Ti0.2mas%, B0.88mas%, antioxidant composition 0.4 mas%, and the balance of iron; wherein the antioxidant composition consists of the following components: poly-alpha-olefin 40 mas%; 20 mas% of butyl oleate; fatty acid methyl ester 10 mas%; 30 mas% of solvent oil, wherein the mass% of each component accounts for the mass percent of the antioxidant composition.
The invention also provides a sintered magnet, which comprises the following components in percentage by mass:
r: 29-33 mas percent, wherein R is rare earth element;
B：0.86mas％～1mas％；
ga: 0 to 0.7 mas%, and not 0;
cu: 0 to 0.5 mas% and not 0;
m: 0 to 0.4 mas%, and not 0; the M comprises at least one of Ti, Zr and Nb;
al: 0 to 0.5 mas% and not 0;
Fe：64mas％～70mas％；
C：0.1～0.2mas％；
co: 0-2 mas%; and mas% is the mass percentage of each component in the sintered magnet.
In the present invention, preferably, the R includes PrNd and/or Nd. Wherein, preferably, the R also comprises heavy rare earth element RH. Preferably, the RH includes one or more of Tb, Dy, Ho and Gd. Preferably, the RH content is 0 to 2.5 mas% and is not 0, for example, 1.5 mas%, and mas% is a mass percentage of each component in the sintered magnet.
In the present invention, preferably, the content of R is 29.5 to 32 mas%, for example, 31 mas%, where mas% is a mass percentage of each component in the sintered magnet.
In the present invention, the content of B is preferably 0.86 to 0.99 mass%, for example, 0.88 mass% or 0.95 mass%, and the mass% is the mass percentage of each component in the sintered magnet.
In the present invention, the Ga content is preferably 0 to 0.5 mas%, and is not 0, for example, 0.05 or 0.25 mas%, and mas% is the mass percentage of each component in the sintered magnet.
In the present invention, the content of Cu is preferably 0 to 0.4 mas%, and is not 0, for example, 0.36 mas% or 0.16 mas%, and mas% is the mass percentage of each component in the sintered magnet.
In the present invention, the content of M is preferably 0 to 0.3 mas%, and is not 0, for example, 0.2 mas% or 0.28 mas%, and mas% is the mass percentage of each component in the sintered magnet.
When the M includes Nb, the content of Nb is preferably 0 to 0.1 mas% and is not 0, and mas% is a mass percentage of each component in the sintered magnet.
When M includes Ti, the content of Ti is preferably 0 to 0.2 mass% and is not 0, for example, 0.18 mass%, and mass% is a mass percentage of each component in the sintered magnet.
When the M includes Zr, the content of Zr is preferably 0 to 0.3 mas% and is not 0, and mas% is a mass percentage of each component in the sintered magnet.
In the present invention, preferably, the content of Co is 0 to 1.5 mas%, for example, 0.5 or 1 mas%, and mas% is the mass percentage of each component in the sintered magnet.
In the present invention, preferably, the content of Al is 0 to 0.3 mas% and is not 0, and mas% is a mass percentage of each component in the sintered magnet.
In the present invention, preferably, the content of C is 0.1126 mas%, 0.1378 mas%, 0.109 mas%, 0.117 mas%, 0.1209 mas%, 0.1140 mas%, 0.1165 mas%, 0.1178 mas%, or 0.1255 mas%, and mas% is the mass percentage of each component in the sintered magnet.
In the present invention, the sintered magnet generally further includes Fe (iron). The content of Fe is preferably 64-70 mas%.
In a preferred embodiment of the present invention, the sintered magnet is composed of, by mass: nd29.5 mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, and C0.1126 mas%, with the balance being iron.
In a preferred embodiment of the present invention, the sintered magnet is composed of, by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, C0.1378mas%, and the balance iron.
In a preferred embodiment of the present invention, the sintered magnet is composed of, by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, C0.109mas%, and the balance being iron.
In a preferred embodiment of the present invention, the sintered magnet is composed of, by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, C0.117mas%, and the balance being iron.
In a preferred embodiment of the present invention, the sintered magnet is composed of, by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, C0.1209mas%, and the balance of iron.
In a preferred embodiment of the present invention, the sintered magnet is composed of, by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, C0.114mas%, and the balance iron.
In a preferred embodiment of the present invention, the sintered magnet is composed of, by mass: PrNd31 mas%, Co0.5mas%, Cu0.4mas%, Ga0.5mas%, Ti0.2mas%, B0.88mas%, C0.1165mas%, and the balance of iron.
In a preferred embodiment of the present invention, the sintered magnet is composed of, by mass: PrNd29.5mas%, Dy2.5mas%, Co1.5mas%, Cu0.16mas%, Ga0.25mas%, Al0.3mas%, Zr0.3mas%, B0.95mas%, and C0.1178mas%, with the balance being iron.
In a preferred embodiment of the present invention, the sintered magnet is composed of, by mass: PrNd31 mas%, Co0.5mas%, Cu0.4mas%, Ga0.5mas%, Ti0.2mas%, B0.88mas%, C0.1255mas%, and the balance being iron.
