WO2023124527A1 - Grain boundary diffusion material, r-t-b magnet, and preparation method therefor - Google Patents

Grain boundary diffusion material, r-t-b magnet, and preparation method therefor Download PDF

Info

Publication number
WO2023124527A1
WO2023124527A1 PCT/CN2022/129743 CN2022129743W WO2023124527A1 WO 2023124527 A1 WO2023124527 A1 WO 2023124527A1 CN 2022129743 W CN2022129743 W CN 2022129743W WO 2023124527 A1 WO2023124527 A1 WO 2023124527A1
Authority
WO
WIPO (PCT)
Prior art keywords
phase
grain boundary
diffusion
content
mol
Prior art date
Application number
PCT/CN2022/129743
Other languages
French (fr)
Chinese (zh)
Inventor
廖宗博
谢菊华
王若澍
黄佳莹
Original Assignee
福建省长汀金龙稀土有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 福建省长汀金龙稀土有限公司 filed Critical 福建省长汀金龙稀土有限公司
Publication of WO2023124527A1 publication Critical patent/WO2023124527A1/en

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
    • H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
    • H01F1/047—Alloys characterised by their composition
    • H01F1/053—Alloys characterised by their composition containing rare earth metals
    • H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
    • H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
    • H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
    • H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
    • H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/18—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
    • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
    • H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
    • H01F41/0293—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets diffusion of rare earth elements, e.g. Tb, Dy or Ho, into permanent magnets

Definitions

  • the invention relates to a grain boundary diffusion material, an R-T-B magnet and a preparation method thereof.
  • NdFeB magnets have excellent magnetic properties and have been widely used in hybrid vehicles, electrical engineering, and electronic information fields.
  • the methods for improving sintered NdFe magnets mainly include alloying, grain refinement and grain boundary diffusion.
  • the grain boundary diffusion method refers to depositing a layer of heavy rare earth powder on the surface of the magnet by sputtering, vapor deposition, electrophoresis, coating, etc., and diffusing the heavy rare earth elements on the surface of the magnet into the interior of the magnet through heat treatment.
  • the boundary layer forms a magnetically hardened shell to increase the coercive force, and this method can greatly increase the coercive force only by using a small amount of heavy rare earth elements.
  • the present invention mainly aims to solve the defect in the prior art that the addition of heavy rare earth elements in the grain boundary diffusion process has a low degree of improvement in the coercive force, and provides a grain boundary diffusion material, an R-T-B magnet and a preparation method thereof.
  • the R-T-B magnet prepared by adopting the grain boundary diffusion material of the present invention has significantly improved coercive force and temperature stability, and the remanence is basically unchanged.
  • the present invention mainly solves the above technical problems through the following technical solutions.
  • the invention provides a grain boundary diffusion material of an R-T-B magnet, which includes a diffusion matrix and a diffusion source;
  • the diffusion matrix includes the following components:
  • R 28.5 ⁇ 33.5wt.%, R is a rare earth element
  • Ga 0 ⁇ 0.5wt.%
  • Fe 65-70wt.%, wt.% is the percentage of the mass of each component to the total mass of the diffusion matrix
  • the diffusion source includes the following components:
  • the HR 0-70wt.% but not 0wt.%; the HR is a heavy rare earth element, and the HR includes Dy and/or Tb;
  • Fe 0-8wt.%; wt.% is the percentage of the mass of each component to the total mass of the diffusion source.
  • the diffusion matrix generally refers to the magnet material after sintering, aging or grain boundary diffusion, or a mixture of two or more kinds.
  • the diffusion matrix generally refers to the magnet material after sintering and/or aging, such as a sintered body.
  • the content of R is preferably 28-32wt.%, such as 29wt.%, 30wt.% or 31wt.%.
  • the R can be conventional in the field, and generally contains at least LR, and LR is a light rare earth element, and the LR includes Nd and/or Pr.
  • the rare earth elements are mainly Nd and/or Pr, that is, at least two-thirds of the rare earth elements.
  • the content of Nd may be 21-32wt.%, such as 25wt.%, 26wt.% or 27wt.%, where wt.% is the percentage of the total mass of the diffusion matrix.
  • the content of Pr can be 4 to 32wt.%, such as 6wt.%, 15wt.%, 20wt.%, 25wt.% or 31wt.%, wt.% is accounted for the diffusion The percentage of the total mass of the matrix.
  • RH is generally added in order to increase the magnetic properties of the R-T-B magnet, and RH is a heavy rare earth element.
  • the RH may be conventional in the art, for example including Dy and/or Tb.
  • the content of the RH may be 0-2wt.% but not 0wt.%, such as 1wt.%, where wt.% is the percentage of the total mass of the diffusion matrix.
  • Ga is preferably not contained.
  • the Ga content is preferably 0.05-0.5 wt.%, such as 0.1 wt.% or 0.2 wt.%.
  • the content of B is preferably 0.9-0.98wt.%, such as 0.95wt.%.
  • the content of Fe is generally the balance.
  • the content of Fe may be 65-69wt.%, such as 66.98wt.%, 69.32wt.%, 65.55wt.% or 67.75wt.%.
  • the diffusion matrix of the present invention generally also includes the conventional additive element M in the field, and the M includes, for example, one or more of Al, Co, Cu, Zr, Ti and Nb.
  • the content of M can be conventional in the art, can be 0 ⁇ 3wt.%, but not 0wt.%, such as 0.7wt.%, 1.12wt.%, 1.3wt.% or 1.5wt.%, wt. % is the percentage of the total mass of the diffusion matrix.
  • the content of the Al can be 0-0.5wt.% but not 0wt.%, such as 0.02wt.% or 0.1wt.%, wt.% is the proportion of the diffusion matrix percentage of the total mass.
  • the content of Co can be 0 to 1wt.% but not 0wt.%, such as 0.2wt.%, 0.5wt.% or 0.6wt.%, wt.% is accounted for The percentage of the total mass of the diffusion matrix.
  • the content of Cu may be 0 to 1wt.% but not 0wt.%, such as 0.2wt.%, 0.4wt.% or 0.5wt.%, and wt.% is accounted for The percentage of the total mass of the diffusion matrix.
  • the content of Zr may be 0-0.5wt.% but not 0wt.%, such as 0.1wt.%, and wt.% is the percentage of the total mass of the diffusion matrix .
  • the content of the Ti can be 0-0.5wt.% but not 0wt.%, such as 0.1wt.%, wt.% is the percentage of the total mass of the diffusion matrix .
  • the diffusion matrix is composed of the following components: Nd 25wt.%, Pr 6wt.%, Fe 66.98wt.%, Al 0.02wt.%, Co 0.6wt.%, Cu 0.4wt. .%, Zr 0.1wt.% and B 0.9wt.%, wt.% is the percentage of the mass of each component to the total mass of the diffusion matrix.
  • the diffusion matrix is composed of the following components: Nd 27wt.%, Dy 2wt.%, Fe 69.32wt.%, Co 0.2wt.%, Cu 0.2wt.%, Ga 0.2wt .%, Ti 0.1wt.% and B 0.98wt.%, wt.% is the percentage of the mass of each component to the total mass of the diffusion matrix.
  • the diffusion matrix is composed of the following components: Pr 31wt.%, Dy 1wt.%, Fe 65.55wt.%, Co 0.5wt.%, Cu 0.5wt.%, Ga 0.5wt. .% and B 0.95wt.%, wt.% is the percentage of the mass of each component and the total mass of the diffusion matrix.
  • the diffusion matrix is composed of the following components: Nd 26wt.%, Pr 4wt.%, Fe 67.75wt.%, Al 0.1wt.%, Co 0.6wt.%, Cu 0.4wt .%, Ga 0.1wt.%, Zr 0.1wt.% and B 0.95wt.%, wt.% is the percentage of the mass of each component to the total mass of the diffusion matrix.
  • the diffusion source generally refers to the raw material to be diffused that is added when the grain boundary diffusion matrix is subjected to grain boundary diffusion treatment.
  • the content of RH is preferably 50-70wt.%, such as 55wt.%, 60wt.% or 65wt.%.
  • the RH content in the diffusion source is greater than 70wt.%, although the coercive force can be increased to the same extent as 70wt.%, it will lead to increased cost and significantly increased difficulty in preparation.
  • the diffusion source preferably does not contain Ho or Gd. Due to the nature of the element itself (the magnetocrystalline anisotropy field HA is significantly lower than that of Dy and Tb), the effect of Ho or Gd on improving Hcj is significantly lower than that of Dy and/or Tb.
  • the Ga content is preferably 10-40wt.%, such as 20wt.% or 30wt.%.
  • the content of Cu is preferably 0-1wt.% or 8-10wt.%, such as 0wt.% or 10wt.%.
  • the content of Co is preferably 0-1wt.% or 8-10wt.%, such as 0wt.% or 10wt.%.
  • the content of Al is preferably 0-1wt.% or 4-5wt.%, such as 0wt.% or 5wt.%.
  • the content of Fe is preferably 0-1wt.% or 4-5wt.%, such as 0wt.% or 5wt.%.
  • the diffusion source is composed of the following components: Tb 70wt.%, Cu 10wt.%, Co 10wt.% and Ga 10wt.%, wt.% is the mass of each component and the The percentage of the total mass of the diffusion source mentioned above.
  • the diffusion source is composed of the following components: Tb 65wt.%, Co 10wt.%, Ga 20wt.% and Al 5wt.%, wt.% is the mass of each component and the The percentage of the total mass of the diffusion source mentioned above.
  • the diffusion source is composed of the following components: Dy 55wt.%, Cu 10wt.%, Ga 30wt.% and Fe 5wt.%, wt.% is the mass of each component and the The percentage of the total mass of the diffusion source mentioned above.
  • the diffusion source is composed of the following components: Tb 70wt.% and Ga 30wt.%, wt.% is the percentage of the mass of each component to the total mass of the diffusion source.
  • the mass ratio of the diffusion source and the diffusion matrix is preferably below 2wt.%, preferably 0.3-1.5wt.%, such as 0.3wt.%, 0.4wt.%, 0.8wt.% or 1.2wt.%. .
  • the present invention also provides a method for preparing an R-T-B magnet, which includes the following steps: diffusing the diffusion source into the diffusion matrix through grain boundary diffusion treatment.
  • the temperature of the grain boundary diffusion treatment can be conventional in the field, preferably below 900°C, for example, 800-900°C.
  • the inventor found in experiments that the temperature of the grain boundary diffusion treatment is below 900°C, and the degree of coercive force achieved is equivalent to that above 900°C (in the present invention, the grain boundary diffusion temperatures of 800°C and 950°C
  • the degree of coercive force improvement, remanence change degree and temperature stability change degree of the obtained magnet materials are equivalent), it can be seen that the grain boundary diffusion material of the present invention not only brings significant improvement of coercive force, but also has low energy consumption.
  • the time for the grain boundary diffusion treatment can be conventional in the field, generally 8-12 hours, for example 10 hours.
  • the diffusion source in order to enable the diffusion source to diffuse into the diffusion matrix through the grain boundary diffusion treatment, the diffusion source generally needs to be pretreated.
  • the pretreatment generally forms a mixed slurry of the diffusion source and an organic solvent on the surface of the diffusion matrix.
  • the diffusion source is generally in the form of an alloy powder.
  • the alloy powder is generally prepared by melting each component in the diffusion source at high temperature and then making it into powder.
  • the organic solvent can be conventional in the art, and can be an alcoholic solvent, such as ethanol.
  • the diffusion source can be formed on the surface of the diffusion matrix by a conventional method in the art, generally by coating or spraying.
  • the thickness of the diffusion source coating formed on the surface of the diffusion substrate after the pretreatment may be less than 100 ⁇ m, for example, 10 ⁇ 50 ⁇ m.
  • the thickness generally refers to the thickness of the diffusion matrix after the organic solvent has completely volatilized.
  • the diffusion source described in the present invention is performing grain boundary diffusion, the excellent effect of the present invention can be realized without adding an antioxidant.
  • the diffusion matrix can be prepared by conventional preparation techniques in the field. Generally, the mixture of the diffusion matrix is smelted, pulverized, formed in a magnetic field and sintered in sequence.
  • the raw material composition of the diffusion matrix is basically the same as the components in the final diffusion matrix, and those skilled in the art can prepare the raw materials according to the required components of the diffusion matrix. , it is necessary to consider the burning loss of rare earths during preparation. It should be noted that there may be variations within the error range during the preparation process.
  • the melting temperature is preferably below 1500°C, such as 1400-1500°C.
  • the vacuum degree of the smelting is preferably 5 ⁇ 10 -2 Pa.
  • conventional casting in the field is generally included after the smelting, and the environment of the casting is an inert atmosphere, such as argon.
  • the atmospheric pressure of the casting is, for example, 55,000 Pa.
  • Quenching treatment is generally performed after the casting and before the pulverization to obtain a quenched alloy.
  • the cooling rate of the rapid cooling treatment is, for example, 102°C/sec to 104°C/sec.
  • the fine pulverization may be a conventional crushing process in the art, for example, hydrogen absorption, dehydrogenation and jet milling are performed sequentially.
  • the magnetic field strength of the magnetic field shaping may be 1.5-2T, for example, 1.6T.
  • the sintering can be carried out under vacuum conditions, such as 5 ⁇ 10 -3 Pa vacuum conditions, and the sintering temperature is preferably 1000-1100°C, such as 1030°C or 1040°C.
  • heat treatment is preferably performed sequentially at temperatures of 300°C, 600°C, and 800°C respectively.
  • the time for the sintering treatment is, for example, 2.5-5 hours, such as 3 hours or 4 hours.
  • sinter at 1030°C for 3h, and then at 1040°C for 1h.
  • cooling treatment is generally performed after the sintering treatment, and the cooling treatment may be to cool the magnet material obtained after sintering to 90-110°C, for example, 100°C; the cooling rate of the cooling treatment may be 10°C/min .
  • the size of the sintered body can be tailored according to actual needs.
  • the length and width are 20mm
  • the thickness is 2mm
  • the thickness direction is the direction of the magnetic field.
  • the present invention also provides an R-T-B magnet, which is prepared by the preparation method.
  • the present invention also provides a R-T-B magnet, which comprises the following components:
  • the R is a rare earth element, the R includes HR, the HR is a heavy rare earth element, and the HR includes Dy and/or Tb;
  • Fe 65-70wt.%, wt.% is the percentage of the mass of each component to the total mass of the R-T-B magnet;
  • the R-T-B magnet includes a main phase and a grain boundary phase, and the grain boundary phase is a two-grain grain boundary phase and a grain boundary triangular region;
  • the grain boundary triangular region includes phase 1 and phase 2; the phase 1 contains Ga 1 and Tb 1 , and the phase 2 contains Ga 2 and Tb 2 ;
  • Tb 1 2 mol% or less and not 0;
  • Tb 2 less than 2 mol% and not 0; mol% is the mole percentage of each component and all components in the grain boundary phase;
  • the ratio of the total area of "the phase 1 and the phase 2" to the total area of the grain boundary phase is more than 50%.
  • the grain boundary triangular region generally refers to the gap between the three main phase grains.
  • the two-grain boundary phase generally refers to the gap between the two main phase grains.
  • the measurement methods of the phase 1 and the phase 2 can be conventional in the field, and generally refer to the detection of the vertical orientation plane of the RTB magnet by using FE-EPMA.
  • Those skilled in the art can know according to the phase 1 or the phase 2 that the phase 1 is generally formed by gathering or combining the Ga 1 and the Tb 1 , and the phase 2 is generally formed by The Ga 2 and the Tb 2 are aggregated or combined to form.
  • the absolute value of the difference between X 1 mol% and X 2 mol% is above 10 mol%, such as 10.1 mol%, 11.85 mol%, 13.8 mol% or 14.34 mol%.
  • the Ga 1 content is preferably 10-20 mol%, such as 11.29 mol%, 16.12 mol%, 17.8 mol% or 18.35 mol%.
  • the content of Tb 1 is preferably 0.1-1 mol%, such as 0.3 mol%, 0.35 mol%, 0.41 mol% or 0.5 mol%.
  • the Ga 2 content is preferably 1-5 mol%, such as 1.19 mol%, 4.01 mol%, 4 mol% or 4.27 mol%.
  • the content of Tb 2 is preferably 0.1-1 mol%, such as 0.3 mol%, 0.31 mol% or 0.32 mol%.
  • the ratio of the total area of "the phase 1 and the phase 2" to the total area of the grain boundary phase is preferably 50-70%, such as 52%, 58%, 61% or 67%.
  • the content of R is preferably 28.5-32wt.%, such as 29.88wt.%, 30.02wt.%, 30.6wt.%, 30.61wt.% or 31.64wt.%.
  • the R generally contains at least LR, and LR is a light rare earth element, and the LR includes Nd and/or Pr.
  • the ratio of the mass of "Nd and/or Pr" to the total mass of the rare earth elements is preferably more than 2/3.
  • the content of LR can be conventional in the field, generally 21-32wt.%, such as 27.5wt.%, 29.73wt.%, 30wt.% or 30.4wt.%.
  • the content of Nd is preferably 21-32wt.%, such as 24.6wt.%, 25.92wt.% or 27.5wt.%. percentage of the total mass.
  • the content of the Pr is preferably 2-31wt.%, such as 3.81wt.%, 5.8wt.% or 30.5wt.%.
  • the content of HR is preferably 0.2-3wt.%, such as 0.21wt.%, 0.29wt.%, 1.64wt.% or 2.38wt.%.
  • the Dy content is preferably 1-2 wt.%, such as 1.64 wt.% or 1.85 wt.%.
  • the content of Tb is preferably 0.2-1 wt.%, such as 0.21 wt.%, 0.29 wt.% or 0.53 wt.%.
  • the Ga content is preferably 0.02-0.85wt.%, such as 0.03wt.%, 0.21wt.%, 0.35wt.% or 0.82wt.%.
  • the content of Cu is preferably 0.1-0.7wt.%, such as 0.2wt.%, 0.4wt.%, 0.43wt.% or 0.61wt.%.
  • the content of Co is preferably 0.2-0.7wt.%, such as 0.28wt.%, 0.5wt.%, 0.6wt.%, 0.62wt.% or 0.63wt.%.
  • the content of Al is preferably 0.01-0.15wt.%, such as 0.03wt.%, 0.05wt.% or 0.12wt.%.
  • the content of B is preferably 0.9-1wt.%, such as 0.91wt.%, 0.95wt.% or 0.98wt.%.
  • the content of Fe is preferably 65-69wt.%, 66.63wt.%, 67.38wt.%, 64.3wt.% or 67.21wt.%.
  • the R-T-B magnet may also include other conventional additive elements in the art, such as one or more of Zr, Ti and Nb.
  • the content of Zr is preferably 0-0.5wt.%, but not 0wt.%, such as 0.1wt.%.
  • the content of Ti is preferably 0-0.5wt.% but not 0wt.%, for example 0.1wt.%.
  • the R-T-B magnet is composed of the following components: Nd 24.6wt.%, Pr 5.8wt.%, Tb 0.2wt.%, Fe 66.63wt.%, Al 0.03wt.%, Co 0.63wt.%, Cu 0.43wt.%, Ga 0.03wt.%, Zr 0.1wt.% and B 0.9wt.%, wt.% is the percentage of the mass of each component and the total mass of the R-T-B magnet;
  • the R-T-B magnet includes a main phase and a grain boundary phase, and the grain boundary phase is a two-grain grain boundary phase and a grain boundary triangular region, and the grain boundary triangular region includes a phase 1 and a phase 2, and the phase 1 contains 11.29 mol% of Ga and 0.35mol% of Tb, the phase 2 contains 1.19mol% of Ga and 0.31mol% of Tb, and mol% is the mole percent of all components in the grain boundary phase
  • the R-T-B magnet is composed of the following components: Nd 27.5wt.%, Dy 1.85wt.%, Tb 0.53wt.%, Fe 67.38wt.%, Al 0.05wt.%, Co 0.28wt.%, Cu 0.2wt.%, Ga 0.35wt.%, Ti 0.1wt.% and B 1wt.%, wt.% is the percentage of the mass of each component and the total mass of the R-T-B magnet;
  • the R-T-B magnet includes a main phase and a grain boundary phase.
  • the grain boundary phase is a two-grain grain boundary phase and a grain boundary triangular area.
  • the grain boundary triangular area includes a phase 1 and a phase 2.
  • the phase 1 contains 16.12mol % of Ga and 0.41mol% of Tb
  • the phase 2 contains 4.27mol% of Ga and 0.32mol% of Tb
  • mol% is the mole percentage of all components in the grain boundary phase, "the The ratio of the total area of phase 1 and the phase 2" to the total area of the grain boundary phase is 61%.
  • the R-T-B magnet is composed of the following components: Pr 30.5wt.%, Dy 1.64wt.%, Fe 64.3wt.%, Co 0.5wt.%, Cu 0.61wt.%, Ga 0.82wt.% and B 0.95wt.%, wt.% is the percentage of the mass of each component and the total mass of the R-T-B magnet;
  • the R-T-B magnet includes a main phase and a grain boundary phase, and the grain boundary phase is two Grain boundary phase and grain boundary triangular region, the grain boundary triangular region includes phase 1 and phase 2, the phase 1 contains 18.35mol% of Ga and 0.3mol% of Tb, and the phase 2 contains 4.01mol% of Ga and 0.32mol% of Tb, mol% is the mole percentage of all components in the grain boundary phase, the total area of "the phase 1 and the phase 2" is related to the grain boundary The ratio of the total area of the phases was 67%.
  • the R-T-B magnet is composed of the following components: Nd 25.92wt.%, Pr 3.81wt.%, Tb 0.29wt.%, Fe 67.21wt.%, Al 0.12wt.%, Co 0.6wt.%, Cu 0.4wt.%, Ga 0.21wt.%, Zr 0.1wt.% and B 0.95wt.%, wt.% is the percentage of the mass of each component and the total mass of the R-T-B magnet;
  • the R-T-B magnet includes a main phase and a grain boundary phase, and the grain boundary phase is a two-grain grain boundary phase and a grain boundary triangular region, and the grain boundary triangular region includes a phase 1 and a phase 2, and the phase 1 contains 17.8 mol% of Ga and 0.5mol% of Tb, the phase 2 contains 4mol% of Ga and 0.3mol% of Tb, and mol% is the mole percentage of all components in the grain boundary phase
  • the reagents and raw materials used in the present invention are all commercially available.
  • the positive progress effect of the present invention is: the diffusion source of specific content Ga and heavy rare earth element in the present invention and control the content of Cu, Co and Al in described diffusion source, coordinate the diffusion matrix of specific composition, pass described grain boundary After diffusion, Ga in the diffusion source preferentially occupies the triangular area of the grain boundary, forming a Ga-containing phase, which is rarely combined with Tb, so that Tb enters the outer layer of the grain more or diffuses inward, thereby significantly improving The diffusion effect is improved, the coercive force is significantly improved while maintaining high remanence and temperature stability.
  • FIG. 1 is the microstructure of the R-T-B magnet of Example 1.
  • Micro-grinding Vacuumize the hydrogen blasting furnace where the quenched alloy is placed at room temperature, and then pass hydrogen gas with a purity of 99.9% into the hydrogen crushing furnace to maintain the hydrogen pressure at 0.1 MPa; after fully absorbing hydrogen, vacuum while Raise the temperature to fully dehydrogenate; then cool down and take out the powder after hydrogen crushing.
  • Oxidizing gas refers to oxygen or moisture.
  • 3Molding Using a right-angle orientation magnetic field molding machine, in an orientation magnetic field of 1.6T, and under a molding pressure of 0.35ton/ cm2 , the above-mentioned powder added with zinc stearate is molded into a cube with a side length of 25mm at one time , Demagnetized in a 0.2T magnetic field after one molding.
  • the sintered body obtained above is processed into a magnet with a length and width of 20mm and a thickness of 2mm, the thickness direction is the direction of magnetic field orientation, and the surface is cleaned for later use;
  • the diffusion source is formulated into alloy powder according to the formula in Table 2 below and prepared into a slurry coating Coated on the surface of the diffusion matrix, the thickness of the coating is less than 100 ⁇ m, and there is no need to add antioxidants.
  • the alloy powder is made by melting all the components in the diffusion source together at high temperature, then spraying the surface of the diffusion matrix with ethanol as a solvent, and then performing grain boundary diffusion treatment on the magnet at 800-900°C. The time is 10h.
  • the formulations of the diffusion matrix and diffusion source of Examples 2-4 and Comparative Examples 1-4 are shown in Table 1 and Table 2 below, and the preparation process is the same as in Example 1, and the diffusion source in Examples 2-4 and Comparative Examples 1-4 is The coating thickness on the diffusion substrate is below 100 ⁇ m.
  • Table 1 Diffusion matrix (unit wt.%, the percentage of the mass of each component to the total mass of the diffusion matrix)
  • ⁇ Hcj refers to the value obtained by subtracting the coercive force of the corresponding sintered body before diffusion from the coercive force of the obtained R-T-B magnet.
  • the test temperature is 20°C.
  • the vertically oriented surfaces of the R-T-B magnets in Examples 1-4 and Comparative Examples 1-4 are polished, and are detected by Field Emission Electron Probe Microanalyzer (FE-EPMA) (JEOL, 8530F) . It is found that phases containing Ga and Tb can be observed at a depth of 0-300 ⁇ m from the diffusion surface (referring to the surface of the diffusion substrate coated with the diffusion source in the preparation of the R-T-B magnet). The contents of Tb and Ga elements at grain boundaries in R-T-B magnets were determined by FE-EPMA single-point quantitative analysis. The test conditions were acceleration voltage 15kv and probe beam current 50nA. The test results are shown in Table 5 below.
  • Figure 1 shows the microstructure of the R-T-B magnet in Example 1 and the grain boundary composition of the triangular grain boundary region, point 6 in the figure is the low Ga phase, and point 7 is the high Ga phase.
  • Ga occupies the triangular grain boundary area, forming more high Ga phases, and the high Ga phase and low Ga phase have a concentration difference of more than 10 mol%, and the Tb content is low, and it will be observed that the two-grain grain boundary phase only contains less Ga.
  • the phase in the triangular region of the grain boundary can lower the melting point of the grain boundary phase, and has better wettability, making the grain boundary uniform and continuous.
  • the high Ga phase and low Ga phase have a phenomenon of rejection relative to Tb, and the Tb content is extremely low, generally not exceeding 2mol%, which can reduce the consumption of Tb elements at the grain boundary, make it diffuse deeper along the grain boundary, and be more effectively absorbed. use.
  • mol% is the ratio of the total molar weight of all elements in the grain boundary phase
  • Phase 1 and phase 2 are located in the grain boundary triangle area, and the area ratio of phase 1+phase 2 refers to the ratio of the total area of phase 1 and phase 2 to the total area of the grain boundary phase.
  • the present invention cooperates through specific diffusion matrix and diffusion source, and after grain boundary diffusion treatment, coercive force is compared with
  • the diffusion matrix has been increased by more than 10kOe, and the amount of heavy rare earth used is also less.
  • the temperature of the grain boundary diffusion treatment is low, which realizes low energy consumption and low material cost, and also significantly improves the coercive force.
  • the remanence is basically unchanged, and the temperature stability has also been significantly improved.
  • the realization of the present invention is obtained by the research and development staff through many experiments by accident, and has passed through many failed experiments in the process of research and development.
  • the content of Ga is too high, and the content of B is too low or too high.
  • the diffusion source was prepared, the content of Ga was too low, and the content of other elements (Cu, Co, Fe, and Al) was not controlled. After the grain boundary diffusion treatment, the coercive force could not be significantly improved.

