CN116403792A - Crystal boundary diffusion material, R-T-B magnet and preparation method thereof - Google Patents
Crystal boundary diffusion material, R-T-B magnet and preparation method thereof Download PDFInfo
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
- H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
-
- 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
Abstract
The invention discloses a crystal boundary diffusion material, an R-T-B magnet and a preparation method thereof. The grain boundary diffusion material comprises a diffusion matrix and a diffusion source; the diffusion matrix comprises the following components: r:28.5 to 33.5wt.% of R is a rare earth element; ga:0 to 0.5wt.%; b:0.9 to 1.02wt.%; fe: 65-70 wt.%; the diffusion source comprises the following components: HR:0 to 70wt.% but not 0wt.%; the HR is a heavy rare earth element, and the HR comprises Dy and/or Tb; ga is more than or equal to 10wt.%; cu:0 to 10wt.%; co:0 to 10wt.%; al:0 to 8wt.%; fe:0 to 8wt.%. Compared with a diffusion matrix before grain boundary diffusion, the R-T-B magnetic body prepared by the grain boundary diffusion material has the advantages that the coercive force and the temperature stability are obviously improved, and the residual magnetism is basically unchanged.
Description
Technical Field
The invention relates to a crystal boundary diffusion material, an R-T-B magnet and a preparation method thereof.
Background
Neodymium-iron-boron magnets have excellent magnetic properties and are widely applied to the fields of hybrid electric vehicles, motor engineering, electronic information and the like. At present, methods for improving sintered neodymium iron magnets mainly comprise alloying, grain refinement and grain boundary diffusion. The grain boundary diffusion method is to deposit a layer of heavy rare earth powder on the surface of a magnet by sputtering, vapor deposition, electrophoresis, coating and other methods, diffuse the heavy rare earth elements on the surface of the magnet into the magnet by heat treatment, and form a magnetic hardening shell layer on the grain boundary layer of a main phase to improve the coercive force. However, the degree of the prior art for improving the coercive force of the sintered body by using heavy rare earth element diffusion is generally limited to 10kOe or less, and a large amount of heavy rare earth element needs to be added or a complicated process is required. How to fully utilize a small amount of heavy rare earth elements to improve the coercive force of the magnet is a technical problem which is not effectively solved at present.
Disclosure of Invention
The invention mainly aims to overcome the defect that the enhancement degree of coercive force is low due to the addition of heavy rare earth elements in a grain boundary diffusion process in the prior art, and provides a grain boundary diffusion material, an R-T-B magnet and a preparation method thereof. Compared with a diffusion matrix before grain boundary diffusion, the R-T-B magnetic body prepared by the grain boundary diffusion material has the advantages that the coercive force and the temperature stability are obviously improved, and the residual magnetism is basically unchanged.
The invention mainly solves the technical problems through the following technical scheme.
The invention provides a grain boundary diffusion material of an R-T-B magnet, which comprises a diffusion matrix and a diffusion source;
the diffusion substrate comprises the following components:
r:28.5 to 33.5wt.% of R is a rare earth element;
Ga：0～0.5wt.％；
B：0.9～1.02wt.％；
fe: 65-70 wt.% of the mass of each component to the total mass of the diffusion matrix;
the diffusion source comprises the following components:
HR:0 to 70wt.% but not 0wt.%; the HR is a heavy rare earth element, and the HR comprises Dy and/or Tb;
Ga≥10wt.％；
Cu：0～10wt.％；
Co：0～10wt.％；
Al：0～8wt.％；
fe:0 to 8wt.%; wt.% is the percentage of the mass of each component to the total mass of the diffusion source.
In the present invention, those skilled in the art will recognize that the diffusion matrix is generally a magnet material after sintering, aging or grain boundary diffusion, or a mixture of two or more thereof, based on the grain boundary diffusion material. Those skilled in the art will appreciate that the diffusion matrix is generally referred to as a sintered and/or aged magnet material, such as a sintered body, because the degree of promotion of the magnet material after re-diffusion is generally limited.
The content of R in the diffusion matrix of the present invention is preferably 28 to 32wt.%, for example 29wt.%, 30wt.% or 31wt.%.
In the diffusion substrate of the present invention, R may be conventional in the art and generally contains at least LR, which is a light rare earth element, including Nd and/or Pr. Those skilled in the art know that the rare earth element is mainly Nd and/or Pr, i.e. at least two thirds of the rare earth element.
When the R comprises Nd, the Nd content may be 21-32 wt.%, e.g., 25wt.%, 26wt.%, or 27wt.%, the wt.% being a percentage of the total mass of the diffusion matrix.
When the R comprises Pr, the Pr content may be 4-32 wt.%, e.g., 6wt.%, 15wt.%, 20wt.%, 25wt.%, or 31wt.%, the wt.% being a percentage of the total mass of the diffusion matrix.
In the present invention, RH, which is a heavy rare earth element, is generally added in order to increase the magnetic properties of the R-T-B magnet.
Wherein the RH may be conventional in the art, e.g. comprising Dy and/or Tb.
Wherein the RH may be present in an amount of 0 to 2wt.% but not 0wt.%, for example 1wt.%, the wt.% being a percentage of the total mass of the diffusion substrate.
The diffusion matrix of the present invention is preferably Ga-free.
The content of Ga in the diffusion matrix of the present invention is preferably 0.05 to 0.5wt.%, e.g., 0.1wt.% or 0.2wt.%.
The content of B in the diffusion matrix of the present invention is preferably 0.9 to 0.98wt.%, for example 0.95wt.%.
In the diffusion substrate of the present invention, the content of Fe is generally the balance. The Fe content may be 65-69 wt.%, e.g., 66.98wt.%, 69.32wt.%, 65.55wt.%, or 67.75wt.%.
The diffusion matrix of the present invention also typically includes an additive element M conventional in the art, including, for example, one or more of Al, co, cu, zr, ti and Nb.
Wherein the amount of M may be conventional in the art, may be 0 to 3wt.% but not 0wt.%, for example 0.7wt.%, 1.12wt.%, 1.3wt.% or 1.5wt.%, the wt.% being a percentage of the total mass of the diffusion matrix.
Wherein when the M comprises Al, the Al content may be 0 to 0.5wt.% but not 0wt.%, for example 0.02wt.% or 0.1wt.%, the wt.% being a percentage of the total mass of the diffusion matrix.
