CN111613407A - R-T-B series permanent magnetic material, raw material composition, preparation method and application thereof - Google Patents
R-T-B series permanent magnetic material, raw material composition, preparation method and application thereof Download PDFInfo
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- CN111613407A CN111613407A CN202010496724.5A CN202010496724A CN111613407A CN 111613407 A CN111613407 A CN 111613407A CN 202010496724 A CN202010496724 A CN 202010496724A CN 111613407 A CN111613407 A CN 111613407A
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- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 48
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- 229910052733 gallium Inorganic materials 0.000 claims abstract description 47
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 47
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 13
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- 229910052737 gold Inorganic materials 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 7
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- 239000000463 material Substances 0.000 claims description 85
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- 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
- H01F1/0576—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 pressed, e.g. hot working
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/02—Making ferrous alloys by powder metallurgy
- C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
- C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
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- C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
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- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
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- C22C38/007—Ferrous alloys, e.g. steel alloys containing silver
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- C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
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- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
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- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
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- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
- H01F1/04—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials metals or alloys
- H01F1/047—Alloys characterised by their composition
- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
- H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
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- 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
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- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
- H01F41/0266—Moulding; Pressing
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- 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
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Abstract
The invention discloses an R-T-B series permanent magnetic material, a raw material composition, a preparation method and application thereof. The raw material composition of the R-T-B series permanent magnetic material comprises the following components in percentage by mass: 29.5 to 32 percent of R, wherein the R is a rare earth element at least containing Nd, and the content of Pr is 0 to 17 percent; 0.15 to 0.50 percent of Zr; cu, 0-0.08%, but not 0, not 0.08; 0-0.3% of Co; 0-3% of M, wherein M is one or more of Al, Ga, Ti, Nb, Hf, Si, Sn, Ge, Ag, Au, Bi and Mn; b, 0.95-1.05%; 64-70% of Fe; the percentage is the mass percentage of the total mass of the raw material composition of the R-T-B series permanent magnetic material, and the sum of the contents of all the components is 100%. The R-T-B series permanent magnetic material has the advantages of good squareness, good high-temperature performance and excellent mechanical performance.
Description
Technical Field
The invention relates to an R-T-B series permanent magnetic material, a raw material composition, a preparation method and application thereof.
Background
Nd-Fe-B permanent magnetic material2Fel4The B compound is used as a matrix, has the advantages of high magnetic property, small thermal expansion coefficient, easy processing, low price and the like, is increased at the speed of 20-30 percent per year on average since the coming of the world, and becomes a permanent magnetic material with the most wide application. According to the preparation method, the Nd-Fe-B permanent magnet can be divided into three types of sintering, bonding and hot pressing, wherein the sintered magnet accounts for more than 80% of the total production and is most widely applied.
In the prior art, Co is the most used and effective element when manufacturing heat-resistant and corrosion-resistant sintered Nd-Fe-B magnets. This is because the addition of Co can reduce the temperature coefficient of the magnetically induced reversible temperature coefficient, effectively increase the curie temperature, and can improve the corrosion resistance of Nd-Fe-B magnets. However, the addition of Co tends to cause a sharp drop in remanence, and the added Co is contained not only in the main phase but also in the grain boundary phase, so that there arises a problem of lowering mechanical strength, and the cost of Co is high.
In order to improve magnetic properties, suppress grain growth and improve sintering temperature width, JP2002075717A discloses the precipitation of a fine ZrB compound, NbB compound or HfB compound (hereinafter referred to as M-B compound) uniformly dispersed in an R-T-B based rare earth permanent magnet containing Co, Al, Cu and Zr, Nb or Hf (hereinafter referred to as "M-B compound") by adding Zr to the R-T-B based rare earth permanent magnet containing Cu, wherein the M-B compound has an average particle diameter of 5 μ M or less and the maximum interval between M-B compounds is 50 μ M or less. JPWO2004030000A1 Zr was similarly added to R-T-B based rare earth permanent magnet, and R was alloyed by a double alloy method2T14The Zr-rich product is present in the B main phase, and it is clearly indicated that the technical problem cannot be solved if the Zr-rich product is present only in the grain boundary phase.
Disclosure of Invention
The invention aims to solve the technical problem that in the prior art, the Curie temperature and the coercive force of an R-T-B series permanent magnetic material are improved by adding Co, and the Co has the defect of high price, and provides an R-T-B series permanent magnetic material, a raw material composition, a preparation method and application thereof. According to the invention, trace Co content is not added or controlled, and the content of Cu and Zr elements is controlled, so that the obtained R-T-B series permanent magnet material has the advantages of good squareness, good high-temperature performance and excellent mechanical performance.
The invention provides a raw material composition of an R-T-B series permanent magnetic material, which comprises the following components in percentage by mass:
29.5 to 32 percent of R, wherein the R is a rare earth element at least containing Nd, and the content of Pr is 0 to 17 percent;
Zr，0.15-0.50％；
cu, 0-0.08%, but not 0, not 0.08;
Co，0-0.3％；
0-3% of M, wherein M is one or more of Al, Ga, Ti, Nb, Hf, Si, Sn, Ge, Ag, Au, Bi and Mn;
B，0.95-1.05％；
Fe，64-70％；
the percentage is the mass percentage of the total mass of the raw material composition of the R-T-B series permanent magnetic material, and the sum of the contents of all the components is 100%.
In the raw material composition of the R-T-B series permanent magnet material, R can be a rare earth element added in a smelting process and/or a diffusion process, for example, the rare earth element added in the smelting process.
In the raw material composition of the R-T-B series permanent magnet material, the content of the R is 29.8%, 30.5%, 30.8%, 31%, 31.5%, 31.6% or 32%, wherein the percentage is the percentage of the total mass of the raw material composition of the R-T-B series permanent magnet material.
The content of Nd in the raw material composition of the R-T-B based permanent magnetic material may be conventional in the art, and is preferably 23.1 to 29.7%, for example, 23.1%, 23.6%, 24.3%, 25%, 25.2%, 29%, or 29.7%, wherein the percentage is a percentage of the total mass of the raw material composition of the R-T-B based permanent magnetic material.
In the raw material composition of the R-T-B system permanent magnetic material, the addition form of Nd in the R can be conventional in the art, for example, in the form of PrNd, or in the form of pure Nd, or in the form of a mixture of pure Pr and Nd, or in combination of PrNd, pure Pr and Nd. When added as PrNd, the mass ratio of Pr to Nd in PrNd is preferably 25:75, 20: 80 or 10: 90.
in the raw material composition of the R-T-B permanent magnet material, the content of Pr is preferably 0 to 10%, and more preferably 0 to 8%, for example, 0, 2.2%, 5.5%, 6.1%, 6.3%, 7.4%, or 7.9%, where the percentage is the percentage of the total mass of the raw material composition of the R-T-B permanent magnet material.
In the raw material composition of the R-T-B based permanent magnetic material, when the R contains Pr, the addition form of Pr may be conventional in the art, for example, in the form of PrNd, or in the form of pure Pr, or in the form of a mixture of pure Pr and Nd, or in combination of PrNd, pure Pr, and Nd. When added as PrNd, the mass ratio of Pr to Nd in PrNd is preferably 25:75, 20: 80 or 10: 90.
in the raw material composition of the R-T-B series permanent magnetic material, the R can also comprise heavy rare earth elements. The heavy rare earth element can be a heavy rare earth element added in a smelting process and/or a diffusion process, and preferably, the heavy rare earth element is a heavy rare earth element added in the smelting process.