The invention also provides a rare earth permanent magnet which comprises the following components in percentage by mass:
r: 29 to 33mas percent; r is a rare earth element and comprises a heavy rare earth element RH;
B：0.86mas％～1mas％；
ga: 0 to 0.7 mas%, and not 0;
cu: 0 to 0.5 mas% and not 0;
m: 0 to 0.4 mas%, and not 0; the M comprises at least one of Ti, Zr and Nb;
al: 0 to 0.5 mas% and not 0;
Fe：64mas％～70mas％；
C：0.1～0.2mas％；
co: 0-2 mas%; and mas percent is the mass percentage of each component in the rare earth permanent magnet.
In the present invention, preferably, the R includes PrNd and/or Nd.
In the present invention, preferably, the content of R is 29.5 to 32 mas%, for example, 31 or 30 mas%, and mas% is the mass percentage of each component in the rare earth permanent magnet.
In the present invention, the RH preferably includes one or more of Tb, Dy, Ho and Gd, and more preferably includes Dy and/or Tb.
In the invention, preferably, the content of RH is 0 to 2.5 mas%, and is not 0, for example, 1.5 mas% or 0.5 mas%, and mas% is the mass percentage of each component in the rare earth permanent magnet.
In the present invention, preferably, the content of B is 0.86 to 0.99 mas%, for example, 0.88 or 0.95 mas%, and mas% is the mass percentage of each component in the rare earth permanent magnet.
In the present invention, preferably, the Ga content is 0 to 0.5 mas%, and is not 0, for example, 0.05 or 0.25 mas%, and mas% is the mass percentage of each component in the rare earth permanent magnet.
In the present invention, preferably, the content of Cu is 0 to 0.4 mas%, and is not 0, for example, 0.36 mas% or 0.16 mas%, and mas% is the mass percentage of each component in the rare earth permanent magnet.
In the invention, the content of M is preferably 0-0.3 mas%, and is not 0, for example, 0.2 mas% or 0.28 mas%, and mas% is the mass percentage of each component in the rare earth permanent magnet.
When the M comprises Nb, the content of Nb is preferably 0-0.1 mas% and is not 0, and mas% is the mass percentage of each component in the rare earth permanent magnet.
When the M comprises Ti, the content of Ti is preferably 0-0.2 mas% and is not 0, such as 0.18 mas%, and mas% is the mass percentage of each component in the rare earth permanent magnet.
When the M comprises Zr, the content of Zr is preferably 0-0.3 mas% and is not 0, and mas% is the mass percentage of each component in the rare earth permanent magnet.
In the invention, preferably, the content of Co is 0 to 1.5 mas%, for example, 0.5 or 1 mas%, and mas% is the mass percentage of each component in the rare earth permanent magnet.
In the invention, preferably, the content of Al is 0-0.3 mas% and is not 0, and the mas% is the mass percentage of each component in the rare earth permanent magnet.
In the invention, preferably, the content of C is 0.115 mas%, 0.1392 mas%, 0.111 mas%, 0.1195 mas%, 0.1225 mas%, 0.1165 mas%, 0.1165 mas%, 0.1178 mas% or 0.1255 mas%, and the mas% is the mass percentage of each component in the rare earth permanent magnet.
In the present invention, the rare earth permanent magnet generally further includes Fe (iron). The content of Fe is preferably 64-70 mas%.
In a preferred embodiment of the invention, the rare earth permanent magnet consists of the following components in percentage by mass: nd29.5 mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, Tb0.5mas%, and C0.115mas%, with the balance being iron.
In a preferred embodiment of the invention, the rare earth permanent magnet consists of the following components in percentage by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, Tb0.5mas%, and C0.1392mas%, with the balance being iron.
In a preferred embodiment of the invention, the rare earth permanent magnet consists of the following components in percentage by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, Tb0.5mas%, and C0.111mas%, with the balance being iron.
In a preferred embodiment of the invention, the rare earth permanent magnet consists of the following components in percentage by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, Tb0.5mas%, and C0.1195mas%, with the balance being iron.
In a preferred embodiment of the invention, the rare earth permanent magnet consists of the following components in percentage by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, Tb0.5mas%, and C0.1225mas%, with the balance being iron.
In a preferred embodiment of the invention, the rare earth permanent magnet consists of the following components in percentage by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, Tb0.5mas%, and C0.1165mas%, with the balance being iron.
In a preferred embodiment of the invention, the rare earth permanent magnet consists of the following components in percentage by mass: PrNd31 mas%, Co0.5mas%, Cu0.4mas%, Ga0.5mas%, Ti0.2mas%, B0.88mas%, C0.1165mas%, and the balance of iron.
In a preferred embodiment of the invention, the rare earth permanent magnet consists of the following components in percentage by mass: PrNd29.5mas%, Dy2.5mas%, Co1.5mas%, Cu0.16mas%, Ga0.25mas%, Al0.3mas%, Zr0.3mas%, B0.95mas%, and C0.1178mas%, with the balance being iron.
In a preferred embodiment of the invention, the rare earth permanent magnet consists of the following components in percentage by mass: PrNd31 mas%, Co0.5mas%, Cu0.4mas%, Ga0.5mas%, Ti0.2mas%, B0.88mas%, C0.1255mas%, and the balance being iron.
The invention also provides a preparation method of the sintered magnet, which comprises the following steps:
melting and coarsely crushing the components except the antioxidant composition in the material for the sintered magnet to obtain coarse powder; then finely crushing the mixture of the coarse powder and the antioxidant composition with the dosage of 40-60% to obtain fine powder; and then molding and sintering the mixture of the fine powder and the rest of the antioxidant composition.