Wherein when the M comprises Co, the content of Co may be 0 to 1wt.% but not 0wt.%, for example 0.2wt.%, 0.5wt.% or 0.6wt.%, the wt.% being a percentage of the total mass of the diffusion matrix.
Wherein when the M comprises Cu, the Cu content may be 0-1 wt.% but not 0wt.%, e.g., 0.2wt.%, 0.4wt.%, or 0.5wt.%, the wt.% being a percentage of the total mass of the diffusion matrix.
Wherein when the M comprises Zr, the Zr content may be 0 to 0.5wt.% but not 0wt.%, for example 0.1wt.%, wt.% based on the total mass of the diffusion substrate.
Wherein when the M comprises Ti, the Ti content may be 0 to 0.5wt.% but not 0wt.%, for example 0.1wt.%, the wt.% being a percentage of the total mass of the diffusion matrix.
In a preferred embodiment of the present invention, the diffusion substrate 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 B0.9 wt.%, the wt.% being percentages of the mass of the components to the total mass of the diffusion matrix.
In a preferred embodiment of the present invention, the diffusion substrate 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 B0.98 wt.%, the wt.% being the percentage of the mass of the respective components to the total mass of the diffusion matrix.
In a preferred embodiment of the present invention, the diffusion substrate is composed of the following components: pr 31wt.%, dy 1wt.%, fe 65.55wt.%, co 0.5wt.%, cu 0.5wt.%, ga 0.5wt.% and B0.95 wt.%, the wt.% being the percentage of the mass of each component to the total mass of the diffusion matrix.
In a preferred embodiment of the present invention, the diffusion substrate 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 B0.95 wt.%, the wt.% being the percentage of the mass of each component to the total mass of the diffusion matrix.
In the present invention, the diffusion source is generally referred to as a raw material to be diffused added when the grain boundary diffusion substrate is subjected to grain boundary diffusion treatment, as known to those skilled in the art.
In the diffusion source of the present invention, the RH is preferably present in an amount of 50 to 70wt.%, e.g., 55wt.%, 60wt.%, or 65wt.%. The RH content in the diffusion source is more than 70wt.%, although the coercivity is improved to an extent comparable to 70wt.%, this results in increased costs and significant manufacturing difficulties.
In the present invention, the diffusion source preferably does not contain Ho or Gd. Ho or Gd HAs significantly lower lifting effect on Hcj than Dy and/or Tb due to the nature of the element itself (the magnetic crystal anisotropy field HA is significantly lower than Dy, tb).
In the diffusion source of the present invention, the Ga content is preferably 10 to 40wt.%, for example 20wt.% or 30wt.%.
In the diffusion source of the present invention, the Cu content is preferably 0 to 1wt.% or 8 to 10wt.%, for example 0wt.% or 10wt.%.
In the diffusion source of the present invention, the content of Co is preferably 0 to 1wt.% or 8 to 10wt.%, for example 0wt.% or 10wt.%.
In the diffusion source of the present invention, the Al content is preferably 0 to 1wt.% or 4 to 5wt.%, for example 0wt.% or 5wt.%.
In the diffusion source of the present invention, the content of Fe is preferably 0 to 1wt.% or 4 to 5wt.%, for example 0wt.% or 5wt.%.
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.% being percentages of the mass of each component to the total mass of the diffusion source.
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.% are percentages of the mass of each component to the total mass of the diffusion source.
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.% being percentages of the mass of each component to the total mass of the diffusion source.
In a preferred embodiment of the present invention, the diffusion source is composed of the following components: tb 70wt.% and Ga 30wt.%, wt.% are percentages of the mass of the components to the total mass of the diffusion source.
In the present invention, those skilled in the art know that excessive addition of heavy rare earth elements may result in an increase in cost and may also result in an excessive decrease in remanence. Thus, the mass ratio of the diffusion source to the diffusion substrate is preferably below 2wt.%, preferably 0.3 to 1.5wt.%, e.g., 0.3wt.%, 0.4wt.%, 0.8wt.%, or 1.2wt.%.
The invention also provides a preparation method of the R-T-B magnet, which comprises the following steps: and diffusing the diffusion source into the diffusion matrix through grain boundary diffusion treatment.
In the present invention, the temperature of the grain boundary diffusion treatment may be conventional in the art, and is preferably 900 ℃ or less, for example, 800 to 900 ℃. The inventors found in experiments that the temperature of the grain boundary diffusion treatment is below 900 ℃, and the achieved enhancement degree of the coercive force is equivalent to that of the magnet material obtained at the grain boundary diffusion temperature of above 900 ℃ (in the invention, the enhancement degree of the coercive force, the residual magnetism change degree and the temperature stability change degree of the magnet material obtained at the grain boundary diffusion temperature of 800 ℃ and 950 ℃ are equivalent), so that the grain boundary diffusion material not only brings about remarkable enhancement of the coercive force, but also has low energy consumption.
In the present invention, the time of the grain boundary diffusion treatment may be conventional in the art, and is generally 8 to 12 hours, for example, 10 hours.
In the present invention, the diffusion source generally needs to be pretreated in order to allow the diffusion source to diffuse into the diffusion substrate through the grain boundary diffusion treatment.
Wherein the pretreatment generally forms a mixed slurry of the diffusion source and the organic solvent on the surface of the diffusion substrate.
The diffusion source is typically 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 pulverizing.
The organic solvent may be conventional in the art and may be an alcoholic solvent such as ethanol.
Wherein the diffusion source may be formed on the surface of the diffusion substrate by means conventional in the art, typically by coating or spraying.
Wherein the diffusion source after the pretreatment is coated on the surface of the diffusion substrate to form a thickness of 100 μm or less, for example, 10 to 50 μm. The thickness is generally referred to as the thickness of the diffusion substrate after the organic solvent has evaporated completely, as known to those skilled in the art.
The diffusion source of the present invention can achieve the excellent effects of the present invention without adding an antioxidant when performing grain boundary diffusion.
In the invention, the diffusion substrate can be prepared by adopting a preparation process conventional in the art, and the mixture of the diffusion substrate is generally subjected to smelting, micro-grinding, magnetic field forming and sintering treatment in sequence.