Landscapes

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

Abstract

Disclosed are a grain boundary diffusion material, an R-T-B magnet, and a preparation method therefor. The grain boundary diffusion material comprises a diffusion matrix and a diffusion source. The diffusion matrix comprises the following components: 28.5-33.5 wt% of R, R being a rare earth element; 0-0.5 wt% of Ga; 0.9-1.02 wt% of B; and 65-70 wt% of Fe. The diffusion source comprises the following components: 0-70 wt% of HR (but not including 0 wt%), HR being a heavy rare earth element and comprising Dy and/or Tb; greater than or equal to 10 wt% of Ga; 0-10 wt% of Cu; 0-10 wt% of Co; 0-8 wt% of Al; and 0-8 wt% of Fe. Compared with diffusion matrices before grain boundary diffusion, an R-T-B magnet prepared by using the grain boundary diffusion material of the present invention has significantly improved coercivity and temperature stability, and the remanence thereof is basically unchanged.

Description

一种晶界扩散材料、R-T-B磁体及其制备方法A kind of grain boundary diffusion material, R-T-B magnet and preparation method thereof 技术领域technical field
本发明涉及一种晶界扩散材料、R-T-B磁体及其制备方法。The invention relates to a grain boundary diffusion material, an R-T-B magnet and a preparation method thereof.
背景技术Background technique
钕铁硼磁体具有优异的磁性能，已被广泛应用于混合动力汽车、电机工程、电子信息领域等。目前，提高烧结钕铁磁体的方法主要有合金化、晶粒细化和晶界扩散。其中，晶界扩散方法是指通过溅射、气相沉积、电泳、涂覆等方法在磁体表面沉积一层重稀土粉末，通过热处理使磁体表面的重稀土元素扩散进入磁体内部，在主相晶粒边界层形成磁硬化壳层来提高矫顽力，这种方法只需使用少量的重稀土元素就能大幅度的提高矫顽力。但是现有技术中采用重稀土元素扩散来提高烧结体的矫顽力的程度一般只限于10kOe或者更低，而且需要添加较多量的重稀土元素或者需要复杂的工艺。如何充分利用少量的重稀土元素来提高磁体的矫顽力是目前还未有效解决的技术问题。NdFeB magnets have excellent magnetic properties and have been widely used in hybrid vehicles, electrical engineering, and electronic information fields. At present, the methods for improving sintered NdFe magnets mainly include alloying, grain refinement and grain boundary diffusion. Among them, the grain boundary diffusion method refers to depositing a layer of heavy rare earth powder on the surface of the magnet by sputtering, vapor deposition, electrophoresis, coating, etc., and diffusing the heavy rare earth elements on the surface of the magnet into the interior of the magnet through heat treatment. The boundary layer forms a magnetically hardened shell to increase the coercive force, and this method can greatly increase the coercive force only by using a small amount of heavy rare earth elements. However, in the prior art, the use of heavy rare earth element diffusion to increase the coercive force of the sintered body is generally limited to 10kOe or lower, and a large amount of heavy rare earth element needs to be added or a complicated process is required. How to make full use of a small amount of heavy rare earth elements to increase the coercive force of magnets is a technical problem that has not been effectively solved yet.
发明内容Contents of the invention
本发明主要是为了解决现有技术中存在的晶界扩散工艺添加重稀土元素对矫顽力的提升程度较低的缺陷，而提供了一种晶界扩散材料、R-T-B磁体及其制备方法。采用本发明的晶界扩散材料制备的R-T-B磁体相较于晶界扩散前的扩散基体，矫顽力和温度稳定性有显著的提升，且剩磁基本不变。The present invention mainly aims to solve the defect in the prior art that the addition of heavy rare earth elements in the grain boundary diffusion process has a low degree of improvement in the coercive force, and provides a grain boundary diffusion material, an R-T-B magnet and a preparation method thereof. Compared with the diffusion matrix before the grain boundary diffusion, the R-T-B magnet prepared by adopting the grain boundary diffusion material of the present invention has significantly improved coercive force and temperature stability, and the remanence is basically unchanged.
本发明主要是通过以下技术方案解决以上技术问题的。The present invention mainly solves the above technical problems through the following technical solutions.
本发明提供了一种R-T-B磁体的晶界扩散材料，其包括扩散基体和扩散源；The invention provides a grain boundary diffusion material of an R-T-B magnet, which includes a diffusion matrix and a diffusion source;
所述扩散基体包括以下组分：The diffusion matrix includes the following components:
R：28.5～33.5wt.％，R为稀土元素；R: 28.5～33.5wt.%, R is a rare earth element;
Ga：0～0.5wt.％；Ga: 0～0.5wt.%;
B：0.9～1.02wt.％；B: 0.9～1.02wt.%;
Fe：65～70wt.％，wt.％为各组分的质量与所述扩散基体的总质量的百分比；Fe: 65-70wt.%, wt.% is the percentage of the mass of each component to the total mass of the diffusion matrix;
所述扩散源包括以下组分：The diffusion source includes the following components:
HR：0～70wt.％但不为0wt.％；所述HR为重稀土元素，所述HR包括Dy和/或Tb；HR: 0-70wt.% but not 0wt.%; the HR is a heavy rare earth element, and the HR includes Dy and/or Tb;
Ga≥10wt.％；Ga≥10wt.%;
Cu：0～10wt.％；Cu: 0～10wt.%;
Co：0～10wt.％；Co: 0～10wt.%;
Al：0～8wt.％；Al: 0～8wt.%;
Fe：0～8wt.％；wt.％为各组分的质量与所述扩散源的总质量的百分比。Fe: 0-8wt.%; wt.% is the percentage of the mass of each component to the total mass of the diffusion source.
本发明中，本领域技术人员根据所述的晶界扩散材料可知，所述的扩散基体一般是指经烧结、时效或晶界扩散之后的磁体材料，或者是两种以上的混合物。本领域技术人员知晓，由于再次扩散之后的磁体材料一般提升程度有限，因此，所述的扩散基体一般是指经烧结和/或时效之后的磁体材料，例如烧结体。In the present invention, those skilled in the art know from the grain boundary diffusion material that the diffusion matrix generally refers to the magnet material after sintering, aging or grain boundary diffusion, or a mixture of two or more kinds. Those skilled in the art know that since the magnet material after re-diffusion generally has a limited improvement, the diffusion matrix generally refers to the magnet material after sintering and/or aging, such as a sintered body.
本发明所述扩散基体中，所述R的含量较佳地为28～32wt.％，例如29wt.％、30wt.％或31wt.％。In the diffusion matrix of the present invention, the content of R is preferably 28-32wt.%, such as 29wt.%, 30wt.% or 31wt.%.
本发明所述扩散基体中，所述R可为本领域常规，一般至少含有LR，LR为轻稀土元素，所述LR包括Nd和/或Pr。本领域技术人员知晓，所述稀土元素主要以Nd和/或Pr为主，即占所述稀土元素的至少三分之二。In the diffusion matrix of the present invention, the R can be conventional in the field, and generally contains at least LR, and LR is a light rare earth element, and the LR includes Nd and/or Pr. Those skilled in the art know that the rare earth elements are mainly Nd and/or Pr, that is, at least two-thirds of the rare earth elements.
当所述R包含Nd时，所述Nd的含量可为21～32wt.％，例如25wt.％、26wt.％或27wt.％，wt.％为占所述扩散基体的总质量的百分比。When the R contains Nd, the content of Nd may be 21-32wt.%, such as 25wt.%, 26wt.% or 27wt.%, where wt.% is the percentage of the total mass of the diffusion matrix.
当所述R包含Pr时，所述Pr的含量可为4～32wt.％，例如6wt.％、15wt.％、20wt.％、25wt.％或31wt.％，wt.％为占所述扩散基体的总质量的百分比。When the R includes Pr, the content of Pr can be 4 to 32wt.%, such as 6wt.%, 15wt.%, 20wt.%, 25wt.% or 31wt.%, wt.% is accounted for the diffusion The percentage of the total mass of the matrix.
本发明中，为了增加所述R-T-B磁体的磁性能一般会添加RH，RH为重 稀土元素。In the present invention, RH is generally added in order to increase the magnetic properties of the R-T-B magnet, and RH is a heavy rare earth element.
其中，所述RH可为本领域常规，例如包括Dy和/或Tb。Wherein, the RH may be conventional in the art, for example including Dy and/or Tb.
其中，所述RH的含量可为0～2wt.％但不为0wt.％，例如1wt.％，wt.％为占所述扩散基体的总质量的百分比。Wherein, the content of the RH may be 0-2wt.% but not 0wt.%, such as 1wt.%, where wt.% is the percentage of the total mass of the diffusion matrix.
本发明所述扩散基体中，较佳地不含Ga。In the diffusion matrix of the present invention, Ga is preferably not contained.
本发明所述扩散基体中，所述Ga的含量较佳地为0.05～0.5wt.％，例如0.1wt.％或0.2wt.％。In the diffusion matrix of the present invention, the Ga content is preferably 0.05-0.5 wt.%, such as 0.1 wt.% or 0.2 wt.%.
本发明所述扩散基体中，所述B的含量较佳地为0.9～0.98wt.％，例如0.95wt.％。In the diffusion matrix of the present invention, the content of B is preferably 0.9-0.98wt.%, such as 0.95wt.%.
本发明所述扩散基体中，所述Fe的含量一般为余量。所述Fe的含量可为65～69wt.％，例如66.98wt.％、69.32wt.％、65.55wt.％或67.75wt.％。In the diffusion matrix of the present invention, the content of Fe is generally the balance. The content of Fe may be 65-69wt.%, such as 66.98wt.%, 69.32wt.%, 65.55wt.% or 67.75wt.%.
本发明所述扩散基体中，一般还包括本领域内常规的添加元素M，所述M例如包括Al、Co、Cu、Zr、Ti和Nb中的一种或多种。The diffusion matrix of the present invention generally also includes the conventional additive element M in the field, and the M includes, for example, one or more of Al, Co, Cu, Zr, Ti and Nb.
其中，所述M的含量可为本领域常规，可为0～3wt.％但不为0wt.％，例如0.7wt.％、1.12wt.％、1.3wt.％或1.5wt.％，wt.％为占所述扩散基体的总质量的百分比。Wherein, the content of M can be conventional in the art, can be 0～3wt.%, but not 0wt.%, such as 0.7wt.%, 1.12wt.%, 1.3wt.% or 1.5wt.%, wt. % is the percentage of the total mass of the diffusion matrix.
其中，当所述M包含Al时，所述Al的含量可为0～0.5wt.％但不为0wt.％，例如0.02wt.％或0.1wt.％，wt.％为占所述扩散基体的总质量的百分比。Wherein, when the M contains Al, the content of the Al can be 0-0.5wt.% but not 0wt.%, such as 0.02wt.% or 0.1wt.%, wt.% is the proportion of the diffusion matrix percentage of the total mass.
其中，当所述M包含Co时，所述Co的含量可为0～1wt.％但不为0wt.％，例如0.2wt.％、0.5wt.％或0.6wt.％，wt.％为占所述扩散基体的总质量的百分比。Wherein, when the M contains Co, the content of Co can be 0 to 1wt.% but not 0wt.%, such as 0.2wt.%, 0.5wt.% or 0.6wt.%, wt.% is accounted for The percentage of the total mass of the diffusion matrix.
其中，当所述M包含Cu时，所述Cu的含量可为0～1wt.％但不为0wt.％，例如0.2wt.％、0.4wt.％或0.5wt.％，wt.％为占所述扩散基体的总质量的百分比。Wherein, when the M contains Cu, the content of Cu may be 0 to 1wt.% but not 0wt.%, such as 0.2wt.%, 0.4wt.% or 0.5wt.%, and wt.% is accounted for The percentage of the total mass of the diffusion matrix.
其中，当所述M包含Zr时，所述Zr的含量可为0～0.5wt.％但不为0wt.％，例如0.1wt.％，wt.％为占所述扩散基体的总质量的百分比。Wherein, when the M contains Zr, the content of Zr may be 0-0.5wt.% but not 0wt.%, such as 0.1wt.%, and wt.% is the percentage of the total mass of the diffusion matrix .
其中，当所述M包含Ti时，所述Ti的含量可为0～0.5wt.％但不为0wt.％， 例如0.1wt.％，wt.％为占所述扩散基体的总质量的百分比。Wherein, when the M contains Ti, the content of the Ti can be 0-0.5wt.% but not 0wt.%, such as 0.1wt.%, wt.% is the percentage of the total mass of the diffusion matrix .
本发明一较佳实施例中，所述扩散基体由以下组分组成：Nd 25wt.％、Pr 6wt.％、Fe 66.98wt.％、Al 0.02wt.％、Co 0.6wt.％、Cu 0.4wt.％、Zr 0.1wt.％和B 0.9wt.％，wt.％为各组分的质量与所述扩散基体总质量的百分比。In a preferred embodiment of the present invention, the diffusion matrix is composed of the following components: Nd 25wt.%, Pr 6wt.%, Fe 66.98wt.%, Al 0.02wt.%, Co 0.6wt.%, Cu 0.4wt. .%, Zr 0.1wt.% and B 0.9wt.%, wt.% is the percentage of the mass of each component to the total mass of the diffusion matrix.
本发明一较佳实施例中，所述扩散基体由以下组分组成：Nd 27wt.％、Dy 2wt.％、Fe 69.32wt.％、Co 0.2wt.％、Cu 0.2wt.％、Ga 0.2wt.％、Ti 0.1wt.％和B 0.98wt.％，wt.％为各组分的质量与所述扩散基体总质量的百分比。In a preferred embodiment of the present invention, the diffusion matrix is composed of the following components: Nd 27wt.%, Dy 2wt.%, Fe 69.32wt.%, Co 0.2wt.%, Cu 0.2wt.%, Ga 0.2wt .%, Ti 0.1wt.% and B 0.98wt.%, wt.% is the percentage of the mass of each component to the total mass of the diffusion matrix.
本发明一较佳实施例中，所述扩散基体由以下组分组成：Pr 31wt.％、Dy 1wt.％、Fe 65.55wt.％、Co 0.5wt.％、Cu 0.5wt.％、Ga 0.5wt.％和B 0.95wt.％，wt.％为各组分的质量与所述扩散基体总质量的百分比。In a preferred embodiment of the present invention, the diffusion matrix is composed of the following components: Pr 31wt.%, Dy 1wt.%, Fe 65.55wt.%, Co 0.5wt.%, Cu 0.5wt.%, Ga 0.5wt. .% and B 0.95wt.%, wt.% is the percentage of the mass of each component and the total mass of the diffusion matrix.
本发明一较佳实施例中，所述扩散基体由以下组分组成：Nd 26wt.％、Pr 4wt.％、Fe 67.75wt.％、Al 0.1wt.％、Co 0.6wt.％、Cu 0.4wt.％、Ga 0.1wt.％、Zr 0.1wt.％和B 0.95wt.％，wt.％为各组分的质量与所述扩散基体总质量的百分比。In a preferred embodiment of the present invention, the diffusion matrix is composed of the following components: Nd 26wt.%, Pr 4wt.%, Fe 67.75wt.%, Al 0.1wt.%, Co 0.6wt.%, Cu 0.4wt .%, Ga 0.1wt.%, Zr 0.1wt.% and B 0.95wt.%, wt.% is the percentage of the mass of each component to the total mass of the diffusion matrix.
本发明中，本领域技术人员知晓，所述扩散源一般是指所述晶界扩散基体进行晶界扩散处理时添加的待扩散原料。In the present invention, those skilled in the art know that the diffusion source generally refers to the raw material to be diffused that is added when the grain boundary diffusion matrix is subjected to grain boundary diffusion treatment.
本发明所述扩散源中，所述RH的含量较佳地为50～70wt.％，例如55wt.％、60wt.％或65wt.％。所述扩散源中所述RH含量大于70wt.％，虽然矫顽力的提升程度与70wt.％相当，但是会导致成本增加，而且制备难度显著提升。In the diffusion source of the present invention, the content of RH is preferably 50-70wt.%, such as 55wt.%, 60wt.% or 65wt.%. The RH content in the diffusion source is greater than 70wt.%, although the coercive force can be increased to the same extent as 70wt.%, it will lead to increased cost and significantly increased difficulty in preparation.