In the invention, the smelting operation and conditions can be conventional smelting process in the field, and generally, the smelting casting is carried out by an ingot casting process or a rapid hardening sheet process to obtain alloy sheets.
In the invention, the smelting temperature can be 1300-1700 ℃, for example 1500 ℃.
In the invention, the smelting equipment is generally a high-frequency vacuum smelting furnace and/or a medium-frequency vacuum smelting furnace. The medium-frequency vacuum smelting furnace can be a medium-frequency vacuum induction rapid hardening melt-spun furnace.
As known to those skilled in the art, rare earth elements are usually lost in the melting and sintering processes, in order to ensure the quality of a final product, 0 to 0.3 wt% of a rare earth element (generally Nd element) is generally additionally added to the formula of a raw material composition in the melting process, wherein the percentage is the mass percentage of the additionally added rare earth element in the material for the sintered magnet; in addition, the content of the additionally added rare earth elements is not included in the category of the raw material composition.
In the present invention, the rough crushing is generally hydrogen crushing.
Wherein the hydrogen fragmentation generally comprises hydrogen absorption, dehydrogenation and cooling treatment. The temperature of the hydrogen absorption is generally 20 to 200 ℃, preferably 20 to 40 ℃ (i.e. room temperature). The pressure of the hydrogen absorption is generally 50 to 600kPa, for example 90 kPa. The dehydrogenation temperature is generally 400 to 650 ℃, for example 550 ℃.
In the present invention, the fine pulverization is generally a jet milling powder. The gas flow in the gas flow milled powder can be, for example, nitrogen and/or argon. The pressure of the airflow milled powder is generally 0.1-2 MPa, preferably 0.5-0.7 MPa, such as 0.65 MPa. The efficiency of the jet milled powder may vary depending on the equipment, and may be, for example, 30 to 400kg/h, preferably 200 kg/h.
In the present invention, the molding operation and conditions may be molding processes conventional in the art, such as a magnetic field molding process. The magnetic field intensity of the magnetic field forming method is generally 1.5T or more.
In the present invention, the sintering operation and conditions may be sintering processes conventional in the art, such as a vacuum sintering process and/or an inert atmosphere sintering process. The vacuum sintering process or the inert atmosphere sintering process are all conventional operations in the field. When an inert atmosphere sintering process is used, the sintering initiation stage may be performed under a vacuum of less than 0.5 Pa. The inert gas atmosphere may be an atmosphere containing an inert gas, which is conventional in the art, and is not limited to helium, argon, but may also be nitrogen.
In the invention, the sintering temperature can be 1000-1200 ℃, and preferably 1030-1090 ℃.
In the invention, the sintering time can be 0.5-10 h, preferably 2-8 h.
The invention also provides a sintered magnet prepared by the preparation method of the sintered magnet.
The invention also provides a preparation method of the rare earth permanent magnet, which comprises the following steps: the sintered magnet is prepared by one of the following two methods:
the first method is as follows: sequentially carrying out primary aging treatment and secondary aging treatment;
the second method comprises the following steps: sequentially carrying out grain boundary diffusion treatment and secondary aging treatment.
In the present invention, the heavy rare earth element in the grain boundary diffusion treatment preferably includes Tb and/or Dy.
In the present invention, the grain boundary diffusion treatment may be performed by a conventional technique in the art, for example, by depositing, coating, or sputtering a Tb-containing substance or a Dy-containing substance on the surface of the sintered magnet, and performing diffusion heat treatment.
Wherein, the substance containing Tb or Dy can be Tb or Dy metal, Tb or Dy containing compound or alloy.
Wherein the temperature of the grain boundary diffusion treatment can be 800-900 ℃, for example 850 ℃.
The time of the grain boundary diffusion treatment can be 12-48 h, such as 24 h.
In the present invention, the temperature of the primary aging treatment is preferably 880 ℃ to 920 ℃, for example 900 ℃.
The time of the primary ageing is preferably 2h to 4h, for example 2 h.
In the present invention, the temperature of the secondary aging treatment is preferably 460 to 520 ℃, for example 490 ℃.
The time of the secondary ageing is preferably 2h to 4h, for example 2 h.
The invention also provides a rare earth permanent magnet prepared by the preparation method.
The invention also provides an application of the sintered magnet and/or the rare earth permanent magnet as a permanent magnet motor rotor.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: the antioxidant composition can improve the dispersibility of powder and the milling efficiency, has good bonding property between functional groups carried by organic matters in the antioxidant composition and NdFeB, has excellent wetting property, can well wrap magnetic powder, prevents oxygen and nitrogen from contacting the magnetic powder, plays a role in preventing oxidation and reduces the nitrogen content; meanwhile, on the premise of higher carbon content, the sintered magnet and the rare earth permanent magnet still keep higher remanence and coercive force.
Drawings
FIG. 1 is an EPMA diagram of a rare earth permanent magnet in example 1.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
Examples 1 to 6 and comparative example 1
(1) And (3) smelting: according to the formula shown in table 1 and table 2, the raw materials except the antioxidant composition (the formula of the antioxidant composition is shown in table 2) are prepared, vacuum melting is carried out in a high-frequency vacuum melting furnace at 1500 ℃, argon is introduced into a medium-frequency vacuum induction rapid hardening melt-spun furnace, casting is carried out, and the alloy is rapidly cooled to obtain the alloy sheet.