In the raw material composition of the R-T-B based permanent magnetic material, the heavy rare earth element may be a heavy rare earth species conventional in the art, such as one or more of Dy, Tb, Gd, and Ho.
In the raw material composition of the R-T-B based permanent magnetic material, when the R includes a heavy rare earth element, the content of the heavy rare earth element may be conventional in the art, and is preferably 0 to 7% (excluding 0), and is further preferably 0.1 to 0.5%, for example, 0.1, 0.2%, 0.3%, or 0.5%, where the percentage is a percentage of the total mass of the raw material composition of the R-T-B based permanent magnetic material.
In the raw material composition of the R-T-B permanent magnet material, the Zr content is, for example, 0.15%, 0.2%, 0.3%, 0.35% or 0.5%, wherein the percentage is the percentage of the total mass of the raw material composition of the R-T-B permanent magnet material.
In the raw material composition of the R-T-B series permanent magnet material, the content of Cu is preferably 0.04% to 0.06%, for example, 0.04%, 0.05%, or 0.06%, where the percentage is the percentage of the total mass of the raw material composition of the R-T-B series permanent magnet material.
In the raw material composition of the R-T-B series permanent magnet material, the content of the Co is 0, 0.1% or 0.3%, wherein the percentage is the percentage of the total mass of the raw material composition of the R-T-B series permanent magnet material.
In the raw material composition of the R-T-B series permanent magnet material, the content of B is 0.95%, 0.98% or 1.05%, wherein the percentage is the percentage of the total mass of the raw material composition of the R-T-B series permanent magnet material.
In the raw material composition of the R-T-B series permanent magnet material, the type of M is preferably one or more of Al, Ga, Ti, Nb and Hf.
In the raw material composition of the R-T-B-based permanent magnetic material, the content of M is preferably 0 to 2%, for example, 0, 0.08%, 0.1%, 0.58%, 0.6%, 0.7%, 0.75%, 0.9%, or 1.2%, where the percentage is a percentage of the total mass of the raw material composition of the R-T-B-based permanent magnetic material.
In the raw material composition of the R-T-B based permanent magnetic material, when the M contains Al, the content of Al is preferably 0 to 1% (excluding 0), for example, 0.03%, 0.5%, or 0.6%, where the percentage is a percentage of the total mass of the raw material composition of the R-T-B based permanent magnetic material.
In the raw material composition of the R-T-B based permanent magnetic material, when the M contains Ga, the content of the Ga is preferably 0 to 1% (excluding 0), for example, 0.05%, 0.1%, 0.2%, or 0.4%, where the percentage is a percentage of the total mass of the raw material composition of the R-T-B based permanent magnetic material.
In the raw material composition of the R-T-B based permanent magnetic material, when the M contains Ti, the content of Ti is preferably 0.05 to 0.3%, for example, 0.05%, 0.1%, or 0.3%, where the percentage is a percentage of the total mass of the raw material composition of the R-T-B based permanent magnetic material.
In the raw material composition of the R-T-B based permanent magnet material, when the M contains Nb, the content of Nb is preferably 0 to 0.2% (excluding 0), for example, 0.05%, where the percentage is a percentage of the total mass of the raw material composition of the R-T-B based permanent magnet material.
In the raw material composition of the R-T-B based permanent magnetic material, when the M contains Hf, the content of Hf is preferably 0 to 0.2% (excluding 0), for example, 0.05%, where the percentage is a percentage of the total mass of the raw material composition of the R-T-B based permanent magnetic material.
In one embodiment, in the raw material composition of the R-T-B series permanent magnet material, the definitions of some components may be as follows, and the definitions of the remaining components are as described in any one of the above embodiments: the R does not contain Tb.
In one embodiment, in the raw material composition of the R-T-B based permanent magnetic material, the definitions of some components may be as follows, and the definitions of the remaining components are as described in any one of the above embodiments: the R does not contain heavy rare earth elements except Dy and Tb.
In one embodiment, in the raw material composition of the R-T-B based permanent magnetic material, the definitions of some components may be as follows, and the definitions of the remaining components are as described in any one of the above embodiments: the R does not comprise Ho.
In one embodiment, in the raw material composition of the R-T-B based permanent magnetic material, the definitions of some components may be as follows, and the definitions of the remaining components are as described in any one of the above embodiments: the R contains no rare earth metal other than Nd and Pr, except for inevitable impurities.
In one embodiment, in the raw material composition of the R-T-B based permanent magnetic material, the definitions of some components may be as follows, and the definitions of the remaining components are as described in any one of the above embodiments: the content of Co is 0.
In one embodiment, in the raw material composition of the R-T-B based permanent magnetic material, the definitions of some components may be as follows, and the definitions of the remaining components are as described in any one of the above embodiments: the content of Co is 0-0.3% (excluding 0), for example, 0.1% or 0.3%, wherein the percentage is the percentage of the total mass of the raw material composition of the R-T-B series permanent magnet material.
In one embodiment, in the raw material composition of the R-T-B based permanent magnetic material, the definitions of some components may be as follows, and the definitions of the remaining components are as described in any one of the above embodiments:
the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Al is more than or equal to 0.55 percent; the percentage is the mass percentage of the total mass of the raw material composition of the R-T-B series permanent magnet material.
In one embodiment, in the raw material composition of the R-T-B based permanent magnetic material, the definitions of some components may be as follows, and the definitions of the remaining components are as described in any one of the above embodiments:
the R does not contain Tb; the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Ga is less than 0.2%; the content of the Al is 0.45-0.54%; the percentage is the mass percentage of the total mass of the raw material composition of the R-T-B series permanent magnet material.
In one embodiment, in the raw material composition of the R-T-B based permanent magnetic material, the definitions of some components may be as follows, and the definitions of the remaining components are as described in any one of the above embodiments:
the R contains Tb; the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Ga is less than 0.2%; the content of the Al is 0.45-0.54%; al + Cu is more than or equal to 0.55 percent; the percentage is the mass percentage of the total mass of the raw material composition of the R-T-B series permanent magnet material.
In one embodiment, in the raw material composition of the R-T-B based permanent magnetic material, the definitions of some components may be as follows, and the definitions of the remaining components are as described in any one of the above embodiments:
the Zr content is more than or equal to 0.35 percent; the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Ga is 0.2-0.25%; the content of the Al is 0.45-0.54%; the percentage is the mass percentage of the total mass of the raw material composition of the R-T-B series permanent magnet material.
In one embodiment, in the raw material composition of the R-T-B based permanent magnetic material, the definitions of some components may be as follows, and the definitions of the remaining components are as described in any one of the above embodiments:
the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Ga is more than 0.25 percent; the content of the Al is 0.45-0.54%; the content of Ti is less than 0.15% or more than 0.28%; the percentage is the mass percentage of the total mass of the raw material composition of the R-T-B series permanent magnet material.