The raw material composition of the diffusion matrix is basically consistent with the components in the finally prepared diffusion matrix, and the raw material is prepared according to the required components of the diffusion matrix by the skilled in the art, so that the burning loss of rare earth is required to be considered in the preparation. It should be noted that there may be variations within the error range in the production process.
Wherein the smelting temperature is preferably below 1500 ℃, e.g. 1400-1500 ℃.
Wherein the vacuum degree of the smelting is preferably 5×10 -2 Pa。
Wherein the smelting is also typically followed by casting conventional in the art, the environment of the casting being, for example, an inert atmosphere, such as argon. The ambient air pressure for the casting is, for example, 5.5. 5.5 Mo Pa.
Quenching is also typically performed after the casting and before the micronizing to obtain a quenched alloy.
The cooling rate of the quenching treatment is, for example, 102 ℃ per second to 104 ℃ per second.
Wherein the micronization may be a disruption process conventional in the art, such as a sequential hydrogen absorption, dehydrogenation, and jet milling process.
Wherein the magnetic field strength of the magnetic field shaping can be 1.5-2T, for example 1.6T.
Wherein the sintering may be performed under vacuum conditions, for example at 5X 10 -3 The sintering is carried out under vacuum conditions of Pa, preferably at a temperature of 1000 to 1100℃such as 1030℃or 1040 ℃. The heat treatment is preferably further performed sequentially at a temperature of 300 ℃, 600 ℃, 800 ℃ before the sintering and after the magnetic field molding, respectively.
Wherein the sintering treatment is carried out for a period of time of, for example, 2.5 to 5 hours, for example, 3 hours or 4 hours. For example, at 1030℃for 3 hours and at 1040℃for 1 hour.
Wherein the sintering process is typically followed by a cooling process, which may be cooling the magnet material obtained after sintering to 90-110 ℃, for example 100 ℃; the cooling rate of the cooling treatment may be 10 ℃/min.
In the present invention, the size of the sintered body may be cut according to actual needs. For example, the length and width are 20mm, the thickness is 2mm, and the thickness direction is the magnetic field direction.
The invention also provides an R-T-B magnet which is prepared by the preparation method.
The invention also provides an R-T-B magnet, which comprises the following components:
r:28.5 to 33.5wt.%, said R being a rare earth element, said R comprising HR being a heavy rare earth element, said HR comprising Dy and/or Tb;
Ga：0.01～0.9wt.％；
Cu：0～0.8wt.％；
Co：0～0.8wt.％；
Al：0～0.2wt.％；
B：0.9～1.02wt.％；
fe: 65-70 wt.% of the mass of each component to the total mass of the R-T-B magnet;
the R-T-B magnet comprises a main phase and a grain boundary phase, wherein the grain boundary phase is a two-particle grain boundary phase and a grain boundary triangular area;
the grain boundary triangular region comprises a phase 1 and a phase 2; the phase 1 contains Ga 1 And Tb 1 The phase 2 contains Ga 2 And Tb 2 ；
Ga 1 ：X 1 mol％；
Tb 1 :2mol% or less and not 0;
Ga 2 ：X 2 mol％；
Tb 2 :2mol% or less and not 0; mol% of each componentMole percentages of all components in the grain boundary phase;
the X is 1 mol% with the X 2 The absolute value of the difference of mol% is more than 10 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 50% or more.
In the present invention, the grain boundary triangle generally refers to the gap between three main phase grains, as known to those skilled in the art. The two grain boundary phase generally refers to the gap between two main phase grains.
In the present invention, the measurement methods of the phase 1 and the phase 2 may be conventional in the art, and generally means that the perpendicular orientation planes of the R-T-B magnet are detected by FE-EPMA. As will be appreciated by those skilled in the art based on either phase 1 or phase 2, phase 1 is generally defined by Ga 1 And the Tb is 1 Aggregation or association of the phases 2 is generally formed by the Ga 2 And the Tb is 2 Aggregation or bond formation.
In the invention, the X 1 mol% with the X 2 The absolute value of the difference in mol% is 10mol% or more, for example, 10.1mol%, 11.85mol%, 13.8mol% or 14.34mol%.
In phase 1 of the present invention, the Ga 1 The content of (C) is preferably 10 to 20mol%, for example 11.29mol%, 16.12mol%, 17.8mol% or 18.35mol%.
In phase 1 of the present invention, the Tb 1 The content of (C) is preferably 0.1 to 1mol%, for example 0.3mol%, 0.35mol%, 0.41mol% or 0.5mol%.
In phase 2 of the present invention, the Ga 2 The content of (C) is preferably 1 to 5mol%, for example 1.19mol%, 4.01mol%, 4mol% or 4.27mol%.
In phase 2 of the present invention, the Tb 2 The content of (C) is preferably 0.1 to 1mol%, for example 0.3mol%, 0.31mol% or 0.32mol%.
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 to 70%, for example 52%, 58%, 61% or 67%.
In the present invention, the content of R is preferably 28.5 to 32wt.%, for example 29.88wt.%, 30.02wt.%, 30.6wt.%, 30.61wt.%, or 31.64wt.%.
In the present invention, it is known to those skilled in the art that R generally contains at least LR, LR being a light rare earth element, the LR including Nd and/or Pr. The ratio of the mass of "Nd and/or Pr" to the total mass of the rare earth element is preferably 2/3 or more.
Wherein the LR content may be conventional in the art, typically 21-32 wt.%, e.g., 27.5wt.%, 29.73wt.%, 30wt.%, or 30.4wt.%.
Wherein when the LR contains Nd, the Nd content is preferably 21 to 32wt.%, for example 24.6wt.%, 25.92wt.%, or 27.5wt.%, the wt.% being a percentage of the total mass of the R-T-B magnet.
Wherein when the LR contains Pr, the content of Pr is preferably 2 to 31wt.%, for example 3.81wt.%, 5.8wt.%, or 30.5wt.%.
In the present invention, the HR content is preferably 0.2 to 3wt.%, for example 0.21wt.%, 0.29wt.%, 1.64wt.% or 2.38wt.%.
In the present invention, when the HR content Dy, the Dy content is preferably 1 to 2wt.%, for example, 1.64wt.% or 1.85wt.%.
In the present invention, when the HR contains Tb, the content of Tb is preferably 0.2 to 1wt.%, for example 0.21wt.%, 0.29wt.%, or 0.53wt.%.