本发明中，所述扩散源中较佳地不含Ho或Gd。Ho或Gd由于元素自身的性质原因(磁晶各项异性场HA明显低于Dy、Tb)对Hcj的提升效果明显低于Dy和/或Tb。In the present invention, the diffusion source preferably does not contain Ho or Gd. Due to the nature of the element itself (the magnetocrystalline anisotropy field HA is significantly lower than that of Dy and Tb), the effect of Ho or Gd on improving Hcj is significantly lower than that of Dy and/or Tb.
本发明所述扩散源中，所述Ga的含量较佳地为10～40wt.％，例如20wt.％或30wt.％。In the diffusion source of the present invention, the Ga content is preferably 10-40wt.%, such as 20wt.% or 30wt.%.
本发明所述扩散源中，所述Cu的含量较佳地为0～1wt.％或者8～10wt.％，例如为0wt.％或10wt.％。In the diffusion source of the present invention, the content of Cu is preferably 0-1wt.% or 8-10wt.%, such as 0wt.% or 10wt.%.
本发明所述扩散源中，所述Co的含量较佳地为0～1wt.％或者8～10wt.％， 例如为0wt.％或10wt.％。In the diffusion source of the present invention, the content of Co is preferably 0-1wt.% or 8-10wt.%, such as 0wt.% or 10wt.%.
本发明所述扩散源中，所述Al的含量较佳地为0～1wt.％或者4～5wt.％，例如为0wt.％或5wt.％。In the diffusion source of the present invention, the content of Al is preferably 0-1wt.% or 4-5wt.%, such as 0wt.% or 5wt.%.
本发明所述扩散源中，所述Fe的含量较佳地为0～1wt.％或者4～5wt.％，例如为0wt.％或5wt.％。In the diffusion source of the present invention, the content of Fe is preferably 0-1wt.% or 4-5wt.%, such as 0wt.% or 5wt.%.
本发明一较佳实施例中，所述扩散源由以下组分组成：Tb 70wt.％、Cu 10wt.％、Co 10wt.％和Ga 10wt.％，wt.％为各组分的质量与所述扩散源的总质量的百分比。In a preferred embodiment of the present invention, the diffusion source is composed of the following components: Tb 70wt.%, Cu 10wt.%, Co 10wt.% and Ga 10wt.%, wt.% is the mass of each component and the The percentage of the total mass of the diffusion source mentioned above.
本发明一较佳实施例中，所述扩散源由以下组分组成：Tb 65wt.％、Co 10wt.％、Ga 20wt.％和Al 5wt.％，wt.％为各组分的质量与所述扩散源的总质量的百分比。In a preferred embodiment of the present invention, the diffusion source is composed of the following components: Tb 65wt.%, Co 10wt.%, Ga 20wt.% and Al 5wt.%, wt.% is the mass of each component and the The percentage of the total mass of the diffusion source mentioned above.
本发明一较佳实施例中，所述扩散源由以下组分组成：Dy 55wt.％、Cu 10wt.％、Ga 30wt.％和Fe 5wt.％，wt.％为各组分的质量与所述扩散源的总质量的百分比。In a preferred embodiment of the present invention, the diffusion source is composed of the following components: Dy 55wt.%, Cu 10wt.%, Ga 30wt.% and Fe 5wt.%, wt.% is the mass of each component and the The percentage of the total mass of the diffusion source mentioned above.
本发明一较佳实施例中，所述扩散源由以下组分组成：Tb 70wt.％和Ga 30wt.％，wt.％为各组分的质量与所述扩散源的总质量的百分比。In a preferred embodiment of the present invention, the diffusion source is composed of the following components: Tb 70wt.% and Ga 30wt.%, wt.% is the percentage of the mass of each component to the total mass of the diffusion source.
本发明中，本领域技术人员知晓，重稀土元素过多的添加，会导致成本增加同时还可能会导致剩磁降低过多。因此，所述扩散源与所述扩散基体的质量比较佳地在2wt.％以下，优选0.3～1.5wt.％，例如0.3wt.％、0.4wt.％、0.8wt.％或1.2wt.％。In the present invention, those skilled in the art know that excessive addition of heavy rare earth elements will lead to an increase in cost and may also lead to excessive reduction in remanence. Therefore, the mass ratio of the diffusion source and the diffusion matrix is preferably below 2wt.%, preferably 0.3-1.5wt.%, such as 0.3wt.%, 0.4wt.%, 0.8wt.% or 1.2wt.%. .
本发明还提供了一种R-T-B磁体的制备方法，其包括以下步骤：将所述扩散源扩散经晶界扩散处理扩散至所述扩散基体中即可。The present invention also provides a method for preparing an R-T-B magnet, which includes the following steps: diffusing the diffusion source into the diffusion matrix through grain boundary diffusion treatment.
本发明中，所述晶界扩散处理的温度可为本领域常规，较佳地为900℃以下，例如800～900℃。发明人实验中发现，所述晶界扩散处理的温度在900℃以下，实现的矫顽力的提升程度与在900℃以上是相当的(在本发明中800℃与950℃的晶界扩散温度得到的磁体材料的矫顽力提升程度、剩磁改变程度以及温度稳定性变化程度是相当的)，可见本发明的晶界扩散材料不仅带来 了矫顽力的显著提升，而且能耗低。In the present invention, the temperature of the grain boundary diffusion treatment can be conventional in the field, preferably below 900°C, for example, 800-900°C. The inventor found in experiments that the temperature of the grain boundary diffusion treatment is below 900°C, and the degree of coercive force achieved is equivalent to that above 900°C (in the present invention, the grain boundary diffusion temperatures of 800°C and 950°C The degree of coercive force improvement, remanence change degree and temperature stability change degree of the obtained magnet materials are equivalent), it can be seen that the grain boundary diffusion material of the present invention not only brings significant improvement of coercive force, but also has low energy consumption.
本发明中，所述晶界扩散处理的时间可为本领域常规，一般为8～12h，例如10h。In the present invention, the time for the grain boundary diffusion treatment can be conventional in the field, generally 8-12 hours, for example 10 hours.
本发明中，为了使得所述扩散源能够通过所述晶界扩散处理扩散至所述扩散基体中，所述扩散源一般需要进行预处理。In the present invention, in order to enable the diffusion source to diffuse into the diffusion matrix through the grain boundary diffusion treatment, the diffusion source generally needs to be pretreated.
其中，所述的预处理一般将所述扩散源与有机溶剂的混合浆料形成于所述扩散基体的表面。Wherein, the pretreatment generally forms a mixed slurry of the diffusion source and an organic solvent on the surface of the diffusion matrix.
所述扩散源一般为合金粉末的形式。所述的合金粉末一般为将所述扩散源中各组分高温熔融后制粉即可。The diffusion source is generally in the form of an alloy powder. The alloy powder is generally prepared by melting each component in the diffusion source at high temperature and then making it into powder.
所述有机溶剂可为本领域常规，可为醇类溶剂，例如乙醇。The organic solvent can be conventional in the art, and can be an alcoholic solvent, such as ethanol.
其中，所述的扩散源可通过本领域常规的方式形成于所述扩散基体的表面，一般为涂覆或喷涂。Wherein, the diffusion source can be formed on the surface of the diffusion matrix by a conventional method in the art, generally by coating or spraying.
其中，在经所述预处理之后的扩散源涂覆在所述扩散基体的表面形成的厚度可为100μm以下，例如10～50μm。本领域技术人员知晓，所述的厚度一般是指所述有机溶剂挥发完全之后的扩散基体的厚度。Wherein, the thickness of the diffusion source coating formed on the surface of the diffusion substrate after the pretreatment may be less than 100 μm, for example, 10˜50 μm. Those skilled in the art know that the thickness generally refers to the thickness of the diffusion matrix after the organic solvent has completely volatilized.
本发明中所述扩散源在进行晶界扩散时，可无需添加抗氧化剂即能够实现本发明的优异效果。When the diffusion source described in the present invention is performing grain boundary diffusion, the excellent effect of the present invention can be realized without adding an antioxidant.
本发明中，所述扩散基体可采用本领域常规的制备工艺制得，一般将所述扩散基体的混合物依次经熔炼、微粉碎、磁场成型和烧结处理即可。In the present invention, the diffusion matrix can be prepared by conventional preparation techniques in the field. Generally, the mixture of the diffusion matrix is smelted, pulverized, formed in a magnetic field and sintered in sequence.
其中，本领域技术人员知晓，所述扩散基体的原料组合物与最终制得的所述扩散基体中的组分基本一致，本领域技术人员按照所需的扩散基体的组分去配制原料即可，配制时需要考虑稀土的烧损即可。需要说明的是在制备过程中会存在误差范围内的变动。Among them, those skilled in the art know that the raw material composition of the diffusion matrix is basically the same as the components in the final diffusion matrix, and those skilled in the art can prepare the raw materials according to the required components of the diffusion matrix. , it is necessary to consider the burning loss of rare earths during preparation. It should be noted that there may be variations within the error range during the preparation process.
其中，所述熔炼的温度较佳地在1500℃以下，例如1400～1500℃。Wherein, the melting temperature is preferably below 1500°C, such as 1400-1500°C.
其中，所述熔炼的真空度较佳地为5×10 -2Pa。 Wherein, the vacuum degree of the smelting is preferably 5×10 -2 Pa.
其中，所述熔炼之后一般还包括本领域内常规的铸造，所述铸造的环境如为惰性气氛，例如氩气。所述铸造的环境气压例如为5.5万帕。Wherein, conventional casting in the field is generally included after the smelting, and the environment of the casting is an inert atmosphere, such as argon. The atmospheric pressure of the casting is, for example, 55,000 Pa.
所述铸造之后、所述微粉碎之前一般还进行急冷处理以获得急冷合金。Quenching treatment is generally performed after the casting and before the pulverization to obtain a quenched alloy.
所述急冷处理的冷却速度例如为102℃/秒-104℃/秒。The cooling rate of the rapid cooling treatment is, for example, 102°C/sec to 104°C/sec.
其中，所述微粉碎可为本领域常规的破碎工艺，例如依次进行吸氢、脱氢和气流磨处理。Wherein, the fine pulverization may be a conventional crushing process in the art, for example, hydrogen absorption, dehydrogenation and jet milling are performed sequentially.
其中，所述磁场成型的磁场强度可为1.5～2T，例如1.6T。Wherein, the magnetic field strength of the magnetic field shaping may be 1.5-2T, for example, 1.6T.
其中，所述烧结可在真空条件下进行，例如在5×10 -3Pa的真空条件下进行，烧结温度较佳地为1000～1100℃，例如1030℃或1040℃。所述烧结之前、所述磁场成型之后，较佳地还分别在300℃、600℃、800℃的温度下依次进行热处理。 Wherein, the sintering can be carried out under vacuum conditions, such as 5×10 -3 Pa vacuum conditions, and the sintering temperature is preferably 1000-1100°C, such as 1030°C or 1040°C. Before the sintering and after the magnetic field forming, heat treatment is preferably performed sequentially at temperatures of 300°C, 600°C, and 800°C respectively.
其中，所述烧结处理的时间例如为2.5～5h，例如3h或4h。例如在1030℃下烧结3h，再在1040℃下烧结1h。Wherein, the time for the sintering treatment is, for example, 2.5-5 hours, such as 3 hours or 4 hours. For example, sinter at 1030°C for 3h, and then at 1040°C for 1h.
其中，所述烧结处理之后一般还进行冷却处理，所述冷却处理可为将烧结之后得到的磁体材料冷却至90～110℃，例如100℃；所述冷却处理的冷却速率可为10℃/分。Wherein, cooling treatment is generally performed after the sintering treatment, and the cooling treatment may be to cool the magnet material obtained after sintering to 90-110°C, for example, 100°C; the cooling rate of the cooling treatment may be 10°C/min .
本发明中，所述烧结体的尺寸可根据实际需要进行裁剪。例如长度和宽度分别为20mm，厚度为2mm，厚度方向为磁场方向。In the present invention, the size of the sintered body can be tailored according to actual needs. For example, the length and width are 20mm, the thickness is 2mm, and the thickness direction is the direction of the magnetic field.
本发明还提供了一种R-T-B磁体，其采用所述的制备方法制得。The present invention also provides an R-T-B magnet, which is prepared by the preparation method.
本发明还提供了一种R-T-B磁体，其包括以下组分：The present invention also provides a R-T-B magnet, which comprises the following components:
R：28.5～33.5wt.％，所述R为稀土元素，所述R包括HR，所述HR为重稀土元素，所述HR包括Dy和/或Tb；R: 28.5-33.5wt.%, the R is a rare earth element, the R includes HR, the HR is a heavy rare earth element, and the HR includes Dy and/or Tb;
Ga：0.01～0.9wt.％；Ga: 0.01～0.9wt.%;
Cu：0～0.8wt.％；Cu: 0～0.8wt.%;
Co：0～0.8wt.％；Co: 0～0.8wt.%;
Al：0～0.2wt.％；Al: 0～0.2wt.%;
B：0.9～1.02wt.％；B: 0.9～1.02wt.%;
Fe：65～70wt.％，wt.％为各组分的质量与所述R-T-B磁体的总质量的百分比；Fe: 65-70wt.%, wt.% is the percentage of the mass of each component to the total mass of the R-T-B magnet;
所述R-T-B磁体中包括主相和晶界相，所述晶界相为二颗粒晶界相和晶界三角区；The R-T-B magnet includes a main phase and a grain boundary phase, and the grain boundary phase is a two-grain grain boundary phase and a grain boundary triangular region;
所述晶界三角区中包括物相1和物相2；所述物相1中含有Ga 1和Tb 1，所述物相2中含有Ga 2和Tb 2； The grain boundary triangular region includes phase 1 and phase 2; the phase 1 contains Ga 1 and Tb 1 , and the phase 2 contains Ga 2 and Tb 2 ;
Ga 1：X 1mol％； Ga 1 : X 1 mol%;
Tb 1：2mol％以下且不为0； Tb 1 : 2 mol% or less and not 0;
Ga 2：X 2mol％； Ga 2 : X 2 mol%;
Tb 2：2mol％以下且不为0；mol％为各组分与所述晶界相中所有组分的摩尔百分比； Tb 2 : less than 2 mol% and not 0; mol% is the mole percentage of each component and all components in the grain boundary phase;
所述X 1mol％与所述X 2mol％的差值绝对值在10mol％以上； The absolute value of the difference between X 1 mol% and X 2 mol% is above 10 mol%;
“所述物相1和所述物相2”的总面积与所述晶界相的总面积的比值在50％以上。The ratio of the total area of "the phase 1 and the phase 2" to the total area of the grain boundary phase is more than 50%.
本发明中，本领域技术人员知晓，所述晶界三角区一般是指三个主相晶粒之间的间隙。所述二颗粒晶界相一般是指两个主相晶粒之间的间隙。In the present invention, those skilled in the art know that the grain boundary triangular region generally refers to the gap between the three main phase grains. The two-grain boundary phase generally refers to the gap between the two main phase grains.