In one embodiment, in the raw material composition of the R-T-B based permanent magnetic material, the definitions of some components may be as follows, and the definitions of the remaining components are as described in any one of the above embodiments:
the R does not contain Tb; the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Al is less than 0.04%; the percentage is the mass percentage of the total mass of the raw material composition of the R-T-B series permanent magnet material.
In one embodiment, in the raw material composition of the R-T-B based permanent magnetic material, the definitions of some components may be as follows, and the definitions of the remaining components are as described in any one of the above embodiments:
the R contains Tb; the Zr content is more than or equal to 0.26 percent; the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Al is less than 0.04%; the percentage is the mass percentage of the total mass of the raw material composition of the R-T-B series permanent magnet material.
In one embodiment, in the raw material composition of the R-T-B based permanent magnetic material, the definitions of some components may be as follows, and the definitions of the remaining components are as described in any one of the above embodiments:
said R comprises Tb; the content of Ga is less than 0.05 percent or more than 0.25 percent; the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Al is less than 0.04%; the percentage is the mass percentage of the total mass of the raw material composition of the R-T-B series permanent magnet material.
In a certain scheme, the raw material composition of the R-T-B series permanent magnetic material comprises the following components in percentage by mass:
29.5 to 32 percent of R, wherein the R is a rare earth element at least containing Nd, and the content of Pr is 0 to 17 percent;
Zr，0.15-0.50％；
cu, 0-0.08%, but not 0, not 0.08;
Co，0-0.3％；
0-3% of M, wherein M is one or more of Al, Ga, Ti, Nb and Hf;
B，0.95-1.05％；
Fe，64-70％；
the percentage is the mass percentage of the total mass of the raw material composition of the R-T-B series permanent magnetic material, and the sum of the contents of all the components is 100%.
In a certain scheme, the raw material composition of the R-T-B series permanent magnetic material can be any one of the following numbers 1 to 8, wherein the percentage is the mass percentage of each component in the total mass of the raw material composition of the R-T-B series permanent magnetic material, the sum of the contents of the components is 100 percent,
"/" means that the element is not included.
The invention also provides a preparation method of the R-T-B series permanent magnet material, which comprises the steps of smelting, pulverizing, molding, sintering and aging the raw material composition of the R-T-B series permanent magnet material.
In the preparation method of the R-T-B system permanent magnetic material, the melting operation and conditions may be a conventional melting process in the art, and generally, the raw material composition of the R-T-B system permanent magnetic material is melted and cast by an ingot casting process and a rapid hardening sheet process to obtain an alloy sheet.
As known to those skilled in the art, since rare earth elements are usually lost in the melting and sintering processes, in order to ensure the quality of a final product, 0 to 0.3 wt% of a rare earth element (generally Nd element) is generally additionally added to the formula of a raw material composition in the melting process, wherein the percentage is the weight percentage of the additionally added rare earth element in the total content of the raw material composition; in addition, the content of the additionally added rare earth elements is not included in the category of the raw material composition.
In the preparation method of the R-T-B series permanent magnet material, the smelting temperature can be 1300-1600 ℃.
In the preparation method of the R-T-B series permanent magnet material, the smelting equipment is generally a high-frequency vacuum smelting furnace and/or a medium-frequency vacuum smelting furnace, and the medium-frequency vacuum smelting furnace is a medium-frequency vacuum induction rapid hardening melt-spinning furnace.
In the preparation method of the R-T-B series permanent magnet material, the operation and conditions for milling can be conventional milling processes in the field, and generally comprise hydrogen milling and/or airflow milling.
The hydrogen pulverized powder generally comprises hydrogen absorption, dehydrogenation and cooling treatment. The temperature of the hydrogen absorption is generally 20 to 200 ℃. The dehydrogenation temperature is typically 400-650 ℃. The pressure of the hydrogen absorption is generally 50 to 600 kPa.
The pressure of the airflow grinding chamber is generally 0.1-2 MPa. The gas flow in the gas flow milled powder can be, for example, nitrogen and/or argon. The efficiency of the jet milled powder may vary depending on the equipment, and may be, for example, 30 to 400kg/h, preferably 200 kg/h.
In the preparation method of the R-T-B series permanent magnet material, the molding operation and conditions can be conventional molding processes in the field. Such as magnetic field molding. The magnetic field intensity of the magnetic field forming method is generally 1.5T or more.
In the preparation method of the R-T-B series permanent magnet material, the operation and the condition of the sintering treatment can be a sintering process which is conventional in the field, such as a vacuum sintering process and/or an inert atmosphere sintering process, wherein the vacuum sintering process or the inert atmosphere sintering process is conventional in the field, and when the inert atmosphere sintering process is adopted, the vacuum degree of the initial stage of sintering can be lower than 5 × 10-1Pa, and the like. The inert atmosphere may be an atmosphere containing an inert gas as is conventional in the art, such as helium, argon.
In the preparation method of the R-T-B series permanent magnet material, the sintering treatment temperature can be 1000-1200 ℃, and preferably 1030-1090 ℃.
In the preparation method of the R-T-B series permanent magnet material, the sintering treatment time can be 0.5-10h, and preferably 2-8 h.
In the preparation method of the R-T-B series permanent magnet material, the temperature of the aging treatment can be 450-600 ℃, for example 480-510 ℃.
In the preparation method of the R-T-B series permanent magnet material, the time of the aging treatment can be 1-4h, such as 1-3 h.
Preferably, after the sintering treatment and before the aging treatment, a grain boundary diffusion treatment is further performed.
The grain boundary diffusion treatment may be performed by a conventional technique in the art, and for example, a Tb-containing substance and/or a Dy-containing substance may be deposited on the surface of the sintered body obtained by the sintering treatment by vapor deposition, coating, or sputtering, and then subjected to diffusion heat treatment.
In the grain boundary diffusion treatment, the Tb-containing substance may be Tb metal, a Tb-containing compound (e.g., Tb-containing fluoride), or an alloy.
In the grain boundary diffusion treatment, the Dy-containing substance may be Dy metal, a Dy-containing compound (e.g., a Dy-containing fluoride), or an alloy.
In the grain boundary diffusion treatment, the temperature of the diffusion heat treatment may be 800-.
In the grain boundary diffusion treatment, the time of the diffusion heat treatment can be 12-48h, such as 24 h.
Besides the preparation method, the raw material composition of the R-T-B series permanent magnet material can also be used for preparing the R-T-B series permanent magnet material by adopting a double-phase alloy process. The dual phase alloy process may be conventional in the art.
The invention also provides the R-T-B series permanent magnetic material prepared by the preparation method.
The invention also provides an R-T-B series permanent magnetic material which comprises the following components in percentage by mass:
29.5 to 32 percent of R, wherein the R is a rare earth element at least containing Nd, and the content of Pr is 0 to 17 percent;
Zr，0.15-0.50％；
cu, 0-0.08%, but not 0, not 0.08;
Co，0-0.3％；
0-3% of M, wherein M is one or more of Al, Ga, Ti, Nb, Hf, Si, Sn, Ge, Ag, Au, Bi and Mn;
B，0.95-1.05％；
Fe，64-70％；
the percentage is the mass percentage of the total mass of the R-T-B series permanent magnetic material, and the sum of the contents of all the components is 100 percent.