In the present invention, the Ga content is preferably 0.02 to 0.85wt.%, for example 0.03wt.%, 0.21wt.%, 0.35wt.%, or 0.82wt.%.
In the present invention, the Cu content is preferably 0.1 to 0.7wt.%, for example 0.2wt.%, 0.4wt.%, 0.43wt.%, or 0.61wt.%.
In the present invention, the content of Co is preferably 0.2 to 0.7wt.%, for example 0.28wt.%, 0.5wt.%, 0.6wt.%, 0.62wt.%, or 0.63wt.%.
In the present invention, the Al content is preferably 0.01 to 0.15wt.%, for example 0.03wt.%, 0.05wt.%, or 0.12wt.%.
In the present invention, the content of B is preferably 0.9 to 1wt.%, for example 0.91wt.%, 0.95wt.%, or 0.98wt.%.
In the present invention, the content of Fe is preferably 65 to 69wt.%,66.63wt.%, 67.38wt.%, 64.3wt.%, or 67.21wt.%.
Other conventional additives in the art, such as one or more of Zr, ti and Nb, may also be included in the R-T-B magnet of the present invention.
Wherein when Zr is contained in the R-T-B magnet, the Zr content is preferably 0 to 0.5wt.% but not 0wt.%, for example 0.1wt.%.
Wherein when Ti is contained in the R-T-B magnet, the Ti content is preferably 0 to 0.5wt.% but not 0wt.%, for example 0.1wt.%.
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 B0.9 wt.%, the wt.% being a percentage of the mass of each component to the total mass of the R-T-B magnet; the R-T-B magnet comprises a main phase and a grain boundary phase, wherein the grain boundary phase is a two-grain boundary phase and a grain boundary triangular region, the grain boundary triangular region comprises a phase 1 and a phase 2, the phase 1 contains 11.29mol% of Ga and 0.35mol% of Tb, the phase 2 contains 1.19mol% of Ga and 0.31mol% of Tb, the mol% is the mole percentage of all components in the grain boundary phase, and 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%.
In a preferred embodiment of the present invention, the R-T-B magnet is composed of the following components: 27.5wt.% Nd, 1.85wt.% Dy, 0.53wt.% Tb, 67.38wt.% Fe, 0.05wt.% Al, 0.28wt.% Co, 0.2wt.% Cu, 0.35wt.% Ga, 0.1wt.% Ti, and 1wt.% B, the wt.% being a percentage of the mass of each component to the total mass of the R-T-B magnet; the R-T-B magnet comprises a main phase and a grain boundary phase, wherein the grain boundary phase is a two-grain boundary phase and a grain boundary triangular region, the grain boundary triangular region comprises 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, the mol% is the mole percentage of all components in the grain boundary phase, and the ratio of the total area of the phase 1 and the phase 2 to the total area of the grain boundary phase is 61%.
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 B0.95 wt.%, the wt.% being a percentage of the mass of each component to the total mass of the R-T-B magnet; the R-T-B magnet comprises a main phase and a grain boundary phase, wherein the grain boundary phase is a two-grain boundary phase and a grain boundary triangular region, the grain boundary triangular region comprises a phase 1 and a phase 2, the phase 1 contains 18.35mol% of Ga and 0.3mol% of Tb, the phase 2 contains 4.01mol% of Ga and 0.32mol% of Tb, the mol% is the mole percentage of all components in the grain boundary phase, and the ratio of the total area of the phase 1 and the phase 2 to the total area of the grain boundary phase is 67%.
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 B0.95 wt.%, the wt.% being the percentage of the mass of each component to the total mass of the R-T-B magnet; the R-T-B magnet comprises a main phase and a grain boundary phase, wherein the grain boundary phase is a two-grain boundary phase and a grain boundary triangular region, the grain boundary triangular region comprises a phase 1 and a phase 2, 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, the mol% is the mole percentage of all components in the grain boundary phase, and the ratio of the total area of the phase 1 and the phase 2 to the total area of the grain boundary phase is 58%.
On the basis of conforming to the common knowledge in the field, the above preferred conditions can be arbitrarily combined to obtain the preferred examples of the invention.
The reagents and materials used in the present invention are commercially available.
The invention has the positive progress effects that: according to the invention, the Ga and heavy rare earth element diffusion source with specific content is used for controlling the Cu, co and Al content in the diffusion source, and the diffusion source is matched with a diffusion matrix with specific components, after the diffusion through the grain boundary, ga in the diffusion source preferentially occupies a grain boundary triangular area to form a Ga-containing phase, and the combination of the Ga-containing phase and Tb is extremely small, so that Tb enters a grain crust layer more or diffuses inwards, the diffusion effect is remarkably improved, and the coercive force is remarkably improved while higher remanence and temperature stability are maintained.
Drawings
FIG. 1 is a microstructure of an R-T-B magnet of example 1.
Detailed Description
The invention is further illustrated by means of the following examples, which are not intended to limit the scope of the invention. The experimental methods, in which specific conditions are not noted in the following examples, were selected according to conventional methods and conditions, or according to the commercial specifications.
Example 1
(1) Preparation of sintered body (diffusion matrix)
(1) Smelting and casting: the raw materials of the respective components required in the sintered body were mixed according to the formulation of Table 1 and in a high frequency vacuum induction furnace at 5X 10 -2 Vacuum melting is performed at a temperature of 1500 ℃ or lower in vacuum of Pa. Ar gas is introduced into a smelting furnace after vacuum smelting to ensure that the air pressure reaches 5.5 Pa, casting is carried out, and the pressure is 10 percent 2 C/s-10 4 The quench alloy is obtained at a cooling rate of c/sec.
(2) Micronizing: vacuumizing a hydrogen breaking furnace in which the quenched alloy is placed at room temperature, and then introducing hydrogen with the purity of 99.9% into the hydrogen breaking furnace, and maintaining the hydrogen pressure at 0.1MPa; after the hydrogen is fully absorbed, vacuumizing is carried out, heating is carried out, and dehydrogenation is fully carried out; then cooling, and taking out the crushed powder.
The pulverized powder was subjected to jet milling under nitrogen atmosphere having an oxidizing gas content of 150ppm or less at a pulverizing chamber pressure of 0.38MPa for 3 hours to obtain a fine powder. Oxidizing gas refers to oxygen or moisture.