本发明中，所述物相1和所述物相2的测定方法可为本领域常规，一般是指所述R-T-B磁体的垂直取向面采用FE-EPMA检测得到。本领域技术人员根据所述的物相1或所述的物相2可知，所述物相1一般是由所述Ga 1和所述Tb 1聚集或结合形成，所述物相2一般是由所述Ga 2和所述Tb 2聚集或结合形成。 In the present invention, the measurement methods of the phase 1 and the phase 2 can be conventional in the field, and generally refer to the detection of the vertical orientation plane of the RTB magnet by using FE-EPMA. Those skilled in the art can know according to the phase 1 or the phase 2 that the phase 1 is generally formed by gathering or combining the Ga 1 and the Tb 1 , and the phase 2 is generally formed by The Ga 2 and the Tb 2 are aggregated or combined to form.
本发明中，所述X 1mol％与所述X 2mol％的差值绝对值在10mol％以上，例如10.1mol％、11.85mol％、13.8mol％或14.34mol％。 In the present invention, the absolute value of the difference between X 1 mol% and X 2 mol% is above 10 mol%, such as 10.1 mol%, 11.85 mol%, 13.8 mol% or 14.34 mol%.
本发明所述物相1中，所述Ga 1的含量较佳地为10～20mol％，例如11.29mol％、16.12mol％、17.8mol％或18.35mol％。 In the phase 1 of the present invention, the Ga 1 content is preferably 10-20 mol%, such as 11.29 mol%, 16.12 mol%, 17.8 mol% or 18.35 mol%.
本发明所述物相1中，所述Tb 1的含量较佳地为0.1～1mol％，例如0.3mol％、0.35mol％、0.41mol％或0.5mol％。 In the phase 1 of the present invention, the content of Tb 1 is preferably 0.1-1 mol%, such as 0.3 mol%, 0.35 mol%, 0.41 mol% or 0.5 mol%.
本发明所述物相2中，所述Ga 2的含量较佳地为1～5mol％，例如1.19mol％、4.01mol％、4mol％或4.27mol％。 In the phase 2 of the present invention, the Ga 2 content is preferably 1-5 mol%, such as 1.19 mol%, 4.01 mol%, 4 mol% or 4.27 mol%.
本发明所述物相2中，所述Tb 2的含量较佳地为0.1～1mol％，例如0.3mol％、0.31mol％或0.32mol％。 In the phase 2 of the present invention, the content of Tb 2 is preferably 0.1-1 mol%, such as 0.3 mol%, 0.31 mol% or 0.32 mol%.
本发明中，“所述物相1和所述物相2”的总面积与所述晶界相的总面积的比值较佳地为50～70％，例如52％、58％、61％或67％。In the present invention, the ratio of the total area of "the phase 1 and the phase 2" to the total area of the grain boundary phase is preferably 50-70%, such as 52%, 58%, 61% or 67%.
本发明中，所述R的含量较佳地为28.5～32wt.％，例如29.88wt.％、30.02wt.％、30.6wt.％、30.61wt.％或31.64wt.％。In the present invention, the content of R is preferably 28.5-32wt.%, such as 29.88wt.%, 30.02wt.%, 30.6wt.%, 30.61wt.% or 31.64wt.%.
本发明中，本领域技术人员知晓，所述R一般至少含有LR，LR为轻稀土元素，所述LR包括Nd和/或Pr。所述“Nd和/或Pr”的质量与所述稀土元素的总质量的比值较佳地在2/3以上。In the present invention, those skilled in the art know that the R generally contains at least LR, and LR is a light rare earth element, and the LR includes Nd and/or Pr. The ratio of the mass of "Nd and/or Pr" to the total mass of the rare earth elements is preferably more than 2/3.
其中，所述LR的含量可为本领域常规，一般为21～32wt.％，例如27.5wt.％、29.73wt.％、30wt.％或30.4wt.％。Wherein, the content of LR can be conventional in the field, generally 21-32wt.%, such as 27.5wt.%, 29.73wt.%, 30wt.% or 30.4wt.%.
其中，当所述LR含有Nd时，所述Nd的含量较佳地为21～32wt.％，例如24.6wt.％、25.92wt.％或27.5wt.％，wt.％为占所述R-T-B磁体的总质量的百分比。Wherein, when the LR contains Nd, the content of Nd is preferably 21-32wt.%, such as 24.6wt.%, 25.92wt.% or 27.5wt.%. percentage of the total mass.
其中，当所述LR含有Pr时，所述Pr的含量较佳地为2～31wt.％，例如3.81wt.％、5.8wt.％或30.5wt.％。Wherein, when the LR contains Pr, the content of the Pr is preferably 2-31wt.%, such as 3.81wt.%, 5.8wt.% or 30.5wt.%.
本发明中，所述HR的含量较佳地为0.2～3wt.％，例如0.21wt.％、0.29wt.％、1.64wt.％或2.38wt.％。In the present invention, the content of HR is preferably 0.2-3wt.%, such as 0.21wt.%, 0.29wt.%, 1.64wt.% or 2.38wt.%.
本发明中，当所述HR含量Dy时，所述Dy的含量较佳地为1～2wt.％，例如1.64wt.％或1.85wt.％。In the present invention, when the HR content is Dy, the Dy content is preferably 1-2 wt.%, such as 1.64 wt.% or 1.85 wt.%.
本发明中，当所述HR含有Tb时，所述Tb的含量较佳地为0.2～1wt.％，例如0.21wt.％、0.29wt.％或0.53wt.％。In the present invention, when the HR contains Tb, the content of Tb is preferably 0.2-1 wt.%, such as 0.21 wt.%, 0.29 wt.% or 0.53 wt.%.
本发明中，所述Ga的含量较佳地为0.02～0.85wt.％，例如0.03wt.％、0.21wt.％、0.35wt.％或0.82wt.％。In the present invention, the Ga content is preferably 0.02-0.85wt.%, such as 0.03wt.%, 0.21wt.%, 0.35wt.% or 0.82wt.%.
本发明中，所述Cu的含量较佳地为0.1～0.7wt.％，例如0.2wt.％、0.4wt.％、0.43wt.％或0.61wt.％。In the present invention, the content of Cu is preferably 0.1-0.7wt.%, such as 0.2wt.%, 0.4wt.%, 0.43wt.% or 0.61wt.%.
本发明中，所述Co的含量较佳地为0.2～0.7wt.％，例如0.28wt.％、0.5wt.％、 0.6wt.％、0.62wt.％或0.63wt.％。In the present invention, the content of Co is preferably 0.2-0.7wt.%, such as 0.28wt.%, 0.5wt.%, 0.6wt.%, 0.62wt.% or 0.63wt.%.
本发明中，所述Al的含量较佳地为0.01～0.15wt.％，例如0.03wt.％、0.05wt.％或0.12wt.％。In the present invention, the content of Al is preferably 0.01-0.15wt.%, such as 0.03wt.%, 0.05wt.% or 0.12wt.%.
本发明中，所述B的含量较佳地为0.9～1wt.％，例如0.91wt.％、0.95wt.％或0.98wt.％。In the present invention, the content of B is preferably 0.9-1wt.%, such as 0.91wt.%, 0.95wt.% or 0.98wt.%.
本发明中，所述Fe的含量较佳地为65～69wt.％，66.63wt.％、67.38wt.％、64.3wt.％或67.21wt.％。In the present invention, the content of Fe is preferably 65-69wt.%, 66.63wt.%, 67.38wt.%, 64.3wt.% or 67.21wt.%.
本发明中，所述R-T-B磁体中还可包括本领域内其他的常规添加元素，例如Zr、Ti和Nb中的一种或多种。In the present invention, the R-T-B magnet may also include other conventional additive elements in the art, such as one or more of Zr, Ti and Nb.
其中，当所述R-T-B磁体中包含Zr，所述Zr的含量较佳地为0～0.5wt.％但不为0wt.％，例如0.1wt.％。Wherein, when the R-T-B magnet contains Zr, the content of Zr is preferably 0-0.5wt.%, but not 0wt.%, such as 0.1wt.%.
其中，当所述R-T-B磁体中包含Ti，所述Ti的含量较佳地为0～0.5wt.％但不为0wt.％，例如0.1wt.％。Wherein, when the R-T-B magnet contains Ti, the content of Ti is preferably 0-0.5wt.% but not 0wt.%, for example 0.1wt.%.
本发明一较佳实施例中，所述R-T-B磁体由以下组分组成：Nd 24.6wt.％、Pr 5.8wt.％、Tb 0.2wt.％、Fe 66.63wt.％、Al 0.03wt.％、Co 0.63wt.％、Cu 0.43wt.％、Ga 0.03wt.％、Zr 0.1wt.％和B 0.9wt.％，wt.％为各组分的质量与所述R-T-B磁体的总质量的百分比；所述R-T-B磁体包括主相和晶界相，所述晶界相为二颗粒晶界相和晶界三角区，所述晶界三角区包括物相1和物相2，所述物相1含有11.29mol％的Ga和0.35mol％的Tb，所述物相2中含有1.19mol％的Ga和0.31mol％的Tb，mol％为占所述晶界相中所有组分的摩尔百分比，“所述物相1和所述物相2”的总面积与所述晶界相的总面积的比值为52％。In a preferred embodiment of the present invention, the R-T-B magnet is composed of the following components: Nd 24.6wt.%, Pr 5.8wt.%, Tb 0.2wt.%, Fe 66.63wt.%, Al 0.03wt.%, Co 0.63wt.%, Cu 0.43wt.%, Ga 0.03wt.%, Zr 0.1wt.% and B 0.9wt.%, wt.% is the percentage of the mass of each component and the total mass of the R-T-B magnet; The R-T-B magnet includes a main phase and a grain boundary phase, and the grain boundary phase is a two-grain grain boundary phase and a grain boundary triangular region, and the grain boundary triangular region includes a phase 1 and a phase 2, and the phase 1 contains 11.29 mol% of Ga and 0.35mol% of Tb, the phase 2 contains 1.19mol% of Ga and 0.31mol% of Tb, and mol% is the mole percent of all components in the grain boundary phase, "the The ratio of the total area of the phase 1 and the phase 2" to the total area of the grain boundary phase was 52%.
本发明一较佳实施例中，所述R-T-B磁体由以下组分组成：Nd 27.5wt.％、Dy 1.85wt.％、Tb 0.53wt.％、Fe 67.38wt.％、Al 0.05wt.％、Co 0.28wt.％、Cu 0.2wt.％、Ga 0.35wt.％、Ti 0.1wt.％和B 1wt.％，wt.％为各组分的质量与所述R-T-B磁体的总质量的百分比；所述R-T-B磁体包括主相和晶界相，所述晶界相为二颗粒晶界相和晶界三角区，所述晶界三角区包括物相1和物相2， 所述物相1含有16.12mol％的Ga和0.41mol％的Tb，所述物相2中含有4.27mol％的Ga和0.32mol％的Tb，mol％为占所述晶界相中所有组分的摩尔百分比，“所述物相1和所述物相2”的总面积与所述晶界相的总面积的比值为61％。In a preferred embodiment of the present invention, the R-T-B magnet is composed of the following components: Nd 27.5wt.%, Dy 1.85wt.%, Tb 0.53wt.%, Fe 67.38wt.%, Al 0.05wt.%, Co 0.28wt.%, Cu 0.2wt.%, Ga 0.35wt.%, Ti 0.1wt.% and B 1wt.%, wt.% is the percentage of the mass of each component and the total mass of the R-T-B magnet; The R-T-B magnet includes a main phase and a grain boundary phase. The grain boundary phase is a two-grain grain boundary phase and a grain boundary triangular area. The grain boundary triangular area includes a phase 1 and a phase 2. The phase 1 contains 16.12mol % of Ga and 0.41mol% of Tb, the phase 2 contains 4.27mol% of Ga and 0.32mol% of Tb, and mol% is the mole percentage of all components in the grain boundary phase, "the The ratio of the total area of phase 1 and the phase 2" to the total area of the grain boundary phase is 61%.
本发明一较佳实施例中，所述R-T-B磁体由以下组分组成：Pr 30.5wt.％、Dy 1.64wt.％、Fe 64.3wt.％、Co 0.5wt.％、Cu 0.61wt.％、Ga 0.82wt.％和B 0.95wt.％，wt.％为各组分的质量与所述R-T-B磁体的总质量的百分比；所述R-T-B磁体包括主相和晶界相，所述晶界相为二颗粒晶界相和晶界三角区，所述晶界三角区包括物相1和物相2，所述物相1含有18.35mol％的Ga和0.3mol％的Tb，所述物相2中含有4.01mol％的Ga和0.32mol％的Tb，mol％为占所述晶界相中所有组分的摩尔百分比，“所述物相1和所述物相2”的总面积与所述晶界相的总面积的比值为67％。In a preferred embodiment of the present invention, the R-T-B magnet is composed of the following components: Pr 30.5wt.%, Dy 1.64wt.%, Fe 64.3wt.%, Co 0.5wt.%, Cu 0.61wt.%, Ga 0.82wt.% and B 0.95wt.%, wt.% is the percentage of the mass of each component and the total mass of the R-T-B magnet; the R-T-B magnet includes a main phase and a grain boundary phase, and the grain boundary phase is two Grain boundary phase and grain boundary triangular region, the grain boundary triangular region includes phase 1 and phase 2, the phase 1 contains 18.35mol% of Ga and 0.3mol% of Tb, and the phase 2 contains 4.01mol% of Ga and 0.32mol% of Tb, mol% is the mole percentage of all components in the grain boundary phase, the total area of "the phase 1 and the phase 2" is related to the grain boundary The ratio of the total area of the phases was 67%.
本发明一较佳实施例中，所述R-T-B磁体由以下组分组成：Nd 25.92wt.％、Pr 3.81wt.％、Tb 0.29wt.％、Fe 67.21wt.％、Al 0.12wt.％、Co 0.6wt.％、Cu 0.4wt.％、Ga 0.21wt.％、Zr 0.1wt.％和B 0.95wt.％，wt.％为各组分的质量与所述R-T-B磁体的总质量的百分比；所述R-T-B磁体包括主相和晶界相，所述晶界相为二颗粒晶界相和晶界三角区，所述晶界三角区包括物相1和物相2，所述物相1含有17.8mol％的Ga和0.5mol％的Tb，所述物相2中含有4mol％的Ga和0.3mol％的Tb，mol％为占所述晶界相中所有组分的摩尔百分比，“所述物相1和所述物相2”的总面积与所述晶界相的总面积的比值为58％。In a preferred embodiment of the present invention, the R-T-B magnet is composed of the following components: Nd 25.92wt.%, Pr 3.81wt.%, Tb 0.29wt.%, Fe 67.21wt.%, Al 0.12wt.%, Co 0.6wt.%, Cu 0.4wt.%, Ga 0.21wt.%, Zr 0.1wt.% and B 0.95wt.%, wt.% is the percentage of the mass of each component and the total mass of the R-T-B magnet; The R-T-B magnet includes a main phase and a grain boundary phase, and the grain boundary phase is a two-grain grain boundary phase and a grain boundary triangular region, and the grain boundary triangular region includes a phase 1 and a phase 2, and the phase 1 contains 17.8 mol% of Ga and 0.5mol% of Tb, the phase 2 contains 4mol% of Ga and 0.3mol% of Tb, and mol% is the mole percentage of all components in the grain boundary phase, "the The ratio of the total area of phase 1 and the phase 2" to the total area of the grain boundary phase is 58%.
在符合本领域常识的基础上，上述各优选条件，可任意组合，即得本发明各较佳实例。On the basis of conforming to common knowledge in the field, the above-mentioned preferred conditions can be combined arbitrarily to obtain preferred examples of the present invention.
本发明所用试剂和原料均市售可得。The reagents and raw materials used in the present invention are all commercially available.
本发明的积极进步效果在于：本发明中特定含量Ga和重稀土元素的扩散源并控制所述扩散源中Cu、Co和Al的含量，配合特定组分的扩散基体，通过所述的晶界扩散之后，扩散源中的Ga优先占据晶界三角区，形成含Ga物相，这种物相和Tb结合极少，使Tb更多地进入晶粒外壳层或是向内扩散， 进而显著提高了扩散效果，使得矫顽力有显著的提升同时还维持较高的剩磁和温度稳定性。The positive progress effect of the present invention is: the diffusion source of specific content Ga and heavy rare earth element in the present invention and control the content of Cu, Co and Al in described diffusion source, coordinate the diffusion matrix of specific composition, pass described grain boundary After diffusion, Ga in the diffusion source preferentially occupies the triangular area of the grain boundary, forming a Ga-containing phase, which is rarely combined with Tb, so that Tb enters the outer layer of the grain more or diffuses inward, thereby significantly improving The diffusion effect is improved, the coercive force is significantly improved while maintaining high remanence and temperature stability.
附图说明Description of drawings
图1为实施例1的R-T-B磁体的微观结构。FIG. 1 is the microstructure of the R-T-B magnet of Example 1. FIG.
具体实施方式Detailed ways
下面通过实施例的方式进一步说明本发明，但并不因此将本发明限制在所述的实施例范围之中。下列实施例中未注明具体条件的实验方法，按照常规方法和条件，或按照商品说明书选择。The present invention is further illustrated below by means of examples, but the present invention is not limited to the scope of the examples. For the experimental methods that do not specify specific conditions in the following examples, select according to conventional methods and conditions, or according to the product instructions.