(2) The coarse crushing process: placing the alloy sheet in a hydrogen breaking furnace, vacuumizing the hydrogen breaking furnace in which the quenching alloy is placed at room temperature, introducing hydrogen with the purity of 99.9% into the hydrogen breaking furnace, maintaining the pressure of the hydrogen at 90kPa, fully absorbing the hydrogen, raising the temperature while vacuumizing, fully dehydrogenating, cooling, and taking out the powder after hydrogen breaking and crushing. Wherein the temperature for hydrogen absorption is room temperature, and the temperature for dehydrogenation is 550 ℃.
(3) Fine crushing: a mixture of the hydrogen-milled powder and 50% of the antioxidant composition was subjected to jet milling (the efficiency of jet milling may vary depending on the equipment, and may be, for example, 200kg/h) under a nitrogen atmosphere at a pressure of 0.65MPa in the milling chamber to obtain a fine powder.
(4) And (3) forming: mixing the powder after air flow milling with the rest antioxidant composition, and press-molding in a magnetic field strength of 1.5T or more to obtain a molded body.
(5) And (3) sintering: and (3) carrying each molded body to a sintering furnace for sintering, and sintering for 8h at the temperature of 1030-1090 ℃ under the vacuum condition of less than 0.5Pa to obtain the sintered magnet.
(6) Grain boundary diffusion and aging treatment: and (2) purifying the surface of the sintered magnet, coating Tb alloy containing 0.5 mas% of Tb on the surface of the sintered magnet, diffusing at 850 ℃ for 24h, cooling to room temperature, and performing vacuum heat treatment at 490 ℃ for 2h to obtain the rare earth permanent magnet.
TABLE 1 sintered magnet Material (mas%)
Figure BDA0003375519600000151
Note: in the above table, "/" indicates that the element is not contained
TABLE 2
Figure BDA0003375519600000152
Figure BDA0003375519600000161
Examples 7 to 9 and comparative examples 2 to 3
The preparation method is different from the preparation methods of examples 1 to 6 and comparative example 1 only in that the step (6) is as follows:
(6) and (3) aging treatment process: and (3) carrying out vacuum heat treatment on the sintered magnet for 2h at 900 ℃, and then carrying out vacuum heat treatment for 2h at 490 ℃ to obtain the rare earth permanent magnet.
Effects of the embodiment
The sintered magnets and rare earth permanent magnets of examples 1 to 9 and comparative examples 1 to 3 were each measured for magnetic properties and components.
(1) Each component of the sintered magnets and the rare earth permanent magnets of examples 1 to 9 and comparative examples 1 to 3 was measured using a high-frequency inductively coupled plasma emission spectrometer (ICP-OES, Icap 6300); the following tables 3 and 4 show the results of component detection.
TABLE 3 sintered magnet (mas%)
Numbering Nd PrNd Dy Co Cu Ga Al Nb Ti Zr B Fe C/ppm
Example 1 29.5 / / / 0.36 0.05 / 0.10 0.18 / 0.99 Bal. 1126
Example 2 29.5 / / / 0.36 0.05 / 0.10 0.18 / 0.99 Bal. 1378
Example 3 29.5 / / / 0.36 0.05 / 0.10 0.18 / 0.99 Bal. 1090
Example 4 29.5 / / / 0.36 0.05 / 0.10 0.18 / 0.99 Bal. 1170
Example 5 29.5 / / / 0.36 0.05 / 0.10 0.18 / 0.99 Bal. 1209
Example 6 29.5 / / / 0.36 0.05 / 0.10 0.18 / 0.99 Bal. 1140
Example 7 / 31 / 0.5 0.4 0.5 / / 0.2 / 0.88 Bal. 1165
Example 8 / 29.5 2.5 1.5 0.16 0.25 0.3 / / 0.3 0.95 Bal. 1178
Example 9 / 31 / 0.5 0.4 0.5 / / 0.2 / 0.88 Bal. 1255
Comparative example 1 29.5 / / / 0.36 0.05 / 0.10 0.18 / 0.99 Bal. 873
Comparative example 2 / 31 / 0.5 0.4 0.5 / / 0.2 / 0.88 Bal. 845
Comparative example 3 / 29.5 2.5 1.5 0.16 0.25 0.3 / / 0.3 0.95 Bal. 880
Note: in the above table, "/" indicates that the element is not contained
TABLE 4 rare earth permanent magnet (mas%)
Figure BDA0003375519600000162
Figure BDA0003375519600000171
Note: in the above table, "/" indicates that the element is not contained
(2) Evaluation of magnetic Properties: the sintered magnets and the rare earth permanent magnets of examples 1 to 9 and comparative examples 1 to 3 were subjected to magnetic property detection using a PFM-14 magnetic property measuring instrument of Hirst, UK; the following Table 5 shows the results of magnetic property measurements.
As can be seen from table 5, the oxygen content in the examples is equivalent to the comparative example, which shows that the antioxidant effect of the antioxidant composition of the present application is equivalent to that of the existing antioxidant; meanwhile, the nitrogen content in the embodiment is obviously reduced to more than 100 ppm from about 400ppm, because the nitrogen in the magnet is mainly introduced from the powder of the jet mill, the working gas of the jet mill is nitrogen (if the working gas is argon when the powder is milled by the jet mill, the nitrogen cannot appear), and the instantaneous temperature is higher when the air flow drives the coarse powder to mutually collide, so that the magnetic powder is combined with the nitrogen; and although the carbon content in the embodiment is higher, the sintered magnet and the rare earth permanent magnet still keep higher remanence and coercive force.