Zinc stearate is added into the powder after jet milling, the addition amount of the zinc stearate is 0.12% of the weight of the powder after mixing, and the powder is fully mixed by a V-shaped mixer.
(3) And (3) forming: using a right angle orientation type magnetic field forming machine in an orientation magnetic field of 1.6T and at 0.35ton/cm 2 The powder added with zinc stearate is formed into a cube with a side length of 25mm at one time under the forming pressure, and demagnetized in a magnetic field of 0.2T after one time forming.
(4) Sintering: the molded bodies were transported to a sintering furnace and sintered at a temperature of 5X 10 -3 Maintaining under Pa for 1 hr at 300 deg.C, 600 deg.C and 800 deg.C, sintering at 1030 deg.C for 3 hr, sintering at 1040 deg.C for 1 hr, introducing Ar gas to make air pressure reach 0.1MPa, and cooling to 100deg.C at a cooling rate of 10deg.C/min.
(2) Preparation of R-T-B magnets
Processing the prepared sintered body into a magnet with the length and the width of 20mm and the thickness of 2mm, wherein the thickness direction is the magnetic field orientation direction, and cleaning the surface for later use; the diffusion sources were formulated as alloy powders and prepared as slurries according to the formulations in table 2 below and applied to the surface of diffusion substrates at thicknesses below 100 μm without the addition of antioxidants. The alloy powder is prepared by melting all components in a diffusion source at a high temperature, pulverizing, spraying ethanol serving as a solvent on the surface of a diffusion substrate, and then carrying out grain boundary diffusion treatment on the magnet at 800-900 ℃ for 10h.
The formulations of the diffusion substrates and diffusion sources of examples 2 to 4 and comparative examples 1 to 4 are shown in tables 1 and 2 below, and the preparation process is the same as that of example 1, examples 2 to 4 and comparative examples 1 to 4 in that the diffusion sources have a coating thickness of 100 μm or less on the diffusion substrates.
Table 1 diffusion matrix (weight percent of each component mass to the total mass of the diffusion matrix)
| Nd | Pr | Dy | Tb | Fe | Al | Co | Cu | Ga | Zr | Ti | B | |
| Example 1 | 25 | 6 | / | / | 66.98 | 0.02 | 0.6 | 0.4 | / | 0.1 | / | 0.9 |
| Example 2 | 27 | / | 2 | / | 69.32 | / | 0.2 | 0.2 | 0.2 | / | 0.1 | 0.98 |
| Example 3 | / | 31 | 1 | / | 65.55 | / | 0.5 | 0.5 | 0.5 | / | / | 0.95 |
| Example 4 | 26 | 4 | / | / | 67.75 | 0.1 | 0.6 | 0.4 | 0.1 | 0.1 | / | 0.95 |
| Comparative example 1 | 25 | 6 | / | / | 66.38 | 0.02 | 0.6 | 0.4 | 0.6 | 0.1 | / | 0.9 |
| Comparative example 2 | 25 | 6 | / | / | 66.93 | 0.02 | 0.6 | 0.4 | 0.1 | 0.1 | / | 0.85 |
| Comparative example 3 | 26 | 4 | / | / | 67.75 | 0.1 | 0.6 | 0.4 | 0.1 | 0.1 | / | 0.95 |
| Comparative example 4 | 26 | 4 | / | / | 67.75 | 0.1 | 0.6 | 0.4 | 0.1 | 0.1 | / | 0.95 |
Table 2 diffusion sources (weight percent of each component mass to the total mass of the diffusion source)
| Tb | Dy | Cu | Co | Ga | Fe | Al | Mass ratio of diffusion source to diffusion substrate | |
| Example 1 | 70 | / | 10 | 10 | 10 | / | / | 0.3％ |
| Example 2 | 65 | / | / | 10 | 20 | / | 5 | 0.8％ |
| Example 3 | / | 55 | 10 | / | 30 | 5 | / | 1.2％ |
| Example 4 | 70 | / | / | / | 30 | / | / | 0.4％ |
| Comparative example 1 | 70 | / | 10 | 10 | 10 | / | / | 0.3％ |
| Comparative example 2 | 70 | / | 10 | 10 | 10 | / | / | 0.3％ |
| Comparative example 3 | 70 | / | 10 | 10 | 5 | 5 | / | 0.4％ |
| Comparative example 4 | 70 | / | 5 | 5 | 10 | / | 10 | 0.4％ |
Effect example 1
1. Component determination of R-T-B magnet
The measurement was performed using a high frequency inductively coupled plasma emission spectrometer (ICP-OES). The test results are shown in table 3 below.
Table 3 (in wt.%) is the mass of each element as a percentage of the total mass of the R-T-B magnet
2. Magnetic performance detection
The sintered bodies and R-T-B magnets in examples and comparative examples were tested for magnetic properties using a PFM pulse demagnetizing profile testing apparatus. The test results are shown in table 4 below. ΔHcj refers to the coercivity of the R-T-B magnet obtained by subtracting the coercivity of the corresponding pre-diffusion sintered body. The test temperature was 20 ℃.
TABLE 4 Table 4
3. Microstructure characterization
The perpendicular orientation surfaces of the R-T-B magnets of examples 1 to 4 and comparative examples 1 to 4 were polished and examined by a field emission electron probe microanalyzer (FE-EPMA) (JEOL, 8530F). It was found that phases containing Ga and Tb were observed at a depth of 0 to 300 μm from the diffusion surface (referring to the surface of the diffusion substrate coated with the diffusion source) in the preparation of R-T-B magnets. The content of Tb and Ga elements at the grain boundary in the R-T-B magnet is determined by single-point quantitative analysis of FE-EPMA, the test condition is that the accelerating voltage is 15kv, and the probe beam current is 50nA. The test results are shown in table 5 below.