实施例1Example 1
(1)烧结体(扩散基体)的制备(1) Preparation of sintered body (diffusion matrix)
①熔炼铸造：按照表1的配方将烧结体中所需的各组分原材料混合，在高频真空感应炉中在5×10 -2Pa的真空中以1500℃以下的温度进行真空熔炼。在真空熔炼后的熔炼炉中通入Ar气体使气压达到5.5万帕后，进行铸造，并以10 2℃/秒-10 4℃/秒的冷却速度获得急冷合金。 ①Smelting and casting: According to the formula in Table 1, mix the raw materials of each component required in the sintered body, and carry out vacuum melting at a temperature below 1500°C in a vacuum of 5×10 -2 Pa in a high-frequency vacuum induction furnace. After vacuum smelting, Ar gas is introduced into the smelting furnace to make the pressure reach 55,000 Pa, and then casting is carried out, and a quenched alloy is obtained at a cooling rate of 10 2 °C/s-10 4 °C/s.
②微粉碎：在室温下将放置急冷合金的氢破用炉抽真空，然后向氢破用炉内通入纯度为99.9％的氢气，维持氢气压力0.1MPa；充分吸氢后，边抽真空边升温，充分脱氢；然后进行冷却，取出氢破粉碎后的粉末。② Micro-grinding: Vacuumize the hydrogen blasting furnace where the quenched alloy is placed at room temperature, and then pass hydrogen gas with a purity of 99.9% into the hydrogen crushing furnace to maintain the hydrogen pressure at 0.1 MPa; after fully absorbing hydrogen, vacuum while Raise the temperature to fully dehydrogenate; then cool down and take out the powder after hydrogen crushing.
在氧化气体含量150ppm以下的氮气气氛下，在粉碎室压力为0.38MPa的条件下对氢破粉碎后的粉末进行3h的气流磨粉碎，得到细粉。氧化气体指的是氧或水分。In a nitrogen atmosphere with an oxidizing gas content of less than 150ppm, and under the condition of a crushing chamber pressure of 0.38 MPa, the powder after hydrogen crushing was pulverized by a jet mill for 3 hours to obtain a fine powder. Oxidizing gas refers to oxygen or moisture.
在气流磨粉碎后的粉末中添加硬脂酸锌，硬脂酸锌的添加量为混合后粉末重量的0.12％，再用V型混料机充分混合。Add zinc stearate to the powder pulverized by the jet mill, and the addition amount of zinc stearate is 0.12% of the powder weight after mixing, and then fully mix with a V-shaped mixer.
③成型：用直角取向型的磁场成型机，在1.6T的取向磁场中，以及在0.35ton/cm 2的成型压力下，将上述添加了硬脂酸锌的粉末一次成型为边长25mm的立方体，一次成型后在0.2T的磁场中退磁。 ③Molding: Using a right-angle orientation magnetic field molding machine, in an orientation magnetic field of 1.6T, and under a molding pressure of 0.35ton/ cm2 , the above-mentioned powder added with zinc stearate is molded into a cube with a side length of 25mm at one time , Demagnetized in a 0.2T magnetic field after one molding.
④烧结：将各成型体搬至烧结炉进行烧结，烧结在5×10 -3Pa的真空下以及分别在300℃、600℃、800℃的温度下各保持1h后，以1030℃的温度烧结3h，再以1040℃的温度烧结1h，之后通入Ar气体使气压达到0.1MPa后，以10℃/分的冷却速度冷却至100℃。 ④ Sintering: Move each molded body to a sintering furnace for sintering, sintering at a vacuum of 5×10 -3 Pa and at a temperature of 300°C, 600°C, and 800°C for 1 hour, and then sintering at a temperature of 1030°C 3h, and then sintered at a temperature of 1040°C for 1h, and then passed Ar gas to make the pressure reach 0.1MPa, and then cooled to 100°C at a cooling rate of 10°C/min.
(2)R-T-B磁体的制备(2) Preparation of R-T-B magnet
将上述制得的烧结体加工成长宽20mm、厚度2mm的磁铁，厚度方向为磁场取向方向，表面洁净化后备用；按照如下表2中的配方将扩散源配制成合金粉末并制备成浆料涂覆在扩散基体的表面，涂覆的厚度在100μm以下，且无需添加抗氧化剂。合金粉末为将扩散源中各组分共同高温熔融后制粉后，使用乙醇作为溶剂喷涂于扩散基体的表面，之后将该磁体在800～900℃下进行晶界扩散处理，晶界扩散处理的时间为10h。The sintered body obtained above is processed into a magnet with a length and width of 20mm and a thickness of 2mm, the thickness direction is the direction of magnetic field orientation, and the surface is cleaned for later use; the diffusion source is formulated into alloy powder according to the formula in Table 2 below and prepared into a slurry coating Coated on the surface of the diffusion matrix, the thickness of the coating is less than 100 μm, and there is no need to add antioxidants. The alloy powder is made by melting all the components in the diffusion source together at high temperature, then spraying the surface of the diffusion matrix with ethanol as a solvent, and then performing grain boundary diffusion treatment on the magnet at 800-900°C. The time is 10h.
实施例2～4和对比例1～4的扩散基体和扩散源的配方如下表1和表2所示，制备工艺同实施例1，实施例2～4和对比例1～4中扩散源在扩散基体上的涂覆厚度在100μm以下。The formulations of the diffusion matrix and diffusion source of Examples 2-4 and Comparative Examples 1-4 are shown in Table 1 and Table 2 below, and the preparation process is the same as in Example 1, and the diffusion source in Examples 2-4 and Comparative Examples 1-4 is The coating thickness on the diffusion substrate is below 100 μm.
表1扩散基体(单位wt.％，各组分质量与扩散基体总质量的百分比)Table 1 Diffusion matrix (unit wt.%, the percentage of the mass of each component to the total mass of the diffusion matrix)
 the NdNd PrPR DyDy TbTb FeFe Alal Coco CuCu GaGa ZrZr TiTi BB
实施例1Example 1 2525 66 // // 66.9866.98 0.020.02 0.60.6 0.40.4 // 0.10.1 // 0.90.9
实施例2Example 2 2727 // 22 // 69.3269.32 // 0.20.2 0.20.2 0.20.2 // 0.10.1 0.980.98
实施例3Example 3 // 3131 11 // 65.5565.55 // 0.50.5 0.50.5 0.50.5 // // 0.950.95
实施例4Example 4 2626 44 // // 67.7567.75 0.10.1 0.60.6 0.40.4 0.10.1 0.10.1 // 0.950.95
对比例1Comparative example 1 2525 66 // // 66.3866.38 0.020.02 0.60.6 0.40.4 0.60.6 0.10.1 // 0.90.9
对比例2Comparative example 2 2525 66 // // 66.9366.93 0.020.02 0.60.6 0.40.4 0.10.1 0.10.1 // 0.850.85
对比例3Comparative example 3 2626 44 // // 67.7567.75 0.10.1 0.60.6 0.40.4 0.10.1 0.10.1 // 0.950.95
对比例4Comparative example 4 2626 44 // // 67.7567.75 0.10.1 0.60.6 0.40.4 0.10.1 0.10.1 // 0.950.95
表2扩散源(单位wt.％，各组分质量与扩散源总质量的百分比)Table 2 Diffusion source (unit wt.%, the percentage of the mass of each component to the total mass of the diffusion source)
Figure PCTCN2022129743-appb-000001
Figure PCTCN2022129743-appb-000001
Figure PCTCN2022129743-appb-000002
Figure PCTCN2022129743-appb-000002
效果实施例1Effect Example 1
1、R-T-B磁体的成分测定1. Composition determination of R-T-B magnet
使用高频电感耦合等离子体发射光谱仪(ICP-OES)进行测定。测试结果如下表3所示。Measurements were performed using a high-frequency inductively coupled plasma optical emission spectrometer (ICP-OES). The test results are shown in Table 3 below.
表3(单位wt.％，为各元素的质量与R-T-B磁体总质量的百分比)Table 3 (unit wt.%, which is the percentage of the mass of each element to the total mass of the R-T-B magnet)
 the NdNd PrPR DyDy TbTb FeFe Alal Coco CuCu GaGa ZrZr TiTi BB
实施例1Example 1 24.624.6 5.85.8 // 0.20.2 66.6366.63 0.030.03 0.630.63 0.430.43 0.030.03 0.10.1 // 0.90.9
实施例2Example 2 27.527.5 // 1.851.85 0.530.53 67.3867.38 0.050.05 0.280.28 0.20.2 0.350.35 // 0.10.1 11
实施例3Example 3 // 30.530.5 1.641.64 // 64.3064.30 // 0.50.5 0.610.61 0.820.82 // // 0.950.95
实施例4Example 4 25.9225.92 3.813.81 // 0.290.29 67.2167.21 0.120.12 0.60.6 0.40.4 0.210.21 0.10.1 // 0.950.95
对比例1Comparative example 1 24.724.7 5.75.7 // 0.210.21 65.8465.84 0.030.03 0.620.62 0.430.43 0.620.62 0.10.1 // 0.910.91
对比例2Comparative example 2 24.624.6 5.65.6 // 0.220.22 66.4866.48 0.030.03 0.630.63 0.420.42 0.120.12 0.10.1 // 0.840.84
对比例3Comparative example 3 25.8925.89 3.963.96 // 0.290.29 67.0867.08 0.120.12 0.640.64 0.440.44 0.110.11 0.10.1 // 0.950.95
对比例4Comparative example 4 25.8525.85 3.933.93 // 0.280.28 67.167.1 0.150.15 0.620.62 0.420.42 0.140.14 0.10.1 // 0.950.95
2、磁性能检测2. Magnetic performance testing
实施例和对比例中的烧结体和R-T-B磁体，使用PFM脉冲式退磁曲线测试设备测试磁性能。测试结果如下表4所示。ΔHcj是指制得的R-T-B磁体的矫顽力减去相应的扩散前烧结体的矫顽力得到的值。测试温度为20℃。The magnetic properties of the sintered bodies and R-T-B magnets in Examples and Comparative Examples were tested using PFM pulsed demagnetization curve testing equipment. The test results are shown in Table 4 below. ΔHcj refers to the value obtained by subtracting the coercive force of the corresponding sintered body before diffusion from the coercive force of the obtained R-T-B magnet. The test temperature is 20°C.
表4Table 4
Figure PCTCN2022129743-appb-000003
Figure PCTCN2022129743-appb-000003
3、微观结构表征3. Microstructure characterization
对实施例1-4和对比例1-4中的R-T-B磁体的垂直取向面进行抛光，采用场发射电子探针显微分析仪(FE-EPMA)(日本电子株式会社(JEOL)，8530F)检测。发现在距离扩散面(是指R-T-B磁体的制备中，扩散基体上涂覆扩散源的表面)的深度0～300μm均可观察到含Ga和Tb的物相。通过FE-EPMA单点定量分析确定R-T-B磁体中晶界处Tb、Ga元素的含量，测试条件为加速电压15kv，探针束流50nA。测试结果如下表5所示。The vertically oriented surfaces of the R-T-B magnets in Examples 1-4 and Comparative Examples 1-4 are polished, and are detected by Field Emission Electron Probe Microanalyzer (FE-EPMA) (JEOL, 8530F) . It is found that phases containing Ga and Tb can be observed at a depth of 0-300 μm from the diffusion surface (referring to the surface of the diffusion substrate coated with the diffusion source in the preparation of the R-T-B magnet). The contents of Tb and Ga elements at grain boundaries in R-T-B magnets were determined by FE-EPMA single-point quantitative analysis. The test conditions were acceleration voltage 15kv and probe beam current 50nA. The test results are shown in Table 5 below.
如图1显示了实施例1中R-T-B磁体的微观结构和三角晶界区的晶界成分，图中点6为低Ga相，点7为高Ga相。Ga占据三角晶界区，形成较多高Ga相，高Ga相和低Ga相具有10mol％以上的浓度差，且Tb含量低，同时将观测二颗粒晶界相中仅含有较少的Ga。经进一步研究推测，该物相在晶界三角区可降低晶界相的熔点，具有较好的润湿性，使得晶界均匀、连续。同时，高Ga相和低Ga相对Tb存在排异现象，Tb含量极低，一般不超过2mol％，可减少Tb元素在晶界处的消耗，使其沿晶界扩散深度更大，更有效被利用。Figure 1 shows the microstructure of the R-T-B magnet in Example 1 and the grain boundary composition of the triangular grain boundary region, point 6 in the figure is the low Ga phase, and point 7 is the high Ga phase. Ga occupies the triangular grain boundary area, forming more high Ga phases, and the high Ga phase and low Ga phase have a concentration difference of more than 10 mol%, and the Tb content is low, and it will be observed that the two-grain grain boundary phase only contains less Ga. After further research, it is speculated that the phase in the triangular region of the grain boundary can lower the melting point of the grain boundary phase, and has better wettability, making the grain boundary uniform and continuous. At the same time, the high Ga phase and low Ga phase have a phenomenon of rejection relative to Tb, and the Tb content is extremely low, generally not exceeding 2mol%, which can reduce the consumption of Tb elements at the grain boundary, make it diffuse deeper along the grain boundary, and be more effectively absorbed. use.
表5table 5
Figure PCTCN2022129743-appb-000004
Figure PCTCN2022129743-appb-000004
注：mol％为占晶界相中所有元素总摩尔量的比值；Note: mol% is the ratio of the total molar weight of all elements in the grain boundary phase;
物相1和物相2位于晶界三角区，物相1+物相2的面积占比是指物相1和物相2的总面积与晶界相总面积的比值。Phase 1 and phase 2 are located in the grain boundary triangle area, and the area ratio of phase 1+phase 2 refers to the ratio of the total area of phase 1 and phase 2 to the total area of the grain boundary phase.
根据上述表1-3的配方、表4的磁性能数据以及表5的微观结构数据可知，本发明通过特定的扩散基体和扩散源的配合，经晶界扩散处理之后，矫顽力相较于扩散基体提升了10kOe以上，同时重稀土使用量也较少，进一步地，晶界扩散处理的温度低，实现了能耗低、材料成本低的前提下，还使得矫顽力有显著的提升且剩磁基本不变，同时温度稳定性还得到明显提升。According to the formula of above-mentioned Table 1-3, the magnetic property data of Table 4 and the microstructure data of Table 5, the present invention cooperates through specific diffusion matrix and diffusion source, and after grain boundary diffusion treatment, coercive force is compared with The diffusion matrix has been increased by more than 10kOe, and the amount of heavy rare earth used is also less. Further, the temperature of the grain boundary diffusion treatment is low, which realizes low energy consumption and low material cost, and also significantly improves the coercive force. The remanence is basically unchanged, and the temperature stability has also been significantly improved.
本发明的实现是研发人员经过多次试验意外获得，在研发的过程中经过了多次失败的实验，例如在制备扩散基体时，Ga的含量过高、B的含量过低或过高，在制备扩散源时，Ga的含量过低、未控制其他元素的含量(Cu、Co、Fe和Al)在经晶界扩散处理时，均未能够实现矫顽力的显著提升。The realization of the present invention is obtained by the research and development staff through many experiments by accident, and has passed through many failed experiments in the process of research and development. For example, when preparing the diffusion matrix, the content of Ga is too high, and the content of B is too low or too high. When the diffusion source was prepared, the content of Ga was too low, and the content of other elements (Cu, Co, Fe, and Al) was not controlled. After the grain boundary diffusion treatment, the coercive force could not be significantly improved.