Cu and M in the R-T-B series permanent magnet material do not enter a main phase basically, are distributed at a grain boundary mainly, and can replace part of Fe in the grain boundary. By controlling the content of R, B, Zr and Cu, an enriched phase is generated at the grain boundary, and the enriched phase is helpful for optimizing the defects of the grain boundary, so that the coercive force of the magnet is improved, the squareness is improved, and the high-temperature performance is improved. Meanwhile, because the content of trace Co is not added or controlled, Co cannot be enriched in the crystal boundary, thereby inhibiting the crystal fracture and improving the mechanical property. The composition of the enriched phase is Rp-(Zrx,Cuy,Mz)q-Fe100-p-qWherein: r is a rare earth element containing at least Nd; m is one or more of Ga, Al, Ti, Nb, Hf, Si, Sn, Ge, Ag, Au, Bi and Mn; p, q, x, y and z satisfy the following conditions: 1P is more than or equal to 5 and less than or equal to 25 (at%); q is more than or equal to 3 and less than or equal to 8 (at%); x/(y + z) ═ 1.0-1.8, at% is atomic%.
In the R-T-B series permanent magnet material, R can be a rare earth element added in a smelting process and/or a diffusion process, for example, the rare earth element added in the smelting process.
In the R-T-B series permanent magnet material, the content of R is 29.8%, 30.5%, 30.8%, 31%, 31.5%, 31.6% or 32%, wherein the percentage is the percentage of the total mass of the R-T-B series permanent magnet material.
The content of Nd in the R-T-B based permanent magnetic material may be conventional in the art, and is preferably 23.1 to 29.7%, for example 23.1%, 23.6%, 24.3%, 25%, 25.2%, 29%, or 29.7%, wherein the percentage is a percentage of the total mass of the R-T-B based permanent magnetic material.
In the R-T-B based permanent magnetic material, the addition form of Nd in R can be conventional in the art, for example, in the form of PrNd, or in the form of pure Nd, or in the form of a mixture of pure Pr and Nd, or in combination of PrNd, pure Pr and Nd. When added as PrNd, the mass ratio of Pr to Nd in PrNd is preferably 25:75, 20: 80 or 10: 90.
in the R-T-B permanent magnet material, the content of Pr is preferably 0 to 10%, and more preferably 0 to 8%, such as 0, 2.2%, 5.5%, 6.1%, 6.3%, 7.4%, or 7.9%, wherein the percentage is the percentage of the total mass of the R-T-B permanent magnet material.
In the R-T-B based permanent magnetic material, when R contains Pr, the addition form of Pr may be conventional in the art, for example, in the form of PrNd, or in the form of pure Pr, or in the form of a mixture of pure Pr and Nd, or in combination of PrNd, pure Pr, and Nd. When added as PrNd, the mass ratio of Pr to Nd in PrNd is preferably 25:75, 20: 80 or 10: 90.
in the R-T-B series permanent magnetic material, the R can also comprise heavy rare earth elements. The heavy rare earth element can be a heavy rare earth element added in a smelting process and/or a diffusion process, and preferably, the heavy rare earth element is a heavy rare earth element added in the smelting process.
In the R-T-B based permanent magnetic material, the heavy rare earth element may be a heavy rare earth species conventional in the art, such as one or more of Dy, Tb, Gd, and Ho.
In the R-T-B based permanent magnetic material, when R includes a heavy rare earth element, the content of the heavy rare earth element may be conventional in the art, and is preferably 0 to 7% (excluding 0), and is more preferably 0.1 to 0.5%, such as 0.1, 0.2%, 0.3%, or 0.5%, where the percentage is a percentage of the total mass of the R-T-B based permanent magnetic material.
In the R-T-B series permanent magnet material, the Zr content is 0.15%, 0.2%, 0.3%, 0.35% or 0.5%, wherein the percentage is the percentage of the total mass of the R-T-B series permanent magnet material.
In the R-T-B series permanent magnet material, the content of Cu is preferably 0.04-0.06%, such as 0.04%, 0.05% or 0.06%, wherein the percentage is the percentage of the total mass of the R-T-B series permanent magnet material.
In the R-T-B series permanent magnet material, the content of Co is 0, 0.1% or 0.3%, wherein the percentage is the percentage of the total mass of the R-T-B series permanent magnet material.
In the R-T-B series permanent magnet material, the content of B is 0.95%, 0.98% or 1.05%, wherein the percentage is the percentage of the total mass of the R-T-B series permanent magnet material.
In the R-T-B series permanent magnet material, the type of M is preferably one or more of Al, Ga, Ti, Nb and Hf.
In the R-T-B series permanent magnet material, the content of M is preferably 0 to 2%, for example, 0, 0.08%, 0.1%, 0.58%, 0.6%, 0.7%, 0.75%, 0.9%, or 1.2%, where the percentage is the percentage of the total mass of the R-T-B series permanent magnet material.
In the R-T-B based permanent magnetic material, when the M contains Al, the content of Al is preferably 0 to 1% (excluding 0), for example, 0.03%, 0.5%, or 0.6%, where the percentage is a percentage of the total mass of the R-T-B based permanent magnetic material.
In the R-T-B based permanent magnetic material, when M contains Ga, the content of Ga is preferably 0 to 1% (excluding 0), for example, 0.05%, 0.1%, 0.2%, or 0.4%, where the percentage is a percentage of the total mass of the R-T-B based permanent magnetic material.
In the R-T-B based permanent magnet material, when the M contains Ti, the content of Ti is preferably 0.05 to 0.3%, for example, 0.05%, 0.1%, or 0.3%, where the percentage is a percentage of the total mass of the R-T-B based permanent magnet material.
In the R-T-B based permanent magnet material, when M includes Nb, the content of Nb is preferably 0 to 0.2% (excluding 0), for example, 0.05%, where the percentage is a percentage of the total mass of the R-T-B based permanent magnet material.
In the R-T-B permanent magnet material, when the M contains Hf, the content of Hf is preferably 0-0.2% (excluding 0), for example, 0.05%, where the percentage is the percentage of the total mass of the R-T-B permanent magnet material.
In one embodiment, in the R-T-B series permanent magnet material, some components may be defined as follows, and the rest components may be defined as any one of the above embodiments: the R does not contain Tb.
In one embodiment, in the R-T-B based permanent magnetic material, some components may be defined as follows, and the rest components may be defined as any one of the above embodiments: the R does not contain heavy rare earth elements except Dy and Tb.
In one embodiment, in the R-T-B based permanent magnetic material, some components may be defined as follows, and the rest components may be defined as any one of the above embodiments: the R does not comprise Ho.
In one embodiment, in the R-T-B based permanent magnetic material, some components may be defined as follows, and the rest components may be defined as any one of the above embodiments: the R contains no rare earth metal other than Nd and Pr, except for inevitable impurities.
In one embodiment, in the R-T-B based permanent magnetic material, some components may be defined as follows, and the rest components may be defined as any one of the above embodiments: the content of Co is 0.
In one embodiment, in the R-T-B based permanent magnetic material, some components may be defined as follows, and the rest components may be defined as any one of the above embodiments: the content of Co is 0-0.3% (excluding 0), such as 0.1% or 0.3%, wherein the percentage is the percentage of the total mass of the R-T-B series permanent magnet material.