As shown in FIG. 1, the microstructure of the R-T-B magnet and the grain boundary composition of the triangular grain boundary region in example 1 are shown, in which point 6 is a low Ga phase and point 7 is a high Ga phase. Ga occupies the triangular grain boundary region, forms more high Ga phase, the high Ga phase and the low Ga phase have concentration difference of more than 10mol%, and Tb content is low, and meanwhile, the two-grain boundary phase is observed to contain less Ga. Further research shows that the phase can lower the melting point of the grain boundary phase in the grain boundary triangular area, has better wettability and ensures that the grain boundary is uniform and continuous. Meanwhile, the high Ga phase and the low Ga phase have rejection phenomenon relative to Tb, the Tb content is extremely low and generally not more than 2mol%, and the consumption of Tb elements at the grain boundary can be reduced, so that the diffusion depth of the Tb elements along the grain boundary is larger and the Tb elements are more effectively utilized.
TABLE 5
Note that: mol% is the ratio of the total molar amount of all elements in the grain boundary phase;
phase 1 and phase 2 are located in the grain boundary triangle, 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.
According to the above formulas of tables 1 to 3, the magnetic property data of table 4 and the microstructure data of table 5, the coercivity is improved by more than 10kOe compared with the diffusion matrix after the grain boundary diffusion treatment by matching the specific diffusion matrix and the diffusion source, and meanwhile, the use amount of heavy rare earth is less, furthermore, the temperature of the grain boundary diffusion treatment is low, and on the premise of low energy consumption and low material cost, the coercivity is obviously improved, the remanence is basically unchanged, and meanwhile, the temperature stability is obviously improved.
The realization of the invention is that research and development personnel obtain the alloy unexpectedly through multiple experiments, and multiple failed experiments are carried out in the research and development process, for example, when a diffusion substrate is prepared, the Ga content is too high, the B content is too low or too high, when a diffusion source is prepared, the Ga content is too low, and the contents (Cu, co, fe and Al) of other elements are not controlled, when the alloy is subjected to grain boundary diffusion treatment, the remarkable improvement of the coercive force can not be realized.
Claims (10)
1. A grain boundary diffusion material for an R-T-B magnet, comprising a diffusion substrate and a diffusion source;
the diffusion substrate comprises the following components: r:28.5 to 33.5wt.% of R is a rare earth element;
Ga：0～0.5wt.％；
B：0.9～1.02wt.％；
fe: 65-70 wt.% of the mass of each component to the total mass of the diffusion matrix;
the diffusion source comprises the following components:
HR:0 to 70wt.% but not 0wt.%;
the HR is a heavy rare earth element, and the HR comprises Dy and/or Tb;
Ga≥10wt.％；
Cu：0～10wt.％；
Co：0～10wt.％；
Al：0～8wt.％；
fe:0 to 8wt.%; wt.% is the percentage of the mass of each component to the total mass of the diffusion source.
2. The grain boundary diffusion material for an R-T-B magnet according to claim 1, wherein the diffusion substrate is a sintered body;
and/or, the content of R in the diffusion matrix is 28-32 wt.%, e.g., 29wt.%, 30wt.%, or 31wt.%;
and/or, in the diffusion matrix, the R contains at least LR, LR being a light rare earth element, the LR preferably including Nd and/or Pr, and the ratio of the mass of the "Nd and/or Pr" to the total mass of the rare earth element being 2/3 or more;
when the R comprises Nd, the Nd content is preferably 21 to 32wt.%, e.g., 25wt.%, 26wt.%, or 27wt.%, the wt.% being a percentage of the total mass of the diffusion matrix;
when the R comprises Pr, the content of Pr is preferably 4 to 32wt.%, for example 6wt.%, 15wt.%, 20wt.%, 25wt.% or 31wt.%, the wt.% being a percentage of the total mass of the diffusion matrix;
and/or, the R also comprises RH, wherein RH is a heavy rare earth element;
wherein the RH preferably comprises Dy and/or Tb;
wherein the RH content is preferably 0-2 wt.% but not 0wt.%, for example 1wt.%, wt.% being a percentage of the total mass of the diffusion substrate;
and/or the content of Ga in the diffusion matrix is 0.05 to 0.5wt.%, e.g., 0.1wt.% or 0.2wt.%; alternatively, the diffusion matrix is Ga-free;
and/or, the content of B in the diffusion matrix is 0.9 to 0.98wt.%, for example 0.95wt.%;
and/or, the content of Fe in the diffusion matrix is 65-69 wt.%, e.g., 66.98wt.%, 69.32wt.%, 65.55wt.%, or 67.75wt.%;
and/or, the diffusion matrix further comprises M, wherein the M comprises one or more of Al, co, cu, zr, ti and Nb;
wherein the content of M is preferably 0-3 wt.% but not 0wt.%, for example 0.7wt.%, 1.12wt.%, 1.3wt.% or 1.5wt.%, the wt.% being a percentage of the total mass of the diffusion matrix;
wherein when the M comprises Al, the Al content is preferably 0 to 0.5wt.% but not 0wt.%, for example 0.02wt.% or 0.1wt.%, the wt.% being a percentage of the total mass of the diffusion matrix;
wherein when the M comprises Co, the content of Co is preferably 0 to 1wt.% but not 0wt.%, for example 0.2wt.%, 0.5wt.% or 0.6wt.%, the wt.% being a percentage of the total mass of the diffusion matrix;
wherein when the M comprises Cu, the content of Cu is preferably 0 to 1wt.% but not 0wt.%, for example 0.2wt.%, 0.4wt.% or 0.5wt.%, the wt.% being a percentage of the total mass of the diffusion matrix;
wherein when the M comprises Zr, the Zr content is preferably 0 to 0.5wt.% but not 0wt.%, for example 0.1wt.%, wt.% being a percentage of the total mass of the diffusion substrate;
wherein when the M comprises Ti, the Ti content is preferably 0 to 0.5wt.% but not 0wt.%, for example 0.1wt.%, the wt.% being a percentage of the total mass of the diffusion matrix.
3. A grain boundary diffusion material for an R-T-B magnet according to claim 1 or 2, wherein the RH content in the diffusion source is 50-70 wt.%, such as 55wt.%, 60wt.%, or 65wt.%;
and/or, the diffusion source does not contain Ho or Gd;
and/or the Ga content in the diffusion source is 10-40 wt.%, e.g., 20wt.% or 30wt.%;
and/or the Cu content in the diffusion source is 0 to 1wt.% or 8 to 10wt.%, for example 0wt.% or 10wt.%;
and/or the content of Co in the diffusion source is 0 to 1wt.% or 8 to 10wt.%, for example 0wt.% or 10wt.%;
and/or the Al content in the diffusion source is 0 to 1wt.% or 4 to 5wt.%, for example 0wt.% or 5wt.%;
and/or the content of Fe in the diffusion source is 0 to 1wt.% or 4 to 5wt.%, for example 0wt.% or 5wt.%;
and/or the mass ratio of the diffusion source to the diffusion substrate is below 2wt.%, preferably 0.3 to 1.5wt.%, e.g., 0.3wt.%, 0.4wt.%, 0.8wt.%, or 1.2wt.%.