Claims (10)

  1. 一种R-T-B磁体的晶界扩散材料，其特征在于，其包括扩散基体和扩散源；A grain boundary diffusion material of an R-T-B magnet, characterized in that it includes a diffusion matrix and a diffusion source;
    所述扩散基体包括以下组分：R：28.5～33.5wt.％，R为稀土元素；The diffusion matrix includes the following components: R: 28.5-33.5wt.%, R is a rare earth element;
    Ga：0～0.5wt.％；Ga: 0～0.5wt.%;
    B：0.9～1.02wt.％；B: 0.9～1.02wt.%;
    Fe：65～70wt.％，wt.％为各组分的质量与所述扩散基体的总质量的百分比；Fe: 65-70wt.%, wt.% is the percentage of the mass of each component to the total mass of the diffusion matrix;
    所述扩散源包括以下组分：The diffusion source includes the following components:
    HR：0～70wt.％但不为0wt.％；HR: 0~70wt.% but not 0wt.%;
    所述HR为重稀土元素，所述HR包括Dy和/或Tb；The HR is a heavy rare earth element, and the HR includes Dy and/or Tb;
    Ga≥10wt.％；Ga≥10wt.%;
    Cu：0～10wt.％；Cu: 0～10wt.%;
    Co：0～10wt.％；Co: 0～10wt.%;
    Al：0～8wt.％；Al: 0～8wt.%;
    Fe：0～8wt.％；wt.％为各组分的质量与所述扩散源的总质量的百分比。Fe: 0-8wt.%; wt.% is the percentage of the mass of each component to the total mass of the diffusion source.
  2. 如权利要求1所述的R-T-B磁体的晶界扩散材料，其特征在于，所述扩散基体为烧结体；The grain boundary diffusion material of the R-T-B magnet according to claim 1, wherein the diffusion matrix is a sintered body;
    和/或，所述扩散基体中，所述R的含量为28～32wt.％，例如29wt.％、30wt.％或31wt.％；And/or, in the diffusion matrix, the R content is 28-32wt.%, such as 29wt.%, 30wt.% or 31wt.%.
    和/或，所述扩散基体中，所述R至少含有LR，LR为轻稀土元素，所述LR较佳地包括Nd和/或Pr，且所述“Nd和/或Pr”的质量与所述稀土元素的总质量的比值为2/3以上；And/or, in the diffusion matrix, the R contains at least LR, and LR is a light rare earth element, and the LR preferably includes Nd and/or Pr, and the quality of the "Nd and/or Pr" is the same as that of the The ratio of the total mass of the rare earth elements is more than 2/3;
    当所述R包含Nd时，所述Nd的含量较佳地为21～32wt.％，例如25wt.％、26wt.％或27wt.％，wt.％为占所述扩散基体的总质量的百分比；When the R contains Nd, the content of Nd is preferably 21-32wt.%, such as 25wt.%, 26wt.% or 27wt.%, and wt.% is the percentage of the total mass of the diffusion matrix ;
    当所述R包含Pr时，所述Pr的含量较佳地为4～32wt.％，例如6wt.％、15wt.％、20wt.％、25wt.％或31wt.％，wt.％为占所述扩散基体的总质量的百分比；When the R contains Pr, the content of the Pr is preferably 4 to 32wt.%, such as 6wt.%, 15wt.%, 20wt.%, 25wt.% or 31wt.%, wt.% is the total The percentage of the total mass of the diffusion matrix;
    和/或，所述R中还包括RH，RH为重稀土元素；And/or, said R also includes RH, and RH is a heavy rare earth element;
    其中，所述RH较佳地包括Dy和/或Tb；Wherein, the RH preferably includes Dy and/or Tb;
    其中，所述RH的含量较佳地为0～2wt.％但不为0wt.％，例如1wt.％，wt.％为占所述扩散基体的总质量的百分比；Wherein, the content of RH is preferably 0-2wt.% but not 0wt.%, such as 1wt.%, where wt.% is the percentage of the total mass of the diffusion matrix;
    和/或，所述扩散基体中，所述Ga的含量为0.05～0.5wt.％，例如0.1wt.％或0.2wt.％；或者，所述扩散基体中不含Ga；And/or, in the diffusion matrix, the Ga content is 0.05-0.5wt.%, such as 0.1wt.% or 0.2wt.%; or, the diffusion matrix does not contain Ga;
    和/或，所述扩散基体中，所述B的含量为0.9～0.98wt.％，例如0.95wt.％；And/or, in the diffusion matrix, the content of B is 0.9-0.98wt.%, such as 0.95wt.%.
    和/或，所述扩散基体中，所述Fe的含量为65～69wt.％，例如66.98wt.％、69.32wt.％、65.55wt.％或67.75wt.％；And/or, in the diffusion matrix, the Fe content is 65-69wt.%, such as 66.98wt.%, 69.32wt.%, 65.55wt.% or 67.75wt.%.
    和/或，所述扩散基体中还包括M，所述M包括Al、Co、Cu、Zr、Ti和Nb中的一种或多种；And/or, the diffusion matrix further includes M, and the M includes one or more of Al, Co, Cu, Zr, Ti and Nb;
    其中，所述M的含量较佳地为0～3wt.％但不为0wt.％，例如0.7wt.％、1.12wt.％、1.3wt.％或1.5wt.％，wt.％为占所述扩散基体的总质量的百分比；Wherein, the content of M is preferably 0 to 3wt.% but not 0wt.%, such as 0.7wt.%, 1.12wt.%, 1.3wt.% or 1.5wt.%, wt.% is the total The percentage of the total mass of the diffusion matrix;
    其中，当所述M包含Al时，所述Al的含量较佳地为0～0.5wt.％但不为0wt.％，例如0.02wt.％或0.1wt.％，wt.％为占所述扩散基体的总质量的百分比；Wherein, when the M contains Al, the content of the Al is preferably 0-0.5wt.% but not 0wt.%, such as 0.02wt.% or 0.1wt.%, wt.% is the proportion of the The percentage of the total mass of the diffusion matrix;
    其中，当所述M包含Co时，所述Co的含量较佳地为0～1wt.％但不为0wt.％，例如0.2wt.％、0.5wt.％或0.6wt.％，wt.％为占所述扩散基体的总质量的百分比；Wherein, when the M contains Co, the content of the Co is preferably 0-1wt.% but not 0wt.%, such as 0.2wt.%, 0.5wt.%, or 0.6wt.%, wt.% is the percentage of the total mass of the diffusion matrix;
    其中，当所述M包含Cu时，所述Cu的含量较佳地为0～1wt.％但不为0wt.％，例如0.2wt.％、0.4wt.％或0.5wt.％，wt.％为占所述扩散基体的总质量的百分比；Wherein, when the M contains Cu, the content of the Cu is preferably 0-1wt.% but not 0wt.%, such as 0.2wt.%, 0.4wt.%, or 0.5wt.%, wt.% is the percentage of the total mass of the diffusion matrix;
    其中，当所述M包含Zr时，所述Zr的含量较佳地为0～0.5wt.％但不为0wt.％，例如0.1wt.％，wt.％为占所述扩散基体的总质量的百分比；Wherein, when the M contains Zr, the content of the Zr is preferably 0-0.5wt.% but not 0wt.%, such as 0.1wt.%, wt.% is the total mass of the diffusion matrix percentage of
    其中，当所述M包含Ti时，所述Ti的含量较佳地为0～0.5wt.％但不为0wt.％，例如0.1wt.％，wt.％为占所述扩散基体的总质量的百分比。Wherein, when the M contains Ti, the content of the Ti is preferably 0-0.5wt.% but not 0wt.%, such as 0.1wt.%, wt.% is the total mass of the diffusion matrix percentage.
  3. 如权利要求1或2所述的R-T-B磁体的晶界扩散材料，其特征在于， 所述扩散源中，所述RH的含量为50～70wt.％，例如55wt.％、60wt.％或65wt.％；The grain boundary diffusion material of R-T-B magnet according to claim 1 or 2, characterized in that, in the diffusion source, the content of RH is 50-70wt.%, such as 55wt.%, 60wt.% or 65wt.%. %;
    和/或，所述扩散源中不含Ho或Gd；And/or, the diffusion source does not contain Ho or Gd;
    和/或，所述扩散源中所述Ga的含量为10～40wt.％，例如20wt.％或30wt.％；And/or, the Ga content in the diffusion source is 10-40wt.%, such as 20wt.% or 30wt.%.
    和/或，所述扩散源中所述Cu的含量为0～1wt.％或者8～10wt.％，例如为0wt.％或10wt.％；And/or, the content of Cu in the diffusion source is 0-1wt.% or 8-10wt.%, such as 0wt.% or 10wt.%.
    和/或，所述扩散源中所述Co的含量为0～1wt.％或者8～10wt.％，例如为0wt.％或10wt.％；And/or, the Co content in the diffusion source is 0-1wt.% or 8-10wt.%, such as 0wt.% or 10wt.%.
    和/或，所述扩散源中所述Al的含量为0～1wt.％或者4～5wt.％，例如为0wt.％或5wt.％；And/or, the Al content in the diffusion source is 0-1wt.% or 4-5wt.%, such as 0wt.% or 5wt.%.
    和/或，所述扩散源中所述Fe的含量为0～1wt.％或者4～5wt.％，例如为0wt.％或5wt.％；And/or, the content of Fe in the diffusion source is 0-1wt.% or 4-5wt.%, such as 0wt.% or 5wt.%.
    和/或，所述扩散源与所述扩散基体的质量比在2wt.％以下，优选0.3～1.5wt.％，例如0.3wt.％、0.4wt.％、0.8wt.％或1.2wt.％。And/or, the mass ratio of the diffusion source to the diffusion matrix is below 2wt.%, preferably 0.3-1.5wt.%, such as 0.3wt.%, 0.4wt.%, 0.8wt.% or 1.2wt.%. .
  4. 如权利要求1所述的R-T-B磁体的晶界扩散材料，其特征在于，所述扩散基体由以下组分组成：Nd 25wt.％、Pr 6wt.％、Fe 66.98wt.％、Al 0.02wt.％、Co 0.6wt.％、Cu 0.4wt.％、Zr 0.1wt.％和B 0.9wt.％，wt.％为各组分的质量与所述扩散基体总质量的百分比；The grain boundary diffusion material of the R-T-B magnet according to claim 1, wherein the diffusion matrix is composed of the following components: Nd 25wt.%, Pr 6wt.%, Fe 66.98wt.%, Al 0.02wt.% , Co 0.6wt.%, Cu 0.4wt.%, Zr 0.1wt.% and B 0.9wt.%, wt.% is the percentage of the mass of each component and the total mass of the diffusion matrix;
    或者，所述扩散基体由以下组分组成：Nd 27wt.％、Dy 2wt.％、Fe 69.32wt.％、Co 0.2wt.％、Cu 0.2wt.％、Ga 0.2wt.％、Ti 0.1wt.％和B 0.98wt.％，wt.％为各组分的质量与所述扩散基体总质量的百分比；Alternatively, the diffusion matrix is composed of the following components: Nd 27wt.%, Dy 2wt.%, Fe 69.32wt.%, Co 0.2wt.%, Cu 0.2wt.%, Ga 0.2wt.%, Ti 0.1wt.%. % and B 0.98wt.%, wt.% is the percentage of the mass of each component and the total mass of the diffusion matrix;
    或者，所述扩散基体由以下组分组成：Pr 31wt.％、Dy 1wt.％、Fe 65.55wt.％、Co 0.5wt.％、Cu 0.5wt.％、Ga 0.5wt.％和B 0.95wt.％，wt.％为各组分的质量与所述扩散基体总质量的百分比；Alternatively, the diffusion matrix is composed of the following components: Pr 31wt.%, Dy 1wt.%, Fe 65.55wt.%, Co 0.5wt.%, Cu 0.5wt.%, Ga 0.5wt.% and B 0.95wt.%. %, wt.% is the percentage of the mass of each component to the total mass of the diffusion matrix;
    或者，所述扩散基体由以下组分组成：Nd 26wt.％、Pr 4wt.％、Fe 67.75wt.％、Al 0.1wt.％、Co 0.6wt.％、Cu 0.4wt.％、Ga 0.1wt.％、Zr 0.1wt.％和B 0.95wt.％，wt.％为各组分的质量与所述扩散基体总质量的百分比；Alternatively, the diffusion matrix is composed of the following components: Nd 26wt.%, Pr 4wt.%, Fe 67.75wt.%, Al 0.1wt.%, Co 0.6wt.%, Cu 0.4wt.%, Ga 0.1wt.%. %, Zr 0.1wt.% and B 0.95wt.%, wt.% is the percentage of the mass of each component and the total mass of the diffusion matrix;
    和/或，所述扩散源由以下组分组成Tb 70wt.％、Cu 10wt.％、Co 10wt.％和Ga 10wt.％，wt.％为各组分的质量与所述扩散源的总质量的百分比；And/or, described diffusion source is made up of following components Tb 70wt.%, Cu 10wt.%, Co 10wt.% and Ga 10wt.%, wt.% is the mass of each component and the total mass of described diffusion source percentage of
    或者，所述扩散源由以下组分组成：Tb 65wt.％、Co 10wt.％、Ga 20wt.％和Al 5wt.％，wt.％为各组分的质量与所述扩散源的总质量的百分比；Or, described diffusion source is made up of following components: Tb 65wt.%, Co 10wt.%, Ga 20wt.% and Al 5wt.%, wt.% is the mass of each component and the total mass of described diffusion source percentage;
    或者，所述扩散源由以下组分组成：Dy 55wt.％、Cu 10wt.％、Ga 30wt.％和Fe 5wt.％，wt.％为各组分的质量与所述扩散源的总质量的百分比；Or, described diffusion source is made up of following components: Dy 55wt.%, Cu 10wt.%, Ga 30wt.% and Fe 5wt.%, wt.% is the mass of each component and the total mass of described diffusion source percentage;
    或者，所述扩散源由以下组分组成：Tb 70wt.％和Ga 30wt.％，wt.％为各组分的质量与所述扩散源的总质量的百分比。Alternatively, the diffusion source is composed of the following components: Tb 70wt.% and Ga 30wt.%, wt.% is the percentage of the mass of each component to the total mass of the diffusion source.
  5. 一种R-T-B磁体的制备方法，其特征在于，其包括以下步骤：将如权利要求1～4中任一项所述扩散源经晶界扩散处理扩散至如权利要求1～4中任一项所述扩散基体中即可。A method for preparing an R-T-B magnet, characterized in that it comprises the following steps: diffusing the diffusion source according to any one of claims 1 to 4 to the source according to any one of claims 1 to 4 through grain boundary diffusion treatment in the diffusion matrix.
  6. 如权利要求5所述的R-T-B磁体的制备方法，其特征在于，所述晶界扩散处理的温度在900℃以下，较佳地为800～900℃；The method for preparing an R-T-B magnet according to claim 5, wherein the temperature of the grain boundary diffusion treatment is below 900°C, preferably 800-900°C;
    和/或，所述扩散源在进行所述晶界扩散处理之前还进行预处理，所述预处理为将所述扩散源与有机溶剂的混合浆料形成于所述扩散基体的表面；And/or, the diffusion source is also pretreated before the grain boundary diffusion treatment, and the pretreatment is to form a mixed slurry of the diffusion source and an organic solvent on the surface of the diffusion matrix;
    其中，所述扩散源较佳地为合金粉末的形式；Wherein, the diffusion source is preferably in the form of alloy powder;
    其中，所述有机溶剂较佳地为醇类溶剂，例如乙醇；Wherein, the organic solvent is preferably an alcoholic solvent, such as ethanol;
    和/或，所述扩散基体的制备方法包括以下步骤：将所述扩散基体中各组分的混合物依次经熔炼、微粉碎、磁场成型和烧结处理即可；And/or, the preparation method of the diffusion matrix includes the following steps: the mixture of the components in the diffusion matrix is sequentially smelted, pulverized, formed in a magnetic field and sintered;
    其中，所述熔炼的温度较佳地为1500℃以下，例如1400～1500℃；Wherein, the melting temperature is preferably below 1500°C, such as 1400-1500°C;
    其中，所述熔炼的真空度较佳地为5×10 -2Pa； Wherein, the vacuum degree of the smelting is preferably 5×10 -2 Pa;
    其中，所述微粉碎较佳地依次进行吸氢、脱氢和气流磨处理；Wherein, the fine pulverization is preferably followed by hydrogen absorption, dehydrogenation and jet milling;
    其中，所述磁场成型的磁场强度为1.5～2T，例如1.6T；Wherein, the magnetic field strength of the magnetic field forming is 1.5-2T, such as 1.6T;