In one embodiment, in the R-T-B based permanent magnetic material, some components may be defined as follows, and the rest components may be defined as any one of the above embodiments:
the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Al is more than or equal to 0.55 percent; the percentage is the mass percentage of the total mass of the R-T-B series permanent magnet material.
In one embodiment, in the R-T-B based permanent magnetic material, some components may be defined as follows, and the rest components may be defined as any one of the above embodiments:
the R does not contain Tb; the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Ga is less than 0.2%; the content of the Al is 0.45-0.54%; the percentage is the mass percentage of the total mass of the R-T-B series permanent magnet material.
In one embodiment, in the R-T-B based permanent magnetic material, some components may be defined as follows, and the rest components may be defined as any one of the above embodiments:
the R contains Tb; the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Ga is less than 0.2%; the content of the Al is 0.45-0.54%; al + Cu is more than or equal to 0.55 percent; the percentage is the mass percentage of the total mass of the R-T-B series permanent magnet material.
In one embodiment, in the R-T-B based permanent magnetic material, some components may be defined as follows, and the rest components may be defined as any one of the above embodiments:
the Zr content is more than or equal to 0.35 percent; the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Ga is 0.2-0.25%; the content of the Al is 0.45-0.54%; the percentage is the mass percentage of the total mass of the R-T-B series permanent magnet material.
In one embodiment, in the R-T-B based permanent magnetic material, some components may be defined as follows, and the rest components may be defined as any one of the above embodiments:
the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Ga is more than 0.25 percent; the content of the Al is 0.45-0.54%; the content of Ti is less than 0.15% or more than 0.28%; the percentage is the mass percentage of the total mass of the R-T-B series permanent magnet material.
In one embodiment, in the R-T-B based permanent magnetic material, some components may be defined as follows, and the rest components may be defined as any one of the above embodiments:
the R does not contain Tb; the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Al is less than 0.04%; the percentage is the mass percentage of the total mass of the R-T-B series permanent magnet material.
In one embodiment, in the R-T-B based permanent magnetic material, some components may be defined as follows, and the rest components may be defined as any one of the above embodiments:
the R contains Tb; the Zr content is more than or equal to 0.26 percent; the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Al is less than 0.04%; the percentage is the mass percentage of the total mass of the R-T-B series permanent magnet material.
In one embodiment, in the R-T-B based permanent magnetic material, some components may be defined as follows, and the rest components may be defined as any one of the above embodiments:
said R comprises Tb; the content of Ga is less than 0.05 percent or more than 0.25 percent; the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Al is less than 0.04%; the percentage is the mass percentage of the total mass of the R-T-B series permanent magnet material.
In a certain scheme, the R-T-B series permanent magnetic material comprises the following components in percentage by mass:
29.5 to 32 percent of R, wherein the R is a rare earth element at least containing Nd, and the content of Pr is 0 to 17 percent;
Zr，0.15-0.50％；
cu, 0-0.08%, but not 0, not 0.08;
Co，0-0.3％；
0-3% of M, wherein M is one or more of Al, Ga, Ti, Nb and Hf;
B，0.95-1.05％；
Fe，64-70％；
the percentage is the mass percentage of the total mass of the R-T-B series permanent magnetic material, and the sum of the contents of all the components is 100 percent.
In a certain scheme, the R-T-B series permanent magnet material can be any one of the following numbers 1-10, wherein the percentage is the mass percentage of each component in the total mass of the R-T-B series permanent magnet material, the sum of the contents of the components is 100%,
"/" means that the element is not included.
The invention also provides application of the R-T-B series permanent magnetic material as an electronic component.
In the invention, carbon impurities are generally inevitably introduced in the preparation process, the dosage is generally 0-0.10%, and the percentage is the mass percentage of the dosage of the C element in the total amount.
In the present invention, unless otherwise specified, "percentage" refers to mass percent.
The above preferred conditions can be arbitrarily combined to obtain preferred embodiments of the present invention without departing from the common general knowledge in the art.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows: simultaneously controlling the content of Cu and Zr elements, and enabling R rich in Zr to exist at the grain boundaryp-(Zrx,Cuy,Mz)q-Fe100-p-qAn enriched phase which is helpful for high-temperature sintering and refining the grain structure, thereby improving the coercive force (H) of the magnetcjNot less than 16.4kOe) and improved squareness (H)k/HcjNot less than 0.98), the high temperature performance is improved (the absolute value of the Hcj temperature coefficient is not more than 0.739 at 80 ℃; the absolute value of the Hcj temperature coefficient is less than or equal to 0.431 at 150 ℃). At the same timeBecause the content of trace Co is not added or controlled, Co cannot be enriched in the crystal boundary, thereby inhibiting the crystal fracture and improving the mechanical property (the bending strength is more than or equal to 473 MPa).
Drawings
FIG. 1 is a FE-EPMA map of the R-T-B system permanent magnetic material obtained in example 7.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
1. Raw material composition of R-T-B series permanent magnetic material
The formulations of the raw material compositions of the R-T-B series permanent magnetic materials in examples 1 to 8 and comparative examples 1 to 5 are shown in Table 1.
TABLE 1 Components and contents (%)% of raw material compositions of R-T-B series permanent magnetic materials in examples 1 to 8 and comparative examples 1 to 5
Note: "/" means that the element is not included.
The preparation method of the R-T-B series permanent magnetic material in the examples 1 to 8 and the comparative examples 1 to 5 is as follows:
(1) smelting and casting processes: according to the formulation in Table 1, the prepared raw materials were put into a crucible of alumina, and vacuum melting was carried out in a high-frequency vacuum melting furnace under a vacuum of 0.05Pa and at 1500 ℃. Introducing argon into the intermediate frequency vacuum induction rapid hardening melt-spun furnace, casting, and rapidly cooling the alloy to obtain an alloy sheet.
(2) Hydrogen crushing powder preparation process: and (3) vacuumizing the hydrogen breaking furnace in which the quenching alloy is placed at room temperature, introducing hydrogen with the purity of 99.9% into the hydrogen breaking furnace, maintaining the pressure of the hydrogen at 90kPa, fully absorbing the hydrogen, vacuumizing while heating, fully dehydrogenating, cooling, and taking out the powder after hydrogen breaking and crushing. Wherein the temperature for hydrogen absorption is room temperature, and the temperature for dehydrogenation is 550 ℃.
(3) And (3) airflow milling powder preparation process: the powder after hydrogen crushing is subjected to jet milling under a nitrogen atmosphere and under the condition that the pressure of a crushing chamber is 0.65MPa (the efficiency of jet milling powder can be different according to equipment, and can be 200kg/h for example), and fine powder is obtained.
(4) And (3) forming: and pressing and molding the powder subjected to the air flow milling in the magnetic field intensity of more than 1.5T.
(5) And (3) sintering treatment process: and (3) carrying the molded bodies to a sintering furnace for sintering, and sintering for 2-8h at the temperature of 1030-1090 ℃ under the vacuum condition of less than 0.5Pa to obtain a sintered body.
(6) And (3) aging treatment process: heating the sintered body in high-purity Ar from 20 ℃ to 500 ℃ at a heating rate of 3-5 ℃/min, carrying out heat treatment at the temperature of 500 ℃ for 3 hours, cooling to room temperature, and taking out.