TABLE 5 evaluation of magnetic Properties
Figure BDA0003375519600000172
Figure BDA0003375519600000181
Note: in the above table, "/" indicates that the element is not contained
(3) Determination of microstructure: according to EPMA-1720 testing of the rare earth permanent magnet (as shown in FIG. 1) of example 1, as can be seen from FIG. 1, C is mainly distributed at grain boundary trigeminal boundaries, and part of the positions coincide with O to form rare earth oxide, but there is no coincidence, and C coincides with the distribution position of rare earth to form rare earth carbide.

Claims (10)

1. The antioxidant composition is characterized by comprising the following components in percentage by mass:
30-60 mas% of poly-alpha-olefin;
10 to 30mas percent of butyl oleate;
1-20 mas% of fatty acid methyl ester;
10 to 40mas percent of solvent oil;
mas% means the mass percentage of each component in the antioxidant composition.
2. The antioxidant composition of claim 1, wherein the polyalphaolefin is present at 30 to 45, such as 40, mas% referring to the mass percent of each component of the antioxidant composition;
and/or the content of the butyl oleate is 10 to 20mas, and mas refers to the mass percentage of each component in the antioxidant composition;
and/or the content of the fatty acid methyl ester is 1 to 15mas percent, such as 5 or 10mas percent, wherein mas percent refers to the mass percentage of each component in the antioxidant composition;
and/or the solvent oil is 90# solvent oil or 120# solvent oil;
and/or the content of the solvent oil is 10 to 30 mas%, such as 20 or 25 mas%, and mas% refers to the mass percentage of each component in the antioxidant composition;
or, the antioxidant composition comprises the following components in percentage by mass: poly-alpha-olefin 40 mas%; 20 mas% of butyl oleate; fatty acid methyl ester 10 mas%; 30 mas% of solvent oil;
or, the antioxidant composition comprises the following components in percentage by mass: polyalphaolefin 60 mas%; 20 mas% of butyl oleate; fatty acid methyl ester 10 mas%; 10 mas% of solvent oil;
or, the antioxidant composition comprises the following components in percentage by mass: poly-alpha-olefin 40 mas%; 10 mas% of butyl oleate; fatty acid methyl ester 10 mas%; 40 mas% of solvent oil;
or, the antioxidant composition comprises the following components in percentage by mass: poly-alpha-olefin 40 mas%; 20 mas% of butyl oleate; 15 mas% of fatty acid methyl ester; 25 mas% of solvent oil;
or, the antioxidant composition comprises the following components in percentage by mass: 30 mas% of polyalphaolefin; butyl oleate 30 mas%; fatty acid methyl ester 20 mas%; 20 mas% of solvent oil;
or, the antioxidant composition comprises the following components in percentage by mass: polyalphaolefin 45 mas%; 20 mas% of butyl oleate; fatty acid methyl ester 5 mas%; 30 mas% of solvent oil.
3. Use of the antioxidant composition of claim 1 or 2 as an antioxidant in the preparation of permanent magnets.
4. A material for sintered magnets, comprising the antioxidant composition as set forth in claim 1 or 2;
the content of the antioxidant composition is preferably 0.15 to 0.45 mas%, for example 0.2 or 0.4 mas%, and mas% is the mass percentage of each component in the sintered magnet material;
the material for a sintered magnet preferably further includes a rare earth element R; the content of R is preferably 29 to 33 mas%, more preferably 29.5 to 32 mas%, for example 31 mas%, and mas% is the mass percentage of each component in the material for sintered magnet;
the R preferably comprises PrNd and/or Nd; more preferably, R further comprises a heavy rare earth element RH; the RH preferably includes one or more of Tb, Dy, Ho, and Gd; preferably, the RH content is 0 to 2.5 mas% and is not 0, for example, 1.5 mas%, and mas% is a mass percentage of each component in the material for sintered magnet;
preferably, the material for sintered magnets further includes B; the content of B is preferably 0.86 to 1 mas%, for example, 0.99, 0.88 or 0.95 mas%, and mas% is the mass percentage of each component in the sintered magnet material;
preferably, the material for sintered magnets further includes Ga; the content of Ga is preferably 0 to 0.7 mas% and is not 0, for example, 0.05, 0.5 or 0.25 mas%, and mas% is the mass percentage of each component in the sintered magnet material;
preferably, the material for sintered magnets further includes Cu; the content of Cu is preferably 0 to 0.5 mas% and is not 0, for example, 0.36, 0.4 or 0.16 mas%, and mas% is the mass percentage of each component in the sintered magnet material;
preferably, the material for sintered magnets further includes M containing at least one of Ti, Zr, and Nb; the content of M is preferably 0 to 0.4 mas% and is not 0, for example, 0.2, 0.28 or 0.3 mas%, and mas% is the mass percentage of each component in the sintered magnet material;
wherein, when the M comprises Nb, the content of Nb is preferably 0-0.1 mas% and is not 0, and mas% is the mass percentage of each component in the material for sintered magnet;
wherein when the M includes Ti, the content of Ti is preferably 0 to 0.2 mas%, and is not 0, for example, 0.18 mas%, and mas% is a mass percentage of each component in the material for sintered magnet;
wherein, when the M comprises Zr, the Zr content is preferably 0 to 0.3 mas% and is not 0, and mas% is the mass percentage of each component in the material for sintered magnet;