    其中，所述烧结的温度较佳地为1000～1100℃，例如1030℃或1040℃；所述烧结的时间例如为2.5～5h，例如3h或4h；所述烧结具体例如在1030℃下烧结3h，再在1040℃下烧结1h；所述烧结之前、所述磁场成型之后，较佳地还分别在300℃、600℃、800℃的温度下依次进行热处理。Wherein, the sintering temperature is preferably 1000-1100°C, such as 1030°C or 1040°C; the sintering time is, for example, 2.5-5h, such as 3h or 4h; the sintering is specifically, for example, sintering at 1030°C for 3h , and then sintered at 1040° C. for 1 h; before the sintering and after the magnetic field shaping, heat treatment is preferably performed sequentially at temperatures of 300° C., 600° C., and 800° C. respectively.
  7. 一种如权利要求5或6所述的R-T-B磁体的制备方法制得的R-T-B磁体。An R-T-B magnet prepared by the method for preparing the R-T-B magnet as claimed in claim 5 or 6.
  8. 一种R-T-B磁体，其特征在于，其包括以下组分：R：28.5～33.5wt.％，所述R为稀土元素，所述R包括HR，所述HR为重稀土元素，所述HR包括Dy和/或Tb；An R-T-B magnet, characterized in that it comprises the following components: R: 28.5-33.5wt.%, said R is a rare earth element, said R includes HR, said HR is a heavy rare earth element, and said HR includes Dy and/or Tb;
    Ga：0.01～0.9wt.％；Ga: 0.01～0.9wt.%;
    Cu：0～0.8wt.％；Cu: 0～0.8wt.%;
    Co：0～0.8wt.％；Co: 0～0.8wt.%;
    Al：0～0.2wt.％；Al: 0～0.2wt.%;
    B：0.9～1.02wt.％；B: 0.9～1.02wt.%;
    Fe：65～70wt.％，百分比为各组分的质量与所述R-T-B磁体的总质量的百分比；Fe: 65-70wt.%, the percentage is the percentage of the mass of each component to the total mass of the R-T-B magnet;
    所述R-T-B磁体包括主相和晶界相，所述晶界相为二颗粒晶界相和晶界三角区；The R-T-B magnet includes a main phase and a grain boundary phase, and the grain boundary phase is a two-grain grain boundary phase and a grain boundary triangular region;
    所述晶界三角区包括物相1和物相2；The grain boundary triangular region includes phase 1 and phase 2;
    所述物相1中含有Ga 1和Tb 1，所述物相2中含有Ga 2和Tb 2；其中： The phase 1 contains Ga 1 and Tb 1 , and the phase 2 contains Ga 2 and Tb 2 ; wherein:
    Ga 1：X 1mol％； Ga 1 : X 1 mol%;
    Tb 1：2mol％以下且不为0； Tb 1 : 2 mol% or less and not 0;
    Ga 2：X 2mol％； Ga 2 : X 2 mol%;
    Tb 2：2mol％以下且不为0；mol％为各组分与所述晶界相中所有组分的摩尔百分比； Tb 2 : less than 2 mol% and not 0; mol% is the mole percentage of each component and all components in the grain boundary phase;
    所述X 1mol％与所述X 2mol％的差值绝对值在10mol％以上； The absolute value of the difference between X 1 mol% and X 2 mol% is above 10 mol%;
    “所述物相1和所述物相2”的总面积与所述晶界相的总面积的比值在50％以上。The ratio of the total area of "the phase 1 and the phase 2" to the total area of the grain boundary phase is more than 50%.
  9. 如权利要求8所述的R-T-B磁体，其特征在于，所述X 1mol％与所述X 2mol％的差值绝对值在10mol％以上，例如10.1mol％、11.85mol％、13.8mol％或14.34mol％； The RTB magnet according to claim 8, wherein the absolute value of the difference between the X 1 mol% and the X 2 mol% is above 10 mol%, such as 10.1 mol%, 11.85 mol%, 13.8 mol% or 14.34mol%;
    和/或，所述Ga 1的含量为10～20mol％，例如11.29mol％、16.12mol％、17.8mol％或18.35mol％； And/or, the Ga 1 content is 10-20 mol%, such as 11.29 mol%, 16.12 mol%, 17.8 mol% or 18.35 mol%;
    和/或，所述Tb 1的含量为0.1～1mol％，例如0.3mol％、0.35mol％、0.41mol％或0.5mol％； And/or, the content of Tb 1 is 0.1-1 mol%, such as 0.3 mol%, 0.35 mol%, 0.41 mol% or 0.5 mol%;
    和/或，所述Ga 2的含量为1～5mol％，例如1.19mol％、4.01mol％、4mol％或4.27mol％； And/or, the Ga 2 content is 1-5 mol%, such as 1.19 mol%, 4.01 mol%, 4 mol% or 4.27 mol%;
    和/或，所述Tb 2的含量为0.1～1mol％，例如0.3mol％、0.31mol％或0.32mol％； And/or, the content of Tb 2 is 0.1-1mol%, such as 0.3mol%, 0.31mol% or 0.32mol%;
    和/或，“所述物相1和所述物相2”的总面积与所述晶界相的总面积的比值为50～70％，例如52％、58％、61％或67％；And/or, the ratio of the total area of "the phase 1 and the phase 2" to the total area of the grain boundary phase is 50-70%, such as 52%, 58%, 61% or 67%;
    和/或，所述R至少含有LR，LR为轻稀土元素，所述LR包括Nd和/或Pr；And/or, the R contains at least LR, LR is a light rare earth element, and the LR includes Nd and/or Pr;
    其中，所述“Nd和/或Pr”的质量与所述稀土元素的总质量的比值较佳地在2/3以上；Wherein, the ratio of the mass of "Nd and/or Pr" to the total mass of the rare earth elements is preferably more than 2/3;
    其中，所述LR的含量较佳地为21～32wt.％，例如27.5wt.％、29.73wt.％、30wt.％或30.4wt.％；Wherein, the content of the LR is preferably 21-32wt.%, such as 27.5wt.%, 29.73wt.%, 30wt.% or 30.4wt.%.
    当所述LR含有Nd时，所述Nd的含量较佳地为21～32wt.％，例如24.6wt.％、24.7wt.％、25.92wt.％或27.5wt.％，wt.％为占所述R-T-B磁体的总质量的百分比；When the LR contains Nd, the content of Nd is preferably 21-32wt.%, such as 24.6wt.%, 24.7wt.%, 25.92wt.% or 27.5wt.%. The percentage of the total mass of the R-T-B magnet;
    当所述LR含有Pr时，所述Pr的含量较佳地为2～31wt.％，例如3.81wt.％、5.7wt.％、5.8wt.％或30wt.％；When the LR contains Pr, the content of the Pr is preferably 2-31wt.%, such as 3.81wt.%, 5.7wt.%, 5.8wt.% or 30wt.%.
    和/或，所述HR的含量为0.2～3wt.％，例如0.21wt.％、0.29wt.％、1.64wt.％或2.38wt.％；And/or, the HR content is 0.2-3wt.%, such as 0.21wt.%, 0.29wt.%, 1.64wt.% or 2.38wt.%.
    和/或，当所述HR含量Dy时，所述Dy的含量为1～2wt.％，例如1.64wt.％或1.85wt.％；And/or, when the HR content is Dy, the Dy content is 1-2wt.%, such as 1.64wt.% or 1.85wt.%.
    和/或，当所述HR含有Tb时，所述Tb的含量为0.2～1wt.％，例如0.21wt.％、0.29wt.％或0.53wt.％；And/or, when the HR contains Tb, the content of Tb is 0.2-1wt.%, such as 0.21wt.%, 0.29wt.% or 0.53wt.%.
    和/或，所述Ga的含量为0.02～0.85wt.％，例如0.03wt.％、0.21wt.％、0.35wt.％、0.62wt.％或0.82wt.％And/or, the Ga content is 0.02-0.85wt.%, such as 0.03wt.%, 0.21wt.%, 0.35wt.%, 0.62wt.% or 0.82wt.%.
    和/或，所述Cu的含量为0.1～0.7wt.％，例如0.2wt.％、0.4wt.％、0.43wt.％或0.61wt.％；And/or, the content of Cu is 0.1-0.7wt.%, such as 0.2wt.%, 0.4wt.%, 0.43wt.% or 0.61wt.%.
    和/或，所述Co的含量为0.2～0.7wt.％，0.28wt.％、0.5wt.％、0.6wt.％、0.62wt.％或0.63wt.％；And/or, the content of Co is 0.2-0.7wt.%, 0.28wt.%, 0.5wt.%, 0.6wt.%, 0.62wt.% or 0.63wt.%.
    和/或，所述Al的含量为0.01～0.15wt.％，例如0.03wt.％、0.05wt.％或0.12wt.％；And/or, the content of Al is 0.01-0.15wt.%, such as 0.03wt.%, 0.05wt.% or 0.12wt.%.
    和/或，所述B的含量为0.9～1wt.％，例如0.91wt.％、0.95wt.％或0.98wt.％；And/or, the content of B is 0.9-1wt.%, such as 0.91wt.%, 0.95wt.% or 0.98wt.%.
    和/或，所述Fe的含量为65～69wt.％，66.63wt.％、67.38wt.％、65.42wt.％、67.21wt.％或65.84wt.％；And/or, the content of Fe is 65-69wt.%, 66.63wt.%, 67.38wt.%, 65.42wt.%, 67.21wt.% or 65.84wt.%.
    和/或，所述R-T-B磁体中还包括Zr、Ti和Nb中的一种或多种；And/or, the R-T-B magnet also includes one or more of Zr, Ti and Nb;
    其中，当所述R-T-B磁体中包含Zr，所述Zr的含量较佳地为0～0.5wt.％但不为0wt.％，例如0.1wt.％；Wherein, when the R-T-B magnet contains Zr, the content of Zr is preferably 0-0.5wt.% but not 0wt.%, such as 0.1wt.%;
    其中，当所述R-T-B磁体中包含Ti，所述Ti的含量较佳地为0～0.5wt.％但不为0wt.％，例如0.1wt.％。Wherein, when the R-T-B magnet contains Ti, the content of Ti is preferably 0-0.5wt.% but not 0wt.%, for example 0.1wt.%.
  10. 如权利要求8所述的R-T-B磁体，其特征在于，所述R-T-B磁体由以下组分组成：Nd 24.6wt.％、Pr 5.8wt.％、Tb 0.2wt.％、Fe 66.63wt.％、Al 0.03wt.％、Co 0.63wt.％、Cu 0.43wt.％、Ga 0.03wt.％、Zr 0.1wt.％和B 0.9wt.％，wt.％为各组分的质量与所述R-T-B磁体的总质量的百分比；所述R-T-B磁体包括主相和晶界相，所述晶界相为二颗粒晶界相和晶界三角区，所述晶界三角区包括物相1和物相2，所述物相1含有11.29mol％的Ga和0.35mol％的Tb，所述物相2中含有1.19mol％的Ga和0.31mol％的Tb，mol％为占所述晶界相中所有组分的摩尔百分比，“所述物相1和所述物相2”的总面积与所述晶界相的总面积的比值为52％；The R-T-B magnet according to claim 8, wherein the R-T-B magnet is composed of the following components: Nd 24.6wt.%, Pr 5.8wt.%, Tb 0.2wt.%, Fe 66.63wt.%, Al 0.03 wt.%, Co 0.63wt.%, Cu 0.43wt.%, Ga 0.03wt.%, Zr 0.1wt.% and B 0.9wt.%, wt.% is the mass of each component and the total of the R-T-B magnet The percentage of mass; the R-T-B magnet includes a main phase and a grain boundary phase, and the grain boundary phase is a two-grain grain boundary phase and a grain boundary triangular region, and the grain boundary triangular region includes a phase 1 and a phase 2, and the Phase 1 contains 11.29mol% Ga and 0.35mol% Tb, and phase 2 contains 1.19mol% Ga and 0.31mol% Tb, and mol% is the mole of all components in the grain boundary phase Percentage, the ratio of the total area of "the phase 1 and the phase 2" to the total area of the grain boundary phase is 52%;
    或者，所述R-T-B磁体由以下组分组成：Nd 27.5wt.％、Dy 1.85wt.％、Tb 0.53wt.％、Fe 67.38wt.％、Al 0.05wt.％、Co 0.28wt.％、Cu 0.2wt.％、Ga  0.35wt.％、Ti 0.1wt.％和B 1wt.％，wt.％为各组分的质量与所述R-T-B磁体的总质量的百分比；所述R-T-B磁体包括主相和晶界相，所述晶界相为二颗粒晶界相和晶界三角区，所述晶界三角区包括物相1和物相2，所述物相1含有16.12mol％的Ga和0.41mol％的Tb，所述物相2中含有4.27mol％的Ga和0.32mol％的Tb，mol％为占所述晶界相中所有组分的摩尔百分比，“所述物相1和所述物相2”的总面积与所述晶界相的总面积的比值为61％；Alternatively, the R-T-B magnet consists of the following components: Nd 27.5wt.%, Dy 1.85wt.%, Tb 0.53wt.%, Fe 67.38wt.%, Al 0.05wt.%, Co 0.28wt.%, Cu 0.2 wt.%, Ga 0.35wt.%, Ti 0.1wt.% and B 1wt.%, wt.% is the percentage of the mass of each component and the total mass of the R-T-B magnet; the R-T-B magnet includes main phase and crystal Boundary phase, the grain boundary phase is a two-grain grain boundary phase and a grain boundary triangular area, the grain boundary triangular area includes a phase 1 and a phase 2, and the phase 1 contains 16.12mol% Ga and 0.41mol% Tb, the phase 2 contains 4.27mol% of Ga and 0.32mol% of Tb, and the mol% is the mole percentage of all components in the grain boundary phase, "the phase 1 and the phase The ratio of the total area of 2" to the total area of the grain boundary phase is 61%;
    或者，所述R-T-B磁体由以下组分组成：Nd/wt.％、Pr 30.5wt.％、Dy 1.64wt.％、Fe 64.3wt.％、Co 0.5wt.％、Cu 0.61wt.％、Ga 0.82wt.％和B 0.95wt.％，wt.％为各组分的质量与所述R-T-B磁体的总质量的百分比；所述R-T-B磁体包括主相和晶界相，所述晶界相为二颗粒晶界相和晶界三角区，所述晶界三角区包括物相1和物相2，所述物相1含有18.35mol％的Ga和0.3mol％的Tb，所述物相2中含有4.01mol％的Ga和0.32mol％的Tb，mol％为占所述晶界相中所有组分的摩尔百分比，“所述物相1和所述物相2”的总面积与所述晶界相的总面积的比值为67％；Alternatively, the R-T-B magnet consists of the following components: Nd/wt.%, Pr 30.5wt.%, Dy 1.64wt.%, Fe 64.3wt.%, Co 0.5wt.%, Cu 0.61wt.%, Ga 0.82 wt.% and B 0.95wt.%, wt.% is the percentage of the mass of each component and the total mass of the R-T-B magnet; the R-T-B magnet includes a main phase and a grain boundary phase, and the grain boundary phase is two particles A grain boundary phase and a grain boundary triangular area, the grain boundary triangular area includes a phase 1 and a phase 2, the phase 1 contains 18.35mol% of Ga and 0.3mol% of Tb, and the phase 2 contains 4.01 mol% of Ga and 0.32mol% of Tb, mol% is the mole percentage of all components in the grain boundary phase, the total area of "the phase 1 and the phase 2" is the same as that of the grain boundary phase The ratio of the total area is 67%;
    或者，所述R-T-B磁体由以下组分组成：Nd 25.92wt.％、Pr 3.81wt.％、Tb 0.29wt.％、Fe 67.21wt.％、Al 0.12wt.％、Co 0.6wt.％、Cu 0.4wt.％、Ga 0.21wt.％、Zr 0.1wt.％和B 0.95wt.％，wt.％为各组分的质量与所述R-T-B磁体的总质量的百分比；所述R-T-B磁体包括主相和晶界相，所述晶界相为二颗粒晶界相和晶界三角区，所述晶界三角区包括物相1和物相2，所述物相1含有17.8mol％的Ga和0.5mol％的Tb，所述物相2中含有4mol％的Ga和0.3mol％的Tb，mol％为占所述晶界相中所有组分的摩尔百分比，“所述物相1和所述物相2”的总面积与所述晶界相的总面积的比值为58％。Alternatively, the R-T-B magnet consists of the following components: Nd 25.92wt.%, Pr 3.81wt.%, Tb 0.29wt.%, Fe 67.21wt.%, Al 0.12wt.%, Co 0.6wt.%, Cu 0.4 wt.%, Ga 0.21wt.%, Zr 0.1wt.% and B 0.95wt.%, wt.% is the percentage of the mass of each component and the total mass of the R-T-B magnet; the R-T-B magnet includes the main phase and Grain boundary phase, the grain boundary phase is a two-grain grain boundary phase and a grain boundary triangular area, the grain boundary triangular area includes a phase 1 and a phase 2, and the phase 1 contains 17.8mol% of Ga and 0.5mol % of Tb, the phase 2 contains 4mol% of Ga and 0.3mol% of Tb, and the mol% is the mole percentage of all components in the grain boundary phase, "the phase 1 and the phase The ratio of the total area of 2" to the total area of the grain boundary phase was 58%.
PCT/CN2022/129743 2021-12-28 2022-11-04 Grain boundary diffusion material, r-t-b magnet, and preparation method therefor WO2023124527A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202111681329.5 2021-12-28
CN202111681329.5A CN116403792A (en) 2021-12-28 2021-12-28 Crystal boundary diffusion material, R-T-B magnet and preparation method thereof