Example 9
The sintered body obtained by the sintering treatment in example 4 was subjected to grain boundary diffusion treatment and then to aging treatment. The rest of the procedure was the same as in example 4. The grain boundary diffusion treatment process is as follows:
processing the sintered body into a magnet of 20mm × 20mm and sheet thickness less than 7mm, the thickness direction being the magnetic field orientation direction, cleaning the surface, respectively using raw materials prepared from Dy fluoride, spray-coating the whole surface of the magnet, drying the coated magnet, and then diffusion heat-treating at 850 ℃ for 24 hours in a high-purity Ar atmosphere. And cooling to room temperature.
Example 10
The sintered body obtained by the sintering treatment in example 2 was subjected to grain boundary diffusion treatment and then to aging treatment. The rest of the procedure was the same as in example 2. The grain boundary diffusion treatment process is as follows:
processing the sintered body into a magnet with a thickness of 20mm × 20mm and a sheet thickness of less than 7mm, wherein the thickness direction is a magnetic field orientation direction, cleaning the surface, respectively using a raw material prepared from Tb fluoride, spray-coating the whole surface of the raw material on the magnet, drying the coated magnet, and then performing diffusion heat treatment at a temperature of 850 ℃ for 24 hours in a high-purity Ar atmosphere. And cooling to room temperature.
Effect example 1
The R-T-B series permanent magnet materials in examples 1 to 10 and comparative examples 1 to 5 were respectively taken, the magnetic properties and the components thereof were measured, and the microstructure of the magnet was observed.
(1) Each component of the R-T-B series permanent magnetic material was measured by using a high-frequency inductively coupled plasma emission spectrometer (ICP-OES, instrument model: Icap 6300). The following table 2 shows the results of component detection. Taking example 1 as an example, the types and the amounts of the elements detected by the R-T-B permanent magnetic material were the same as those of the raw material composition disclosed in table 1.
TABLE 2 compositions and contents (%)
Note: "/" means that the element is not included.
(2) Evaluation of magnetic Properties: the R-T-B series permanent magnetic material uses an NIM-10000H type BH bulk rare earth permanent magnetic nondestructive measurement system of China measuring institute to carry out magnetic property detection (a test sample is a wafer with the diameter of D10mm multiplied by the thickness of 5 mm); the results of magnetic property measurements are shown in Table 3.
And (3) evaluating the mechanical property: the bending strength of the R-T-B series permanent magnet material universal testing machine is detected, the size of a test sample is 20mm multiplied by 7.5mm multiplied by 6.5mm, and 6.5mm is the orientation direction.
TABLE 3
(3) Determination of microstructure: the perpendicular orientation plane of the R-T-B system permanent magnetic material was polished and examined with a field emission electron probe microanalyzer (FE-EPMA) (JEOL, 8530F). Firstly, determining the distribution of Zr, Cu and other elements in the permanent magnetic material by FE-EPMA surface scanning. And then determining the content of Zr, Cu and other elements through FE-EPMA single-point quantitative analysis under the test conditions of 15kv of acceleration voltage and 50nA of probe beam current.
The results of FE-EPMA tests on the R-T-B series permanent magnetic material obtained in example 7 are shown in FIG. 1 and Table 4. In fig. 1, the concentration profiles of Cu and Zr are shown. As can be seen from fig. 1, a Zr rich phase exists at the grain boundary, and the content of Cu in this Zr rich phase is higher than that in the main phase. The main phase is shown as arrow 1 in FIG. 1, and the Zr-rich phase is shown as arrow 2 in FIG. 1. As is clear from Table 4, the amount of rare earth in the Zr-rich phase was about 17.57 at%, and the ratio of Zr to Cu was 1.1. Similarly, the presence of R at the grain boundaries was observed in the FE-EPMA assay of the other examplesp-(Zrx,Cuy,Mz)q-Fe100-p-qEnriched phase, p is more than or equal to 15 and less than or equal to 25 (at%); q is more than or equal to 3 and less than or equal to 8 (at%); x/(y + z) ═ 1.0 to 1.8 (at% means atomic percent).
TABLE 4
In table 4, the content of each element means atomic percent (at%).
The specific examples and comparative examples were analyzed as follows:
(1) in the invention, the contents of Cu and Zr are controlled simultaneously, and the obtained R-T-B series permanent magnetic material has excellent magnetic property: b isr≥14.17kGs，Hcj≥16.4kOe；Hk/HcjNot less than 0.98; the absolute value of the Hcj temperature coefficient is less than or equal to 0.739 at 80 ℃; the absolute value of the Hcj temperature coefficient is less than or equal to 0.431 at 150 ℃. Excellent mechanical property: the bending strength was not less than 473MPa (examples 1 to 10).
(2) Based on the formula of the invention, the change of the dosage of Zr, B, Co or Pr of the raw materials, the magnetic performance of the R-T-B permanent magnetic material anda significant reduction in mechanical properties, especially HcjAbsolute value of Hcj temperature coefficient at 80 ℃ and bending strength (comparative examples 1 to 5);
(3) the inventor finds that Zr-rich R can exist at the grain boundary by controlling the content of Cu and Zr simultaneously in the research processp-(Zrx,Cuy,Mz)q-Fe100-p-qAnd the phase is enriched and is beneficial to high-temperature sintering and grain structure refinement, so that the coercive force of the magnet is improved, the squareness degree is improved, and the high-temperature performance is improved. Meanwhile, because the content of trace Co is not added or controlled, Co cannot be enriched in the crystal boundary, thereby inhibiting the crystal fracture and improving the mechanical property.
Claims (10)
1. A raw material composition of an R-T-B series permanent magnet material is characterized by comprising the following components in percentage by mass:
29.5 to 32 percent of R, wherein the R is a rare earth element at least containing Nd, and the content of Pr is 0 to 17 percent;
Zr，0.15-0.50％；
cu, 0-0.08%, but not 0, not 0.08;
Co，0-0.3％；
0-3% of M, wherein M is one or more of Al, Ga, Ti, Nb, Hf, Si, Sn, Ge, Ag, Au, Bi and Mn;
B，0.95-1.05％；
Fe，64-70％；
the percentage is the mass percentage of the total mass of the raw material composition of the R-T-B series permanent magnetic material, and the sum of the contents of all the components is 100%.