preferably, the material for sintered magnets further includes Co; the content of Co is preferably 0 to 2 mas%, more preferably 0 to 1.5 mas%, for example 0.5 or 1 mas%, and mas% is the mass percentage of each component in the sintered magnet material;
preferably, the material for sintered magnets further includes Al; the content of Al is preferably 0 to 0.5 mas%, for example, 0.3 mas%, and mas% is the mass percentage of each component in the material for sintered magnets;
the material for the sintered magnet further comprises Fe, and the content of the Fe is preferably 64-70 mas%;
preferably, the first and second liquid crystal films are made of a polymer,
the material for the sintered magnet comprises the following components in percentage by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, antioxidant composition 0.2 mas%, and the balance of iron; wherein the antioxidant composition consists of the following components: poly-alpha-olefin 40 mas%; 20 mas% of butyl oleate; fatty acid methyl ester 10 mas%; 30 mas% of solvent oil, wherein the mass% of each component accounts for the mass percent of the antioxidant composition;
or, the material for the sintered magnet comprises the following components in percentage by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, antioxidant composition 0.2 mas%, and the balance of iron; wherein the antioxidant composition consists of the following components: polyalphaolefin 60 mas%; 20 mas% of butyl oleate; fatty acid methyl ester 10 mas%; 10 mas% of solvent oil, wherein the mass% of each component accounts for the mass percent of the antioxidant composition;
or, the material for the sintered magnet comprises the following components in percentage by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, antioxidant composition 0.2 mas%, and the balance of iron; wherein the antioxidant composition consists of the following components: poly-alpha-olefin 40 mas%; 10 mas% of butyl oleate; fatty acid methyl ester 10 mas%; 40 mas% of solvent oil, wherein the mass% of each component accounts for the mass percent of the antioxidant composition;
or, the material for the sintered magnet comprises the following components in percentage by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, antioxidant composition 0.2 mas%, and the balance of iron; wherein the antioxidant composition consists of the following components: poly-alpha-olefin 40 mas%; 20 mas% of butyl oleate; 15 mas% of fatty acid methyl ester; 25 mas% of solvent oil, wherein the mass% of each component accounts for the mass percent of the antioxidant composition;
or, the material for the sintered magnet comprises the following components in percentage by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, antioxidant composition 0.2 mas%, and the balance of iron; wherein the antioxidant composition consists of the following components: 30 mas% of polyalphaolefin; butyl oleate 30 mas%; fatty acid methyl ester 20 mas%; 20 mas% of solvent oil, wherein the mass% of each component accounts for the mass percent of the antioxidant composition;
or, the material for the sintered magnet comprises the following components in percentage by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, antioxidant composition 0.2 mas%, and the balance of iron; wherein the antioxidant composition consists of the following components: polyalphaolefin 45 mas%; 20 mas% of butyl oleate; fatty acid methyl ester 5 mas%; 30 mas% of solvent oil, wherein the mass% of each component accounts for the mass percent of the antioxidant composition;
or, the material for the sintered magnet comprises the following components in percentage by mass: PrNd31 mas%, Co0.5mas%, Cu0.4mas%, Ga0.5mas%, Ti0.2mas%, B0.88mas%, antioxidant composition 0.2 mas%, and the balance of iron; wherein the antioxidant composition consists of the following components: poly-alpha-olefin 40 mas%; 20 mas% of butyl oleate; fatty acid methyl ester 10 mas%; 30 mas% of solvent oil, wherein the mass% of each component accounts for the mass percent of the antioxidant composition;
or, the material for the sintered magnet comprises the following components in percentage by mass: PrNd29.5mas%, Dy2.5mas%, Co1.5mas%, Cu0.16mas%, Ga0.25mas%, Al0.3mas%, Zr0.3mas%, B0.95mas%, antioxidant composition 0.2 mas%, and the balance of iron; wherein the antioxidant composition consists of the following components: poly-alpha-olefin 40 mas%; 20 mas% of butyl oleate; fatty acid methyl ester 10 mas%; 30 mas% of solvent oil, wherein the mass% of each component accounts for the mass percent of the antioxidant composition;
or, the material for the sintered magnet comprises the following components in percentage by mass: PrNd31 mas%, Co0.5mas%, Cu0.4mas%, Ga0.5mas%, Ti0.2mas%, B0.88mas%, antioxidant composition 0.4 mas%, and the balance of iron; wherein the antioxidant composition consists of the following components: poly-alpha-olefin 40 mas%; 20 mas% of butyl oleate; fatty acid methyl ester 10 mas%; 30 mas% of solvent oil, wherein the mass% of each component accounts for the mass percent of the antioxidant composition.
5. A sintered magnet is characterized by comprising the following components in percentage by mass:
r: 29-33 mas percent, wherein R is rare earth element;
B：0.86mas％～1mas％；
ga: 0 to 0.7 mas%, and not 0;
cu: 0 to 0.5 mas% and not 0;
m: 0 to 0.4 mas%, and not 0; the M comprises at least one of Ti, Zr and Nb;
al: 0 to 0.5 mas% and not 0;
Fe：64mas％～70mas％；
C：0.1～0.2mas％；
co: 0-2 mas%; and mas% is the mass percentage of each component in the sintered magnet.