4. The grain boundary diffusion material of an R-T-B magnet according to claim 1, wherein the diffusion matrix consists of: nd 25wt.%, pr 6wt.%, fe 66.98wt.%, al 0.02wt.%, co 0.6wt.%, cu 0.4wt.%, zr 0.1wt.% and B0.9 wt.%, the wt.% being the percentage of the mass of each component to the total mass of the diffusion matrix;
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 B0.98 wt.%, the wt.% being percentages of the mass of each component to the total mass of the diffusion matrix;
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 B0.95 wt.%, the wt.% being the mass of the components as a percentage of the total mass of the diffusion matrix;
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 B0.95 wt.%, the wt.% being the percentage of the mass of each component to the total mass of the diffusion matrix;
and/or the diffusion source consists of Tb 70wt.%, cu 10wt.%, co 10wt.% and Ga 10wt.%, the wt.% being the percentage of the mass of the respective components to the total mass of the diffusion source;
alternatively, the diffusion source is composed of the following components: tb 65wt.%, co 10wt.%, ga 20wt.% and Al 5wt.%, wt.% being the percentage of the mass of each component to the total mass of the diffusion source;
alternatively, the diffusion source is composed of the following components: dy 55wt.%, cu 10wt.%, ga 30wt.% and Fe 5wt.%, wt.% being the percentage of the mass of the components to the total mass of the diffusion source;
alternatively, the diffusion source is composed of the following components: tb 70wt.% and Ga 30wt.%, wt.% are percentages of the mass of the components to the total mass of the diffusion source.
5. The preparation method of the R-T-B magnet is characterized by comprising the following steps of: the diffusion source according to any one of claims 1 to 4 may be diffused into the diffusion substrate according to any one of claims 1 to 4 by grain boundary diffusion treatment.
6. The method for producing an R-T-B magnet according to claim 5, wherein the temperature of the grain boundary diffusion treatment is 900 ℃ or less, preferably 800 to 900 ℃;
and/or the diffusion source is further subjected to pretreatment before the grain boundary diffusion treatment, wherein the pretreatment is to form a mixed slurry of the diffusion source and an organic solvent on the surface of the diffusion substrate;
wherein the diffusion source is preferably in the form of an alloy powder;
wherein the organic solvent is preferably an alcoholic solvent, such as ethanol;
and/or, the preparation method of the diffusion substrate comprises the following steps: sequentially carrying out smelting, micro-grinding, magnetic field forming and sintering treatment on the mixture of each component in the diffusion matrix;
wherein the smelting temperature is preferably below 1500 ℃, for example 1400-1500 ℃;
wherein the vacuum degree of the smelting is preferably 5×10 -2 Pa；
Wherein the micro-pulverization is preferably sequentially subjected to hydrogen absorption, dehydrogenation and jet milling;
wherein the magnetic field strength of the magnetic field shaping is 1.5-2T, such as 1.6T;
wherein the sintering temperature is preferably 1000-1100 ℃, such as 1030 ℃ or 1040 ℃; the sintering time is, for example, 2.5 to 5 hours, for example, 3 hours or 4 hours; the sintering is specifically carried out, for example, at 1030 ℃ for 3 hours and at 1040 ℃ for 1 hour; the heat treatment is preferably further performed sequentially at a temperature of 300 ℃, 600 ℃, 800 ℃ before the sintering and after the magnetic field molding, respectively.
7. An R-T-B magnet produced by the production method of an R-T-B magnet as claimed in claim 5 or 6.
8. An R-T-B magnet, characterized in that it comprises the following components: r:28.5 to 33.5wt.%, said R being a rare earth element, said R comprising HR being a heavy rare earth element, said HR comprising Dy and/or Tb;
Ga：0.01～0.9wt.％；
Cu：0～0.8wt.％；
Co：0～0.8wt.％；
Al：0～0.2wt.％；
B：0.9～1.02wt.％；
fe: 65-70 wt.%, the percentages being the mass of the components and the total mass of the R-T-B magnet;
the R-T-B magnet comprises a main phase and a grain boundary phase, wherein the grain boundary phase is a two-particle grain boundary phase and a grain boundary triangular region;
the grain boundary triangular region comprises a phase 1 and a phase 2;
the phase 1 contains Ga 1 And Tb 1 The phase 2 contains Ga 2 And Tb 2 The method comprises the steps of carrying out a first treatment on the surface of the Wherein:
Ga 1 ：X 1 mol％；
Tb 1 :2mol% or less and not 0;
Ga 2 ：X 2 mol％；
Tb 2 :2mol% or less and not 0; mol% is the mole percentage of each component to all components in the grain boundary phase;
the X is 1 mol% with the X 2 The absolute value of the difference of mol% is more than 10 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 50% or more.