Publications (1)

Publication Number Publication Date
WO2023124527A1 true WO2023124527A1 (en) 2023-07-06

Family

ID=86997534

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/129743 WO2023124527A1 (en) 2021-12-28 2022-11-04 Grain boundary diffusion material, r-t-b magnet, and preparation method therefor

Country Status (2)

Country Link
CN (1) CN116403792A (en)
WO (1) WO2023124527A1 (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170178778A1 (en) * 2015-12-18 2017-06-22 Jl Mag Rare-Earth Co., Ltd. Neodymium Iron Boron Magnet and Preparation Method Thereof
CN108417380A (en) * 2018-05-21 2018-08-17 钢铁研究总院 A kind of low cost diffusion source alloy and grain boundary decision magnet and preparation method thereof
CN112509775A (en) * 2020-12-15 2021-03-16 烟台首钢磁性材料股份有限公司 Neodymium-iron-boron magnet with low-amount heavy rare earth addition and preparation method thereof
CN112908672A (en) * 2020-01-21 2021-06-04 福建省长汀金龙稀土有限公司 Grain boundary diffusion treatment method for R-Fe-B rare earth sintered magnet
JP2021150547A (en) * 2020-03-23 2021-09-27 日立金属株式会社 Method for manufacturing r-t-b based sintered magnet

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20170178778A1 (en) * 2015-12-18 2017-06-22 Jl Mag Rare-Earth Co., Ltd. Neodymium Iron Boron Magnet and Preparation Method Thereof
CN108417380A (en) * 2018-05-21 2018-08-17 钢铁研究总院 A kind of low cost diffusion source alloy and grain boundary decision magnet and preparation method thereof
CN112908672A (en) * 2020-01-21 2021-06-04 福建省长汀金龙稀土有限公司 Grain boundary diffusion treatment method for R-Fe-B rare earth sintered magnet
JP2021150547A (en) * 2020-03-23 2021-09-27 日立金属株式会社 Method for manufacturing r-t-b based sintered magnet
CN112509775A (en) * 2020-12-15 2021-03-16 烟台首钢磁性材料股份有限公司 Neodymium-iron-boron magnet with low-amount heavy rare earth addition and preparation method thereof

Also Published As

Publication number Publication date
CN116403792A (en) 2023-07-07
TW202326765A (en) 2023-07-01

Similar Documents

Publication Publication Date Title
TWI755151B (en) R-t-b series permanent magnetic material and preparation method and application thereof
TW202121452A (en) Ndfeb magnet material, raw material composition, preparation method and application
CN111326307B (en) Coating material for permeable magnet and preparation method of high-coercivity neodymium-iron-boron magnet
TWI755152B (en) NdFeB MAGNET MATERIAL, RAW MATERIAL COMPOSITION, PREPARATION METHOD AND APPLICATION
WO2019242581A1 (en) R-fe-b-based sintered magnet with low b content and preparation method therefor
WO2021109568A1 (en) R-t-b-based permanent magnet material, preparation method therefor and use thereof
CN111223627B (en) Neodymium-iron-boron magnet material, raw material composition, preparation method and application
KR102589802B1 (en) Neodymium iron boron magnetic material, raw material composition, manufacturing method and application
CN109859922B (en) Preparation method of R-Fe-B magnet with low heavy rare earth content
US20210296028A1 (en) High temperature resistant neodymium-iron-boron magnets and method for producing the same
CN111326306A (en) R-T-B series permanent magnetic material and preparation method and application thereof
CN111261355B (en) Neodymium-iron-boron magnet material, raw material composition, preparation method and application
TWI832167B (en) NdFeB MAGNET MATERIAL,PREPARATION METHOD AND APPLICATION
TW202305842A (en) Ndfeb magnet material,preparation method and application
TWI750964B (en) R-t-b series permanent magnetic material, raw material composition, preparation method and application
CN111223628B (en) Neodymium-iron-boron magnet material, raw material composition, preparation method and application
WO2023124527A1 (en) Grain boundary diffusion material, r-t-b magnet, and preparation method therefor
EP3975212A1 (en) A method for preparation of a sintered type ndfeb permanent magnet with an adjusted grain boundary
TWI841103B (en) A grain boundary diffusion material, r-t-b magnet and preparation method thereof
CN113936879A (en) La-containing R-T-B rare earth permanent magnet
CN111768965A (en) Preparation method of annular radiation oriented magnet
EP4354471A1 (en) Auxiliary alloy casting piece, high-remanence and high-coercive force ndfeb permanent magnet, and preparation methods thereof
WO2023207019A1 (en) Neodymium-iron-boron magnet material, preparation therefor, and application thereof
CN115881377A (en) Grain boundary diffusion material, neodymium iron boron magnet material, and preparation method and application thereof
TW202342781A (en) Ndfeb magnet material, preparation method, application, and motor thereof

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22913790

Country of ref document: EP

Kind code of ref document: A1