6. The sintered magnet of claim 5 wherein said R comprises PrNd and/or Nd; preferably, the R also comprises heavy rare earth element RH; preferably, the RH includes one or more of Tb, Dy, Ho, and Gd; preferably, the RH content is 0 to 2.5 mas% and is not 0, for example, 1.5 mas%, and mas% is a mass percentage of each component in the sintered magnet;
and/or the content of R is 29.5 to 32 mas%, such as 31 mas%, and mas% is the mass percentage of each component in the sintered magnet;
and/or the content of B is 0.86 to 0.99 mas%, for example 0.88 or 0.95 mas%, and mas% is the mass percentage of each component in the sintered magnet;
and/or the Ga content is 0 to 0.5 mas%, and is not 0, for example, 0.05 or 0.25 mas%, and mas% is the mass percentage of each component in the sintered magnet;
and/or the content of Cu is 0-0.4 mas% and is not 0, such as 0.36 or 0.16 mas%, and mas% is the mass percentage of each component in the sintered magnet;
and/or the content of M is 0-0.3 mas% and is not 0, for example 0.2 mas% or 0.28 mas%, and mas% is the mass percentage of each component in the sintered magnet;
when the M comprises Nb, the content of Nb is preferably 0-0.1 mas% and is not 0, and mas% is the mass percentage of each component in the sintered magnet;
wherein, when the M includes Ti, the content of Ti is preferably 0 to 0.2 mas%, and is not 0, for example, 0.18 mas%, and mas% is a mass percentage of each component in the sintered magnet;
wherein, when the M includes Zr, the Zr content is preferably 0 to 0.3 mas% and is not 0, and mas% is the mass percentage of each component in the sintered magnet;
and/or the content of Co is 0-1.5 mas%, for example 0.5 or 1 mas%, and mas% is the mass percentage of each component in the sintered magnet;
and/or the Al content is 0-0.3 mas% and is not 0, and the mas% is the mass percentage of each component in the sintered magnet;
and/or the content of C is 0.1126 mas%, 0.1378 mas%, 0.109 mas%, 0.117 mas%, 0.1209 mas%, 0.1140 mas%, 0.1165 mas%, 0.1178 mas% or 0.1255 mas%, wherein mas% is the mass percentage of each component in the sintered magnet;
and/or the sintered magnet further comprises Fe, wherein the content of the Fe is 64-70 mas%;
or, the sintered magnet consists of the following components in percentage by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, C0.1126 mas%, and the balance iron;
or, the sintered magnet consists of the following components in percentage by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, C0.1378mas%, and the balance iron;
or, the sintered magnet consists of the following components in percentage by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, C0.109mas%, and the balance of iron;
or, the sintered magnet consists of the following components in percentage by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, C0.117mas%, and the balance being iron;
or, the sintered magnet consists of the following components in percentage by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, C0.1209mas%, and the balance of iron;
or, the sintered magnet consists of the following components in percentage by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, C0.114mas%, and the balance of iron;
or, the sintered magnet consists of the following components in percentage by mass: PrNd31 mas%, Co0.5mas%, Cu0.4mas%, Ga0.5mas%, Ti0.2mas%, B0.88mas%, C0.1165mas%, and the balance of iron;
or, the sintered magnet consists of the following components in percentage by mass: PrNd29.5mas%, Dy2.5mas%, Co1.5mas%, Cu0.16mas%, Ga0.25mas%, Al0.3mas%, Zr0.3mas%, B0.95mas%, C0.1178mas%, and the balance of iron;
or, the sintered magnet consists of the following components in percentage by mass: PrNd31 mas%, Co0.5mas%, Cu0.4mas%, Ga0.5mas%, Ti0.2mas%, B0.88mas%, C0.1255mas%, and the balance being iron.
7. A rare earth permanent magnet comprises the following components in percentage by mass:
r: 29 to 33mas percent; r is a rare earth element and comprises a heavy rare earth element RH;
B：0.86mas％～1mas％；
ga: 0 to 0.7 mas%, and not 0;
cu: 0 to 0.5 mas% and not 0;
m: 0 to 0.4 mas%, and not 0; the M comprises at least one of Ti, Zr and Nb;
al: 0 to 0.5 mas% and not 0;
Fe：64mas％～70mas％；
C：0.1～0.2mas％；
co: 0-2 mas%; mas% is the mass percentage of each component in the rare earth permanent magnet;
preferably, the R comprises PrNd and/or Nd;
preferably, the content of R is 29.5-32 mas%, for example 31 or 30 mas%, and mas% is the mass percentage of each component in the rare earth permanent magnet;
the RH preferably includes one or more of Tb, Dy, Ho and Gd, more preferably Dy and/or Tb;
the content of the RH is preferably 0-2.5 mas% and is not 0, for example, 1.5 mas% or 0.5 mas%, and mas% is the mass percentage of each component in the rare earth permanent magnet;
preferably, the content of B is 0.86 to 0.99 mas%, for example 0.88 or 0.95 mas%, and mas% is the mass percentage of each component in the rare earth permanent magnet;
preferably, the content of Ga is 0 to 0.5 mas%, and is not 0, for example, 0.05 or 0.25 mas%, and mas% is the mass percentage of each component in the rare earth permanent magnet;
preferably, the content of Cu is 0-0.4 mas%, and is not 0, such as 0.36 mas% or 0.16 mas%, and mas% is the mass percentage of each component in the rare earth permanent magnet;
the content of M is preferably 0-0.3 mas%, and is not 0, for example 0.2 mas% or 0.28 mas%, and mas% is the mass percentage of each component in the rare earth permanent magnet;