9. The R-T-B magnet of claim 8, wherein said X 1 mol% with the X 2 The absolute value of the difference in mol% is 10mol% or more, for example, 10.1mol%, 11.85mol%, 13.8mol% or 14.34mol%;
and/or the Ga 1 The content of (C) is 10 to 20mol%, for example 11.29mol%, 16.12mol%, 17.8mol% or 18.35mol%;
and/or the Tb 1 The content of (C) is 0.1 to 1mol%, for example 0.3mol%, 0.35mol%, 0.41mol% or 0.5mol%;
and/or the Ga 2 The content of (C) is 1 to 5mol%, for example 1.19mol%, 4.01mol%, 4mol% or 4.27mol%;
and/or the Tb 2 The content of (C) is 0.1 to 1mol%, for example 0.3mol%, 0.31mol% or 0.32mol%;
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 to 70%, for example 52%, 58%, 61% or 67%;
and/or, the R at least contains LR, wherein the LR is light rare earth element, and the LR comprises Nd and/or Pr;
wherein the ratio of the mass of "Nd and/or Pr" to the total mass of the rare earth element is preferably 2/3 or more;
wherein the LR content is preferably 21-32 wt.%, e.g., 27.5wt.%, 29.73wt.%, 30wt.%, or 30.4wt.%;
when the LR contains Nd, the Nd content is preferably 21 to 32wt.%, for example 24.6wt.%, 24.7wt.%, 25.92wt.% or 27.5wt.%, the wt.% being a percentage of the total mass of the R-T-B magnet;
when the LR contains Pr, the content of Pr is preferably 2 to 31wt.%, for example 3.81wt.%, 5.7wt.%, 5.8wt.%, or 30wt.%;
and/or the HR is present in an amount of 0.2 to 3wt.%, e.g., 0.21wt.%, 0.29wt.%, 1.64wt.%, or 2.38wt.%;
and/or, when the HR content Dy, the Dy content is 1 to 2wt.%, for example 1.64wt.% or 1.85wt.%;
and/or, when the HR contains Tb, the Tb is present in an amount of 0.2 to 1wt.%, for example 0.21wt.%, 0.29wt.%, or 0.53wt.%;
and/or the Ga content is 0.02-0.85 wt.%, e.g., 0.03wt.%, 0.21wt.%, 0.35wt.%, 0.62wt.%, or 0.82wt.%
And/or the Cu content is 0.1 to 0.7wt.%, e.g., 0.2wt.%, 0.4wt.%, 0.43wt.%, or 0.61wt.%;
and/or the content of Co is 0.2 to 0.7wt.%,0.28wt.%, 0.5wt.%, 0.6wt.%, 0.62wt.%, or 0.63wt.%;
and/or the Al content is 0.01 to 0.15wt.%, e.g., 0.03wt.%, 0.05wt.%, or 0.12wt.%;
and/or the content of B is 0.9 to 1wt.%, e.g., 0.91wt.%, 0.95wt.%, or 0.98wt.%;
and/or, the content of Fe is 65-69 wt.%,66.63wt.%, 67.38wt.%, 65.42wt.%, 67.21wt.%, or 65.84wt.%;
and/or, the R-T-B magnet further comprises one or more of Zr, ti and Nb;
wherein when Zr is contained in the R-T-B magnet, the Zr content is preferably 0 to 0.5wt.% but not 0wt.%, for example 0.1wt.%;
wherein when Ti is contained in the R-T-B magnet, the Ti content is preferably 0 to 0.5wt.% but not 0wt.%, for example 0.1wt.%.
10. The R-T-B magnet of claim 8, wherein the R-T-B magnet consists of: 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 B0.9 wt.%, the wt.% being a percentage of the mass of each component to the total mass of the R-T-B magnet; the R-T-B magnet comprises a main phase and a grain boundary phase, wherein the grain boundary phase is a two-grain boundary phase and a grain boundary triangular area, the grain boundary triangular area comprises a phase 1 and a phase 2, the phase 1 contains 11.29mol% of Ga and 0.35mol% of Tb, the phase 2 contains 1.19mol% of Ga and 0.31mol% of Tb, the mol% is the mole percentage of all components in the grain boundary phase, and 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%;
alternatively, the R-T-B magnet is composed of the following components: 27.5wt.% Nd, 1.85wt.% Dy, 0.53wt.% Tb, 67.38wt.% Fe, 0.05wt.% Al, 0.28wt.% Co, 0.2wt.% Cu, 0.35wt.% Ga, 0.1wt.% Ti, and 1wt.% B, the wt.% being a percentage of the mass of each component to the total mass of the R-T-B magnet; the R-T-B magnet comprises a main phase and a grain boundary phase, wherein the grain boundary phase is a two-grain boundary phase and a grain boundary triangular area, the grain boundary triangular area comprises 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, the mol% is the mole percentage of all components in the grain boundary phase, and the ratio of the total area of the phase 1 and the phase 2 to the total area of the grain boundary phase is 61%;
alternatively, the R-T-B magnet is composed of the following components: nd/wt.%, pr 30.5wt.%, dy 1.64wt.%, fe 64.3wt.%, co 0.5wt.%, cu 0.61wt.%, ga 0.82wt.% and B0.95 wt.%, the wt.% being the percentage of the mass of each component to the total mass of the R-T-B magnet; the R-T-B magnet comprises a main phase and a grain boundary phase, wherein the grain boundary phase is a two-grain boundary phase and a grain boundary triangular area, the grain boundary triangular area comprises a phase 1 and a phase 2, the phase 1 contains 18.35mol% of Ga and 0.3mol% of Tb, the phase 2 contains 4.01mol% of Ga and 0.32mol% of Tb, the mol% is the mole percentage of all components in the grain boundary phase, and the ratio of the total area of the phase 1 and the phase 2 to the total area of the grain boundary phase is 67%;
alternatively, 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 B0.95 wt.%, the wt.% being the percentage of the mass of each component to the total mass of the R-T-B magnet; the R-T-B magnet comprises a main phase and a grain boundary phase, wherein the grain boundary phase is a two-grain boundary phase and a grain boundary triangular region, the grain boundary triangular region comprises a phase 1 and a phase 2, 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, the mol% is the mole percentage of all components in the grain boundary phase, and the ratio of the total area of the phase 1 and the phase 2 to the total area of the grain boundary phase is 58%.
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| CN202111681329.5A CN116403792A (en) | 2021-12-28 | 2021-12-28 | Crystal boundary diffusion material, R-T-B magnet and preparation method thereof |
| PCT/CN2022/129743 WO2023124527A1 (en) | 2021-12-28 | 2022-11-04 | Grain boundary diffusion material, r-t-b magnet, and preparation method therefor |
| TW111147159A TWI841103B (en) | 2021-12-28 | 2022-12-08 | A grain boundary diffusion material, r-t-b magnet and preparation method thereof |
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| EP3182423B1 (en) * | 2015-12-18 | 2019-03-20 | 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 |
| CN112908672B (en) * | 2020-01-21 | 2024-02-09 | 福建省金龙稀土股份有限公司 | Grain boundary diffusion treatment method for R-Fe-B rare earth sintered magnet |
| JP7396148B2 (en) * | 2020-03-23 | 2023-12-12 | 株式会社プロテリアル | Manufacturing method of RTB 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 |
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