2. The raw material composition of R-T-B series permanent magnetic material according to claim 1, wherein R is a rare earth element added in a melting process and/or a diffusion process; such as rare earth elements added in the smelting process;
and/or the content of R is 29.8%, 30.5%, 30.8%, 31%, 31.5%, 31.6% or 32%;
and/or, the Nd content is 23.1-29.7%, such as 23.1%, 23.6%, 24.3%, 25%, 25.2%, 29%, or 29.7%;
and/or the Pr content is 0-10%, preferably 0-8%, such as 0, 2.2%, 5.5%, 6.1%, 6.3%, 7.4% or 7.9%;
and/or, said R further comprises a heavy rare earth element; wherein:
preferably, the heavy rare earth element is a heavy rare earth element added in a smelting process and/or a diffusion process, and more preferably, the heavy rare earth element is a heavy rare earth element added in a smelting process;
preferably, the heavy rare earth element is one or more of Dy, Tb, Gd and Ho;
preferably, the heavy rare earth element is present in an amount of 0-7% but not 0, preferably 0.1-0.5%, such as 0.1, 0.2%, 0.3% or 0.5%;
and/or the Zr content is 0.15%, 0.2%, 0.3%, 0.35% or 0.5%;
and/or the Cu content is 0.04% to 0.06%, such as 0.04%, 0.05% or 0.06%;
and/or the content of Co is 0, 0.1% or 0.3%;
and/or the content of B is 0.95%, 0.98% or 1.05%;
and/or the type of M is one or more of Al, Ga, Ti, Nb and Hf;
and/or, the M content is 0-2%, such as 0, 0.08%, 0.1%, 0.58%, 0.6%, 0.7%, 0.75%, 0.9% or 1.2%;
and/or, when said M comprises Al, said Al is present in an amount of 0-1%, but not 0, such as 0.03%, 0.5% or 0.6%;
and/or, when said M comprises Ga, the Ga content is 0-1%, but not 0, such as 0.05%, 0.1%, 0.2% or 0.4%;
and/or, when said M comprises Ti, said Ti is present in an amount of 0.05-0.3%, such as 0.05%, 0.1% or 0.3%;
and/or, when said M comprises Nb, the content of Nb is 0-0.2%, but not 0, for example 0.05%;
and/or, when said M comprises Hf, said Hf is in an amount of 0-0.2% but not 0, e.g., 0.05%.
3. The raw material composition for R-T-B-based permanent magnetic materials according to claim 1 or 2, wherein R does not contain Tb;
or, the R does not contain heavy rare earth elements except Dy and Tb;
alternatively, the R does not comprise Ho;
or, the R is free of rare earth metals other than Nd and Pr, except for unavoidable impurities;
or, the content of Co is 0;
alternatively, the Co content is 0-0.3% but not 0, e.g. 0.1% or 0.3%;
or M is one or more of Al, Ga, Ti, Nb and Hf; the content of Al is more than or equal to 0.55 percent;
alternatively, said R does not contain Tb; the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Ga is less than 0.2%; the content of the Al is 0.45-0.54%;
alternatively, said R comprises Tb; the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Ga is less than 0.2%; the content of the Al is 0.45-0.54%; al + Cu is more than or equal to 0.55 percent;
or, the Zr content is more than or equal to 0.35 percent; the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Ga is 0.2-0.25%; the content of the Al is 0.45-0.54%;
or M is one or more of Al, Ga, Ti, Nb and Hf; the content of Ga is more than 0.25 percent; the content of the Al is 0.45-0.54%; the content of Ti is less than 0.15% or more than 0.28%;
alternatively, said R does not contain Tb; the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Al is less than 0.04%;
alternatively, said R comprises Tb; the Zr content is more than or equal to 0.26 percent; the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Al is less than 0.04%;
alternatively, said R comprises Tb; the content of Ga is less than 0.05 percent or more than 0.25 percent; the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Al is less than 0.04%;
or the raw material composition of the R-T-B series permanent magnet material comprises the following components in percentage by mass: 29.5 to 32 percent of R, wherein the R is a rare earth element at least containing Nd, and the content of Pr is 0 to 17 percent; 0.15 to 0.50 percent of Zr; cu, 0-0.08%, but not 0, not 0.08; 0-0.3% of Co; 0-3% of M, wherein M is one or more of Al, Ga, Ti, Nb and Hf; b, 0.95-1.05%; 64-70% of Fe; the percentage is the mass percentage of the total mass of the raw material composition of the R-T-B series permanent magnetic material, and the sum of the contents of all the components is 100 percent;
or the raw material composition of the R-T-B series permanent magnet material can be any one of the following numbers 1-8, wherein the percentage is the mass percentage of each component in the total mass of the raw material composition of the R-T-B series permanent magnet material, the sum of the contents of the components is 100%,
"/" means that the element is not included.
4. A method for preparing R-T-B series permanent magnet material, characterized in that the raw material composition of R-T-B series permanent magnet material according to any one of claims 1 to 3 is smelted, pulverized, formed, sintered and aged.
5. The method for preparing an R-T-B series permanent magnetic material according to claim 4, wherein the melting comprises the steps of: the raw material composition of the R-T-B series permanent magnetic material is smelted and cast by adopting an ingot casting process and a rapid hardening sheet process to obtain an alloy sheet;
and/or the smelting temperature is 1300-1600 ℃;
and/or the smelting equipment is a high-frequency vacuum smelting furnace and/or a medium-frequency vacuum smelting furnace;
and/or the milling comprises hydrogen milling and/or airflow milling;
wherein, the hydrogen crushing powder preferably comprises hydrogen absorption, dehydrogenation and cooling treatment; the temperature of the hydrogen absorption is preferably 20 to 200 ℃; the dehydrogenation temperature is preferably 400-650 ℃; the pressure of hydrogen absorption is preferably 50 to 600 kPa;
the pressure of the powder milling chamber of the jet mill is preferably 0.1-2 MPa; the gas flow in the gas flow milling powder is preferably nitrogen and/or argon; the efficiency of the jet milled powder is preferably from 30 to 400kg/h, for example 200 kg/h;
and/or, the molding is a magnetic field molding method, the magnetic field intensity of the magnetic field molding method is preferably more than 1.5T;
and/or the sintering treatment is a vacuum sintering process and/or an inert atmosphere sintering process;
wherein, when adopting the inert atmosphere sintering process, the sintering starting stage can be carried out at the vacuum degree of less than 5 × 10-1Is carried out under the condition of Pa; the inert atmosphere is preferably helium or argon;
and/or the temperature of the sintering treatment is 1000-1200 ℃, preferably 1030-1090 ℃;
and/or the time of the sintering treatment is 0.5-10h, preferably 2-8 h;
and/or the temperature of the aging treatment is 450-600 ℃, such as 480-510 ℃;
and/or the time of the aging treatment can be 1-4h, such as 1-3 h;
and/or performing grain boundary diffusion treatment after the sintering treatment and before the aging treatment;
when the grain boundary diffusion treatment is performed, the grain boundary diffusion treatment preferably includes the steps of: evaporating, coating or sputtering a Tb-containing substance and/or Dy-containing substance on the surface of the sintered body obtained by the sintering treatment, and performing diffusion heat treatment; the Tb-containing substance may be Tb metal, a Tb-containing compound (e.g., Tb-containing fluoride), or an alloy; the Dy-containing substance may be Dy metal, a Dy-containing compound (e.g., a Dy-containing fluoride), or an alloy; the temperature of the diffusion heat treatment may be 800-900 ℃, for example 850 ℃; the diffusion heat treatment time may be 12-48h, for example 24 h.
6. An R-T-B series permanent magnetic material produced by the production method according to claim 4 or 5.
7. An R-T-B series permanent magnetic material is characterized by comprising the following components in percentage by mass:
29.5 to 32 percent of R, wherein the R is a rare earth element at least containing Nd, and the content of Pr is 0 to 17 percent;
Zr，0.15-0.50％；
cu, 0-0.08%, but not 0, not 0.08;
Co，0-0.3％；
0-3% of M, wherein M is one or more of Al, Ga, Ti, Nb, Hf, Si, Sn, Ge, Ag, Au, Bi and Mn;
B，0.95-1.05％；
Fe，64-70％；
the percentage is the mass percentage of the total mass of the R-T-B series permanent magnetic material, and the sum of the contents of all the components is 100 percent.