when the M comprises Nb, the content of Nb is preferably 0-0.1 mas% and is not 0, and the mas% is the mass percentage of each component in the rare earth permanent magnet;
when the M comprises Ti, the content of the Ti is preferably 0-0.2 mas% and is not 0, such as 0.18 mas%, and the mas% is the mass percentage of each component in the rare earth permanent magnet;
when the M comprises Zr, the content of the Zr is preferably 0-0.3 mas% and is not 0, and the mas% is the mass percentage of each component in the rare earth permanent magnet;
preferably, the content of Co is 0-1.5 mas%, for example 0.5 or 1 mas%, and mas% is the mass percentage of each component in the rare earth permanent magnet;
preferably, the content of Al is 0-0.3 mas% and is not 0, and the mas% is the mass percentage of each component in the rare earth permanent magnet;
preferably, the content of C is 0.115 mas%, 0.1392 mas%, 0.111 mas%, 0.1195 mas%, 0.1225 mas%, 0.1165 mas%, 0.1165 mas%, 0.1178 mas% or 0.1255 mas%, and the mas% is the mass percentage of each component in the rare earth permanent magnet;
the rare earth permanent magnet also comprises Fe, and the content of the Fe is preferably 64 to 70 mas%;
preferably, the first and second liquid crystal films are made of a polymer,
the rare earth permanent magnet comprises the following components in percentage by mass: nd29.5 mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, Tb0.5mas%, and C0.115mas%, the balance being iron;
or, the rare earth permanent magnet consists of the following components in percentage by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, Tb0.5mas%, and C0.1392mas%, with the balance being iron;
or, the rare earth permanent magnet consists of the following components in percentage by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, Tb0.5mas%, and C0.111mas%, with the balance being iron;
or, the rare earth permanent magnet consists of the following components in percentage by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, Tb0.5mas%, and C0.1195mas%, with the balance being iron;
or, the rare earth permanent magnet consists of the following components in percentage by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, Tb0.5mas%, and C0.1225mas%, with the balance being iron;
or, the rare earth permanent magnet consists of the following components in percentage by mass: nd29.5mas%, Cu0.36mas%, Ga0.05mas%, Nb0.1mas%, Ti0.18mas%, B0.99mas%, Tb0.5mas%, and C0.1165mas%, with the balance being iron;
or, the rare earth permanent magnet consists of the following components in percentage by mass: PrNd31 mas%, Co0.5mas%, Cu0.4mas%, Ga0.5mas%, Ti0.2mas%, B0.88mas%, C0.1165mas%, and the balance of iron;
or, the rare earth permanent magnet consists of the following components in percentage by mass: PrNd29.5mas%, Dy2.5mas%, Co1.5mas%, Cu0.16mas%, Ga0.25mas%, Al0.3mas%, Zr0.3mas%, B0.95mas%, C0.1178mas%, and the balance of iron;
or, the rare earth permanent magnet consists of the following components in percentage by mass: PrNd31 mas%, Co0.5mas%, Cu0.4mas%, Ga0.5mas%, Ti0.2mas%, B0.88mas%, C0.1255mas%, and the balance being iron.
8. A method for producing a sintered magnet, comprising the steps of:
melting and coarsely pulverizing the components other than the antioxidant composition in the material for sintered magnets as claimed in claim 4 to obtain coarse powder; then finely crushing the mixture of the coarse powder and the antioxidant composition with the dosage of 40-60% to obtain fine powder; and then molding and sintering the mixture of the fine powder and the rest of the antioxidant composition.
9. A preparation method of a rare earth permanent magnet is characterized by comprising the following steps: a sintered magnet according to claim 5 or 6, which is produced by one of the following two methods:
the first method is as follows: sequentially carrying out primary aging treatment and secondary aging treatment;
the second method comprises the following steps: sequentially carrying out grain boundary diffusion treatment and secondary aging treatment;
in the first mode, the temperature of the primary aging treatment is preferably 880-920 ℃, such as 900 ℃;
in the first mode, the time of the first-stage aging is preferably 2 to 4 hours;
in the second mode, the heavy rare earth element in the grain boundary diffusion treatment preferably includes Tb and/or Dy;
wherein the temperature of the grain boundary diffusion treatment is preferably 800-900 ℃, for example 850 ℃;
wherein the time of the grain boundary diffusion treatment is preferably 12 to 48 hours, such as 24 hours;
in the first mode and/or the second mode, the temperature of the secondary aging treatment is preferably 460 ℃ to 520 ℃, for example 490 ℃;
in the first mode and/or the second mode, the time of the secondary aging is preferably 2 to 4 hours.
10. Use of a sintered magnet according to claim 5 or 6 and/or a rare earth permanent magnet according to claim 7 as a rotor for a permanent magnet electrical machine.
CN202111414971.7A 2021-11-25 2021-11-25 Antioxidant composition, rare earth permanent magnet, sintered magnet material and preparation method Pending CN114220622A (en)

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WO2023093496A1 (en) * 2021-11-25 2023-06-01 福建省长汀金龙稀土有限公司 Antioxidant composition, rare earth permanent magnet, sintered magnet material, and preparation method

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CN107275025B (en) * 2016-04-08 2019-04-02 沈阳中北通磁科技股份有限公司 One kind Nd-Fe-B magnet steel containing cerium and manufacturing method
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