8. The R-T-B permanent magnetic material according to claim 7, wherein the R-T-B permanent magnetic material has a grain boundary growth composition of Rp-(Zrx,Cuy,Mz)q-Fe100-p-qWherein: r is a rare earth element containing at least Nd; m is one or more of Ga, Al, Ti, Nb, Hf, Si, Sn, Ge, Ag, Au, Bi and Mn; p, q, x, y and z satisfy the following conditions: p is more than or equal to 15 and less than or equal to 25 (at%); q is more than or equal to 3 and less than or equal to 8 (at%); x/(y + z) ═ 1.0-1.8, at% is atomic percent;
and/or R is a rare earth element added in a smelting process and/or a diffusion process; such as rare earth elements added in the smelting process;
and/or the content of R is 29.8%, 30.5%, 30.8%, 31%, 31.5%, 31.6% or 32%;
and/or, the Nd content is 23.1-29.7%, such as 23.1%, 23.6%, 24.3%, 25%, 25.2%, 29%, or 29.7%;
and/or the Pr content is 0-10%, preferably 0-8%, such as 0, 2.2%, 5.5%, 6.1%, 6.3%, 7.4% or 7.9%;
and/or, said R further comprises a heavy rare earth element; wherein:
preferably, the heavy rare earth element is a heavy rare earth element added in a smelting process and/or a diffusion process, and more preferably, the heavy rare earth element is a heavy rare earth element added in a smelting process;
preferably, the heavy rare earth element is one or more of Dy, Tb, Gd and Ho;
preferably, the heavy rare earth element is present in an amount of 0-7% but not 0, preferably 0.1-0.5%, such as 0.1, 0.2%, 0.3% or 0.5%;
and/or the Zr content is 0.15%, 0.2%, 0.3%, 0.35% or 0.5%;
and/or the Cu content is 0.04% to 0.06%, such as 0.04%, 0.05% or 0.06%;
and/or the content of Co is 0, 0.1% or 0.3%;
and/or the content of B is 0.95%, 0.98% or 1.05%;
and/or the type of M is one or more of Al, Ga, Ti, Nb and Hf;
and/or, the M content is 0-2%, such as 0, 0.08%, 0.1%, 0.58%, 0.6%, 0.7%, 0.75%, 0.9% or 1.2%;
and/or, when said M comprises Al, said Al is present in an amount of 0-1%, but not 0, such as 0.03%, 0.5% or 0.6%;
and/or, when said M comprises Ga, the Ga content is 0-1%, but not 0, such as 0.05%, 0.1%, 0.2% or 0.4%;
and/or, when said M comprises Ti, said Ti is present in an amount of 0.05-0.3%, such as 0.05%, 0.1% or 0.3%;
and/or, when said M comprises Nb, the content of Nb is 0-0.2%, but not 0, for example 0.05%;
and/or, when said M comprises Hf, said Hf is in an amount of 0-0.2% but not 0, e.g., 0.05%.
9. The R-T-B based permanent magnetic material according to claim 7 or 8, wherein R does not contain Tb;
or, the R does not contain heavy rare earth elements except Dy and Tb;
alternatively, the R does not comprise Ho;
or, the R is free of rare earth metals other than Nd and Pr, except for unavoidable impurities;
or, the content of Co is 0;
alternatively, the Co content is 0-0.3% but not 0, e.g. 0.1% or 0.3%;
or M is one or more of Al, Ga, Ti, Nb and Hf; the content of Al is more than or equal to 0.55 percent;
alternatively, said R does not contain Tb; the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Ga is less than 0.2%; the content of the Al is 0.45-0.54%;
alternatively, said R comprises Tb; the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Ga is less than 0.2%; the content of the Al is 0.45-0.54%; al + Cu is more than or equal to 0.55 percent;
or, the Zr content is more than or equal to 0.35 percent; the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Ga is 0.2-0.25%; the content of the Al is 0.45-0.54%;
or M is one or more of Al, Ga, Ti, Nb and Hf; the content of Ga is more than 0.25 percent; the content of the Al is 0.45-0.54%; the content of Ti is less than 0.15% or more than 0.28%;
alternatively, said R does not contain Tb; the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Al is less than 0.04%;
alternatively, said R comprises Tb; the Zr content is more than or equal to 0.26 percent; the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Al is less than 0.04%;
alternatively, said R comprises Tb; the content of Ga is less than 0.05 percent or more than 0.25 percent; the M is one or more of Al, Ga, Ti, Nb and Hf; the content of Al is less than 0.04%;
or the R-T-B series permanent magnetic material comprises the following components in percentage by mass: 29.5 to 32 percent of R, wherein the R is a rare earth element at least containing Nd, and the content of Pr is 0 to 17 percent; 0.15 to 0.50 percent of Zr; cu, 0-0.08%, but not 0, not 0.08; 0-0.3% of Co; 0-3% of M, wherein M is one or more of Al, Ga, Ti, Nb and Hf; b, 0.95-1.05%; 64-70% of Fe; the percentage is the mass percentage of the total mass of the R-T-B series permanent magnetic material, and the sum of the contents of all the components is 100 percent;
or the R-T-B series permanent magnet material can be any one of the following numbers 1-10, wherein the percentage is the mass percentage of each component in the total mass of the R-T-B series permanent magnet material, the sum of the contents of the components is 100%,
"/" means that the element is not included.
10. Use of the R-T-B series permanent magnetic material according to any one of claims 6 to 9 as an electronic component.
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| CN113066625A (en) * | 2021-03-26 | 2021-07-02 | 福建省长汀金龙稀土有限公司 | R-T-B series permanent magnetic material and preparation method and application thereof |
| WO2021244317A1 (en) * | 2020-06-03 | 2021-12-09 | 厦门钨业股份有限公司 | R-t-b-based permanent magnetic material, raw material composition, preparation method therefor and use thereof |
| WO2022170862A1 (en) * | 2021-09-30 | 2022-08-18 | 浙江英洛华磁业有限公司 | High-strength r-t-b rare earth permanent magnet and preparation method therefor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2021244317A1 (en) * | 2020-06-03 | 2021-12-09 | 厦门钨业股份有限公司 | R-t-b-based permanent magnetic material, raw material composition, preparation method therefor and use thereof |
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| WO2022199232A1 (en) * | 2021-03-26 | 2022-09-29 | 福建省长汀金龙稀土有限公司 | R-t-b permanent magnetic material, preparation method therefor and use thereof |
| CN113066625B (en) * | 2021-03-26 | 2023-04-11 | 福建省长汀金龙稀土有限公司 | R-T-B series permanent magnetic material and preparation method and application thereof |
| WO2022170862A1 (en) * | 2021-09-30 | 2022-08-18 | 浙江英洛华磁业有限公司 | High-strength r-t-b rare earth permanent magnet and preparation method therefor |
Also Published As
| Publication number | Publication date |
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| WO2021244317A1 (en) | 2021-12-09 |
| CN111613407B (en) | 2022-05-03 |
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